Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011200707X/sk3430sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIsup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIIsup8.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIIIsup9.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IXsup10.hkl |
CCDC references: 873897; 873898; 873899; 873900; 873901; 873902; 873903; 873904; 873905
For the synthesis of (I)–(IX), sodium tungstate dihydrate (10% mol), followed by 30% aqueous hydrogen peroxide solution (12 mmol), were added to a stirred and cooled (ice-bath) solution of the appropriately substituted 2-allyl-N-(heteroarylmethyl)aniline (4 mmol) in methanol (30 ml). The resulting mixtures were stirred at 273 K for 2–8 h and then at ambient temperature for an additional 12–20 h. Each mixture was filtered and then extracted with ethyl acetate (2 × 50 ml) and, for each, the combined extracts were dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and toluene (30 ml) was added to the resulting solid residue. These mixtures were heated under reflux for 6–8 h and, after cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was subject to column chromatographic resolution over silica gel using heptane–ethyl acetate (compositions ranged from 50:1 to 10:1 v/v) as eluent. Crystallization from heptane or heptane–ethyl acetate gave crystals suitable for single-crystal X-ray diffraction. Compound (I), pale yellow, yield 64%, m.p. 411 K; MS (70 eV) m/z (%) 272 (M+, 30), 255 (3), 242 (3), 130 (10), 104 (100), 105 (67). Compound (II), colourless, yield 21%, m.p. 427 K; MS (70 eV) m/z (%) 258 (M+, 30), 241 (18), 228 (1), 148 (9), 123 (9), 122 (15), 107 (100). Compound (III), colourless, yield 60%, m.p. 375 K; MS (70 eV) m/z (%) 259 (M+, 33), 242 (18), 229 (6), 148 (9), 123 (27), 122 (52), 108 (100). Compound (IV), colourless, yield 66%, m.p. 399 K; MS (70 eV) m/z (%) 275 (M+, 52), 258 (30), 245 (9), 148 (15), 124 (79), 123 (91), 122 (100). Compound (V), colourless, yield 64%, m.p. 376 K; MS (70 eV) m/z (%) 275 (M+, 52), 258 (36), 245 (12), 148 (12), 124 (100), 123 (82), 122 (79). Compound (VI), colourless, yield 67%, m.p. 386 K; MS (70 eV) m/z (%) 275 (M+, 35Cl, 18), 258 (12), 245 (3), 164 (6), 139 (27), 138 (33), 108 (100). Compound (VII), colourless, yield 57%, m.p. 366 K; MS (70 eV) m/z (%) 325 (M+, 18), 308 (12), 295 (3), 214 (6), 189 (27), 188 (45), 108 (100). Compound (VIII), colourless, yield 69%, m.p. 351 K; MS (70 eV) m/z (%) 341 (M+, 30), 324 (21), 311 (6), 214 (9), 189 (67), 188 (100), 124 (70). Compound (IX), pale yellow, yield 56%, m.p. 438 K; MS (70 eV) m/z (%) 356 (M+, 9), 339 (1), 326 (1), 214 (12), 189 (70), 188 (100).
All H atoms were located in difference maps and then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. Crystals of (IX) diffracted very weakly at high θ and consquently reflections with θ > 25.5° were omitted from the final refinements. Despite this, fewer than 60% (1631 out of 2749) of the reflections out to θ = 25.5° were labelled as observed.
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C14H12N2O4 | F(000) = 568 |
Mr = 272.26 | Dx = 1.464 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2835 reflections |
a = 7.2248 (5) Å | θ = 2.8–27.5° |
b = 18.1447 (19) Å | µ = 0.11 mm−1 |
c = 9.4504 (8) Å | T = 120 K |
β = 94.279 (6)° | Block, pale yellow |
V = 1235.42 (19) Å3 | 0.38 × 0.27 × 0.22 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2835 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1868 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −23→23 |
Tmin = 0.960, Tmax = 0.976 | l = −12→12 |
18226 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0626P)2 + 0.5339P] where P = (Fo2 + 2Fc2)/3 |
2835 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C14H12N2O4 | V = 1235.42 (19) Å3 |
Mr = 272.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2248 (5) Å | µ = 0.11 mm−1 |
b = 18.1447 (19) Å | T = 120 K |
c = 9.4504 (8) Å | 0.38 × 0.27 × 0.22 mm |
β = 94.279 (6)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2835 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1868 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.976 | Rint = 0.047 |
18226 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.28 e Å−3 |
2835 reflections | Δρmin = −0.29 e Å−3 |
181 parameters |
x | y | z | Uiso*/Ueq | ||
O14 | 0.74199 (18) | 0.72903 (7) | 0.26127 (14) | 0.0311 (3) | |
O21 | 0.51992 (18) | 0.53677 (7) | 0.20618 (14) | 0.0302 (3) | |
O51 | 0.0841 (2) | 0.45586 (9) | 0.18575 (17) | 0.0450 (4) | |
O52 | 0.3362 (2) | 0.42819 (9) | 0.31571 (17) | 0.0484 (4) | |
N1 | 0.7940 (2) | 0.65364 (8) | 0.29746 (16) | 0.0269 (4) | |
N25 | 0.2495 (2) | 0.46536 (9) | 0.22568 (19) | 0.0360 (4) | |
C2 | 0.7725 (3) | 0.61739 (11) | 0.15524 (19) | 0.0290 (4) | |
H2 | 0.8569 | 0.5737 | 0.1540 | 0.035* | |
C3 | 0.8342 (3) | 0.67659 (11) | 0.0504 (2) | 0.0342 (5) | |
H3A | 0.9554 | 0.6638 | 0.0145 | 0.041* | |
H3B | 0.7410 | 0.6825 | −0.0310 | 0.041* | |
C4 | 0.8491 (3) | 0.74663 (11) | 0.1412 (2) | 0.0322 (5) | |
H4 | 0.7936 | 0.7897 | 0.0872 | 0.039* | |
C5 | 1.0452 (3) | 0.76363 (11) | 0.1985 (2) | 0.0337 (5) | |
H5A | 1.0484 | 0.8119 | 0.2473 | 0.040* | |
H5B | 1.1270 | 0.7665 | 0.1192 | 0.040* | |
C5a | 1.1144 (3) | 0.70423 (11) | 0.3014 (2) | 0.0296 (4) | |
C6 | 1.2998 (3) | 0.69754 (11) | 0.3510 (2) | 0.0325 (5) | |
H6 | 1.3877 | 0.7317 | 0.3200 | 0.039* | |
C7 | 1.3589 (3) | 0.64225 (12) | 0.4445 (2) | 0.0350 (5) | |
H7 | 1.4864 | 0.6385 | 0.4764 | 0.042* | |
C8 | 1.2311 (3) | 0.59195 (11) | 0.4918 (2) | 0.0334 (5) | |
H8 | 1.2711 | 0.5542 | 0.5566 | 0.040* | |
C9 | 1.0461 (3) | 0.59730 (11) | 0.4442 (2) | 0.0297 (4) | |
H9 | 0.9586 | 0.5632 | 0.4763 | 0.036* | |
C9a | 0.9884 (3) | 0.65272 (10) | 0.34914 (19) | 0.0266 (4) | |
C22 | 0.5770 (3) | 0.59338 (11) | 0.1235 (2) | 0.0301 (4) | |
C23 | 0.4365 (3) | 0.61302 (12) | 0.0268 (2) | 0.0364 (5) | |
H23 | 0.4409 | 0.6505 | −0.0430 | 0.044* | |
C24 | 0.2833 (3) | 0.56748 (11) | 0.0493 (2) | 0.0351 (5) | |
H24 | 0.1647 | 0.5677 | −0.0013 | 0.042* | |
C25 | 0.3422 (3) | 0.52358 (11) | 0.1583 (2) | 0.0304 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0267 (9) | 0.0266 (8) | 0.0273 (8) | 0.0008 (6) | 0.0013 (6) | 0.0001 (7) |
C2 | 0.0302 (10) | 0.0286 (10) | 0.0281 (10) | 0.0027 (8) | 0.0018 (8) | −0.0027 (8) |
C3 | 0.0366 (12) | 0.0378 (12) | 0.0287 (10) | 0.0049 (9) | 0.0043 (8) | 0.0014 (9) |
C4 | 0.0345 (11) | 0.0303 (10) | 0.0327 (11) | 0.0052 (8) | 0.0080 (8) | 0.0071 (8) |
C5 | 0.0365 (12) | 0.0282 (11) | 0.0375 (11) | 0.0002 (8) | 0.0106 (9) | 0.0027 (9) |
C5a | 0.0298 (11) | 0.0293 (10) | 0.0301 (10) | −0.0002 (8) | 0.0056 (8) | −0.0036 (8) |
C6 | 0.0270 (11) | 0.0329 (11) | 0.0382 (11) | −0.0047 (8) | 0.0066 (8) | −0.0067 (9) |
C7 | 0.0285 (11) | 0.0381 (12) | 0.0379 (11) | 0.0019 (9) | −0.0003 (8) | −0.0081 (9) |
C8 | 0.0372 (12) | 0.0291 (10) | 0.0329 (11) | 0.0046 (8) | −0.0045 (9) | −0.0023 (8) |
C9 | 0.0324 (11) | 0.0262 (10) | 0.0303 (10) | −0.0027 (8) | 0.0017 (8) | −0.0014 (8) |
C9a | 0.0264 (10) | 0.0264 (10) | 0.0273 (9) | 0.0001 (7) | 0.0033 (7) | −0.0038 (8) |
O14 | 0.0329 (8) | 0.0273 (7) | 0.0338 (8) | 0.0059 (6) | 0.0066 (6) | 0.0005 (6) |
O21 | 0.0277 (7) | 0.0307 (7) | 0.0314 (7) | −0.0006 (6) | −0.0039 (5) | −0.0019 (6) |
C22 | 0.0329 (11) | 0.0280 (10) | 0.0293 (10) | 0.0040 (8) | 0.0011 (8) | −0.0044 (8) |
C23 | 0.0410 (12) | 0.0336 (11) | 0.0337 (11) | 0.0086 (9) | −0.0037 (9) | −0.0011 (9) |
C24 | 0.0318 (11) | 0.0353 (11) | 0.0365 (11) | 0.0043 (9) | −0.0092 (9) | −0.0052 (9) |
C25 | 0.0268 (10) | 0.0302 (10) | 0.0332 (10) | 0.0024 (8) | −0.0036 (8) | −0.0075 (8) |
N25 | 0.0320 (10) | 0.0340 (10) | 0.0411 (10) | −0.0012 (7) | −0.0033 (8) | −0.0073 (8) |
O51 | 0.0310 (9) | 0.0456 (10) | 0.0565 (10) | −0.0064 (7) | −0.0091 (7) | −0.0078 (8) |
O52 | 0.0413 (9) | 0.0458 (10) | 0.0562 (10) | −0.0029 (7) | −0.0094 (8) | 0.0144 (8) |
N1—C9a | 1.452 (2) | C6—H6 | 0.9500 |
N1—O14 | 1.453 (2) | C7—C8 | 1.396 (3) |
N1—C2 | 1.494 (2) | C7—H7 | 0.9500 |
C2—C22 | 1.487 (3) | C8—C9 | 1.381 (3) |
C2—C3 | 1.550 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.391 (3) |
C3—C4 | 1.533 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | O21—C25 | 1.351 (2) |
C3—H3B | 0.9900 | O21—C22 | 1.373 (2) |
C4—O14 | 1.455 (2) | C22—C23 | 1.362 (3) |
C4—C5 | 1.511 (3) | C23—C24 | 1.410 (3) |
C4—H4 | 1.0000 | C23—H23 | 0.9500 |
C5—C5a | 1.511 (3) | C24—C25 | 1.346 (3) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—N25 | 1.426 (3) |
C5a—C6 | 1.391 (3) | N25—O52 | 1.221 (2) |
C5a—C9a | 1.403 (3) | N25—O51 | 1.238 (2) |
C6—C7 | 1.383 (3) | ||
C9a—N1—O14 | 108.47 (13) | C7—C6—H6 | 119.2 |
C9a—N1—C2 | 109.31 (14) | C5a—C6—H6 | 119.2 |
O14—N1—C2 | 101.25 (13) | C6—C7—C8 | 119.91 (19) |
C22—C2—N1 | 110.14 (15) | C6—C7—H7 | 120.0 |
C22—C2—C3 | 112.87 (16) | C8—C7—H7 | 120.0 |
N1—C2—C3 | 104.74 (15) | C9—C8—C7 | 119.81 (19) |
C22—C2—H2 | 109.7 | C9—C8—H8 | 120.1 |
N1—C2—H2 | 109.7 | C7—C8—H8 | 120.1 |
C3—C2—H2 | 109.7 | C8—C9—C9a | 119.80 (18) |
C4—C3—C2 | 103.18 (15) | C8—C9—H9 | 120.1 |
C4—C3—H3A | 111.1 | C9a—C9—H9 | 120.1 |
C2—C3—H3A | 111.1 | C9—C9a—C5a | 121.28 (18) |
C4—C3—H3B | 111.1 | C9—C9a—N1 | 117.45 (16) |
C2—C3—H3B | 111.1 | C5a—C9a—N1 | 121.24 (17) |
H3A—C3—H3B | 109.1 | N1—O14—C4 | 104.30 (13) |
O14—C4—C5 | 107.72 (15) | C25—O21—C22 | 105.11 (14) |
O14—C4—C3 | 103.62 (15) | C23—C22—O21 | 109.69 (17) |
C5—C4—C3 | 113.24 (16) | C23—C22—C2 | 135.1 (2) |
O14—C4—H4 | 110.7 | O21—C22—C2 | 115.19 (16) |
C5—C4—H4 | 110.7 | C22—C23—C24 | 107.45 (19) |
C3—C4—H4 | 110.7 | C22—C23—H23 | 126.3 |
C4—C5—C5a | 109.96 (16) | C24—C23—H23 | 126.3 |
C4—C5—H5A | 109.7 | C25—C24—C23 | 104.81 (18) |
C5a—C5—H5A | 109.7 | C25—C24—H24 | 127.6 |
C4—C5—H5B | 109.7 | C23—C24—H24 | 127.6 |
C5a—C5—H5B | 109.7 | C24—C25—O21 | 112.93 (18) |
H5A—C5—H5B | 108.2 | C24—C25—N25 | 130.42 (18) |
C6—C5a—C9a | 117.70 (18) | O21—C25—N25 | 116.62 (16) |
C6—C5a—C5 | 122.90 (18) | O52—N25—O51 | 124.64 (18) |
C9a—C5a—C5 | 119.39 (18) | O52—N25—C25 | 119.15 (17) |
C7—C6—C5a | 121.50 (19) | O51—N25—C25 | 116.20 (17) |
C9a—N1—C2—C22 | 159.65 (15) | C2—N1—C9a—C9 | −97.98 (19) |
O14—N1—C2—C22 | −86.02 (17) | O14—N1—C9a—C5a | −29.6 (2) |
C9a—N1—C2—C3 | −78.72 (18) | C2—N1—C9a—C5a | 79.9 (2) |
O14—N1—C2—C3 | 35.61 (17) | C9a—N1—O14—C4 | 66.22 (16) |
C22—C2—C3—C4 | 109.06 (17) | C2—N1—O14—C4 | −48.73 (16) |
N1—C2—C3—C4 | −10.76 (19) | C5—C4—O14—N1 | −78.34 (17) |
C2—C3—C4—O14 | −18.09 (19) | C3—C4—O14—N1 | 41.90 (17) |
C2—C3—C4—C5 | 98.33 (18) | C25—O21—C22—C23 | −0.7 (2) |
O14—C4—C5—C5a | 48.6 (2) | C25—O21—C22—C2 | −179.16 (16) |
C3—C4—C5—C5a | −65.4 (2) | N1—C2—C22—C23 | 113.7 (2) |
C4—C5—C5a—C6 | 167.85 (18) | C3—C2—C22—C23 | −2.9 (3) |
C4—C5—C5a—C9a | −11.6 (2) | N1—C2—C22—O21 | −68.3 (2) |
C9a—C5a—C6—C7 | −0.1 (3) | C3—C2—C22—O21 | 175.00 (15) |
C5—C5a—C6—C7 | −179.59 (19) | O21—C22—C23—C24 | 0.4 (2) |
C5a—C6—C7—C8 | −0.5 (3) | C2—C22—C23—C24 | 178.4 (2) |
C6—C7—C8—C9 | 0.5 (3) | C22—C23—C24—C25 | 0.1 (2) |
C7—C8—C9—C9a | 0.1 (3) | C23—C24—C25—O21 | −0.6 (2) |
C8—C9—C9a—C5a | −0.7 (3) | C23—C24—C25—N25 | −178.3 (2) |
C8—C9—C9a—N1 | 177.17 (17) | C22—O21—C25—C24 | 0.8 (2) |
C6—C5a—C9a—C9 | 0.7 (3) | C22—O21—C25—N25 | 178.89 (16) |
C5—C5a—C9a—C9 | −179.77 (17) | C24—C25—N25—O52 | 173.6 (2) |
C6—C5a—C9a—N1 | −177.09 (16) | O21—C25—N25—O52 | −4.1 (3) |
C5—C5a—C9a—N1 | 2.4 (3) | C24—C25—N25—O51 | −5.6 (3) |
O14—N1—C9a—C9 | 152.45 (15) | O21—C25—N25—O51 | 176.76 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O51i | 0.95 | 2.45 | 3.359 (3) | 161 |
C5—H5B···Cg1ii | 0.99 | 2.66 | 3.458 (2) | 138 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z−1/2. |
C15H15FN2O | F(000) = 1088 |
Mr = 258.29 | Dx = 1.390 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2824 reflections |
a = 27.141 (4) Å | θ = 2.6–27.5° |
b = 5.4082 (7) Å | µ = 0.10 mm−1 |
c = 17.2849 (18) Å | T = 120 K |
β = 103.275 (9)° | Plate, colourless |
V = 2469.3 (6) Å3 | 0.41 × 0.27 × 0.10 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 2824 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1511 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −34→34 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −7→6 |
Tmin = 0.961, Tmax = 0.990 | l = −22→22 |
21463 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0685P)2 + 0.4858P] where P = (Fo2 + 2Fc2)/3 |
2824 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C15H15FN2O | V = 2469.3 (6) Å3 |
Mr = 258.29 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.141 (4) Å | µ = 0.10 mm−1 |
b = 5.4082 (7) Å | T = 120 K |
c = 17.2849 (18) Å | 0.41 × 0.27 × 0.10 mm |
β = 103.275 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2824 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1511 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.990 | Rint = 0.092 |
21463 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.28 e Å−3 |
2824 reflections | Δρmin = −0.23 e Å−3 |
173 parameters |
x | y | z | Uiso*/Ueq | ||
F7 | 0.01915 (5) | 0.3742 (3) | 0.66891 (8) | 0.0505 (5) | |
O14 | 0.19103 (6) | 0.7729 (3) | 0.52314 (8) | 0.0286 (4) | |
N1 | 0.13816 (7) | 0.7982 (3) | 0.48250 (10) | 0.0257 (5) | |
N21 | 0.12186 (6) | 0.9895 (3) | 0.30722 (10) | 0.0257 (5) | |
C2 | 0.13640 (8) | 0.6477 (4) | 0.40853 (12) | 0.0248 (5) | |
H2 | 0.1012 | 0.5856 | 0.3870 | 0.030* | |
C3 | 0.17219 (9) | 0.4283 (4) | 0.43747 (12) | 0.0297 (6) | |
H3A | 0.1528 | 0.2742 | 0.4396 | 0.036* | |
H3B | 0.1958 | 0.4021 | 0.4023 | 0.036* | |
C4 | 0.20074 (9) | 0.5081 (4) | 0.52100 (13) | 0.0278 (5) | |
H4 | 0.2378 | 0.4748 | 0.5290 | 0.033* | |
C5 | 0.17983 (8) | 0.3871 (4) | 0.58606 (13) | 0.0278 (5) | |
H5A | 0.1793 | 0.2053 | 0.5793 | 0.033* | |
H5B | 0.2018 | 0.4268 | 0.6387 | 0.033* | |
C5a | 0.12698 (8) | 0.4803 (4) | 0.58172 (12) | 0.0239 (5) | |
C6 | 0.09639 (9) | 0.3784 (4) | 0.62816 (13) | 0.0284 (5) | |
H6 | 0.1080 | 0.2433 | 0.6626 | 0.034* | |
C7 | 0.04905 (9) | 0.4769 (5) | 0.62322 (14) | 0.0340 (6) | |
C8 | 0.03026 (10) | 0.6729 (5) | 0.57556 (15) | 0.0418 (7) | |
H8 | −0.0027 | 0.7357 | 0.5738 | 0.050* | |
C9 | 0.06068 (9) | 0.7776 (5) | 0.52991 (14) | 0.0357 (6) | |
H9 | 0.0488 | 0.9156 | 0.4969 | 0.043* | |
C9a | 0.10843 (8) | 0.6807 (4) | 0.53242 (12) | 0.0248 (5) | |
C22 | 0.15270 (8) | 0.8044 (4) | 0.34745 (12) | 0.0244 (5) | |
C23 | 0.19743 (9) | 0.8140 (4) | 0.32281 (13) | 0.0298 (6) | |
H23 | 0.2257 | 0.7081 | 0.3404 | 0.036* | |
C24 | 0.19421 (9) | 1.0070 (5) | 0.26726 (13) | 0.0326 (6) | |
H24 | 0.2196 | 1.0547 | 0.2405 | 0.039* | |
C25 | 0.14742 (9) | 1.1130 (4) | 0.25908 (13) | 0.0306 (6) | |
H25 | 0.1348 | 1.2491 | 0.2257 | 0.037* | |
C211 | 0.07125 (9) | 1.0523 (5) | 0.31534 (14) | 0.0358 (6) | |
H21A | 0.0493 | 0.9069 | 0.3031 | 0.054* | |
H21B | 0.0577 | 1.1864 | 0.2784 | 0.054* | |
H21C | 0.0727 | 1.1060 | 0.3700 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0247 (10) | 0.0276 (11) | 0.0263 (10) | −0.0001 (8) | 0.0088 (8) | 0.0006 (9) |
C2 | 0.0269 (13) | 0.0244 (12) | 0.0241 (12) | −0.0015 (10) | 0.0078 (9) | −0.0018 (10) |
C3 | 0.0354 (14) | 0.0279 (13) | 0.0273 (12) | 0.0015 (11) | 0.0102 (10) | −0.0011 (11) |
C4 | 0.0254 (12) | 0.0254 (13) | 0.0324 (12) | 0.0023 (10) | 0.0063 (10) | −0.0004 (11) |
C5 | 0.0270 (13) | 0.0293 (13) | 0.0265 (12) | 0.0006 (10) | 0.0050 (9) | 0.0015 (10) |
C5a | 0.0276 (12) | 0.0210 (12) | 0.0226 (11) | −0.0032 (10) | 0.0049 (9) | −0.0037 (10) |
C6 | 0.0331 (14) | 0.0276 (13) | 0.0243 (12) | −0.0042 (10) | 0.0059 (10) | 0.0005 (11) |
C7 | 0.0322 (14) | 0.0412 (15) | 0.0322 (13) | −0.0072 (12) | 0.0151 (11) | 0.0042 (12) |
F7 | 0.0423 (9) | 0.0647 (11) | 0.0513 (9) | −0.0034 (8) | 0.0248 (7) | 0.0190 (8) |
C8 | 0.0345 (15) | 0.0536 (18) | 0.0427 (15) | 0.0122 (13) | 0.0199 (12) | 0.0132 (14) |
C9 | 0.0367 (15) | 0.0371 (15) | 0.0372 (14) | 0.0114 (12) | 0.0165 (11) | 0.0112 (12) |
C9a | 0.0276 (12) | 0.0253 (13) | 0.0233 (11) | 0.0006 (10) | 0.0096 (10) | −0.0021 (10) |
O14 | 0.0282 (9) | 0.0260 (9) | 0.0317 (9) | −0.0039 (7) | 0.0069 (7) | −0.0026 (7) |
N21 | 0.0225 (10) | 0.0296 (11) | 0.0247 (9) | −0.0002 (8) | 0.0048 (8) | 0.0013 (9) |
C22 | 0.0258 (12) | 0.0245 (12) | 0.0235 (11) | −0.0007 (10) | 0.0071 (9) | −0.0034 (10) |
C23 | 0.0273 (13) | 0.0348 (14) | 0.0288 (12) | −0.0014 (11) | 0.0097 (10) | −0.0021 (11) |
C24 | 0.0356 (14) | 0.0393 (15) | 0.0248 (12) | −0.0085 (12) | 0.0109 (10) | −0.0034 (11) |
C25 | 0.0370 (15) | 0.0319 (14) | 0.0224 (12) | −0.0095 (11) | 0.0058 (10) | 0.0006 (11) |
C211 | 0.0262 (13) | 0.0393 (15) | 0.0407 (14) | 0.0026 (11) | 0.0049 (11) | 0.0013 (13) |
N1—O14 | 1.452 (2) | C7—C8 | 1.368 (3) |
N1—C9a | 1.456 (3) | C7—F7 | 1.373 (3) |
N1—C2 | 1.507 (3) | C8—C9 | 1.387 (3) |
C2—C22 | 1.498 (3) | C8—H8 | 0.9500 |
C2—C3 | 1.542 (3) | C9—C9a | 1.389 (3) |
C2—H2 | 1.0000 | C9—H9 | 0.9500 |
C3—C4 | 1.536 (3) | N21—C25 | 1.373 (3) |
C3—H3A | 0.9900 | N21—C22 | 1.385 (3) |
C3—H3B | 0.9900 | N21—C211 | 1.453 (3) |
C4—O14 | 1.458 (3) | C22—C23 | 1.377 (3) |
C4—C5 | 1.519 (3) | C23—C24 | 1.407 (3) |
C4—H4 | 1.0000 | C23—H23 | 0.9500 |
C5—C5a | 1.506 (3) | C24—C25 | 1.371 (3) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—H25 | 0.9500 |
C5a—C6 | 1.394 (3) | C211—H21A | 0.9800 |
C5a—C9a | 1.399 (3) | C211—H21B | 0.9800 |
C6—C7 | 1.375 (3) | C211—H21C | 0.9800 |
C6—H6 | 0.9500 | ||
O14—N1—C9a | 107.02 (15) | C8—C7—C6 | 123.5 (2) |
O14—N1—C2 | 101.24 (15) | F7—C7—C6 | 118.3 (2) |
C9a—N1—C2 | 110.68 (16) | C7—C8—C9 | 118.1 (2) |
C22—C2—N1 | 109.60 (17) | C7—C8—H8 | 121.0 |
C22—C2—C3 | 113.46 (18) | C9—C8—H8 | 121.0 |
N1—C2—C3 | 104.21 (16) | C8—C9—C9a | 120.1 (2) |
C22—C2—H2 | 109.8 | C8—C9—H9 | 120.0 |
N1—C2—H2 | 109.8 | C9a—C9—H9 | 120.0 |
C3—C2—H2 | 109.8 | C9—C9a—C5a | 120.9 (2) |
C4—C3—C2 | 103.48 (18) | C9—C9a—N1 | 117.2 (2) |
C4—C3—H3A | 111.1 | C5a—C9a—N1 | 121.88 (19) |
C2—C3—H3A | 111.1 | N1—O14—C4 | 104.16 (14) |
C4—C3—H3B | 111.1 | C25—N21—C22 | 108.94 (19) |
C2—C3—H3B | 111.1 | C25—N21—C211 | 124.4 (2) |
H3A—C3—H3B | 109.0 | C22—N21—C211 | 126.59 (18) |
O14—C4—C5 | 107.69 (17) | C23—C22—N21 | 106.96 (19) |
O14—C4—C3 | 104.16 (17) | C23—C22—C2 | 131.6 (2) |
C5—C4—C3 | 112.42 (19) | N21—C22—C2 | 121.37 (19) |
O14—C4—H4 | 110.8 | C22—C23—C24 | 108.5 (2) |
C5—C4—H4 | 110.8 | C22—C23—H23 | 125.7 |
C3—C4—H4 | 110.8 | C24—C23—H23 | 125.7 |
C5a—C5—C4 | 109.42 (19) | C25—C24—C23 | 106.9 (2) |
C5a—C5—H5A | 109.8 | C25—C24—H24 | 126.5 |
C4—C5—H5A | 109.8 | C23—C24—H24 | 126.5 |
C5a—C5—H5B | 109.8 | C24—C25—N21 | 108.6 (2) |
C4—C5—H5B | 109.8 | C24—C25—H25 | 125.7 |
H5A—C5—H5B | 108.2 | N21—C25—H25 | 125.7 |
C6—C5a—C9a | 118.6 (2) | N21—C211—H21A | 109.5 |
C6—C5a—C5 | 121.7 (2) | N21—C211—H21B | 109.5 |
C9a—C5a—C5 | 119.68 (19) | H21A—C211—H21B | 109.5 |
C7—C6—C5a | 118.9 (2) | N21—C211—H21C | 109.5 |
C7—C6—H6 | 120.6 | H21A—C211—H21C | 109.5 |
C5a—C6—H6 | 120.6 | H21B—C211—H21C | 109.5 |
C8—C7—F7 | 118.2 (2) | ||
O14—N1—C2—C22 | −84.41 (19) | C5—C5a—C9a—N1 | 2.2 (3) |
C9a—N1—C2—C22 | 162.38 (17) | O14—N1—C9a—C9 | 148.88 (19) |
O14—N1—C2—C3 | 37.33 (19) | C2—N1—C9a—C9 | −101.6 (2) |
C9a—N1—C2—C3 | −75.9 (2) | O14—N1—C9a—C5a | −30.5 (2) |
C22—C2—C3—C4 | 105.9 (2) | C2—N1—C9a—C5a | 79.0 (2) |
N1—C2—C3—C4 | −13.3 (2) | C9a—N1—O14—C4 | 67.33 (18) |
C2—C3—C4—O14 | −15.5 (2) | C2—N1—O14—C4 | −48.60 (17) |
C2—C3—C4—C5 | 100.8 (2) | C5—C4—O14—N1 | −79.32 (18) |
O14—C4—C5—C5a | 47.7 (2) | C3—C4—O14—N1 | 40.24 (19) |
C3—C4—C5—C5a | −66.4 (2) | C25—N21—C22—C23 | −0.6 (2) |
C4—C5—C5a—C6 | 172.14 (19) | C211—N21—C22—C23 | −178.7 (2) |
C4—C5—C5a—C9a | −10.5 (3) | C25—N21—C22—C2 | 176.10 (18) |
C9a—C5a—C6—C7 | 0.6 (3) | C211—N21—C22—C2 | −2.1 (3) |
C5—C5a—C6—C7 | 178.0 (2) | N1—C2—C22—C23 | 103.2 (3) |
C5a—C6—C7—C8 | −0.8 (4) | C3—C2—C22—C23 | −12.8 (3) |
C5a—C6—C7—F7 | 179.67 (19) | N1—C2—C22—N21 | −72.5 (2) |
F7—C7—C8—C9 | 179.5 (2) | C3—C2—C22—N21 | 171.44 (18) |
C6—C7—C8—C9 | 0.0 (4) | N21—C22—C23—C24 | 0.2 (2) |
C7—C8—C9—C9a | 1.0 (4) | C2—C22—C23—C24 | −176.0 (2) |
C8—C9—C9a—C5a | −1.2 (4) | C22—C23—C24—C25 | 0.2 (2) |
C8—C9—C9a—N1 | 179.5 (2) | C23—C24—C25—N21 | −0.6 (3) |
C6—C5a—C9a—C9 | 0.3 (3) | C22—N21—C25—C24 | 0.7 (2) |
C5—C5a—C9a—C9 | −177.1 (2) | C211—N21—C25—C24 | 178.92 (19) |
C6—C5a—C9a—N1 | 179.65 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O14i | 0.99 | 2.58 | 3.530 (3) | 161 |
C25—H25···Cg1ii | 0.95 | 2.81 | 3.654 (2) | 149 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y+2, z−1/2. |
C15H14FNO2 | F(000) = 544 |
Mr = 259.27 | Dx = 1.409 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2807 reflections |
a = 5.5265 (5) Å | θ = 3.5–27.5° |
b = 10.6652 (19) Å | µ = 0.10 mm−1 |
c = 20.905 (4) Å | T = 120 K |
β = 97.166 (11)° | Block, colourless |
V = 1222.6 (3) Å3 | 0.26 × 0.25 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2807 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1657 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.974, Tmax = 0.986 | l = −27→27 |
17136 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0926P)2 + 0.2769P] where P = (Fo2 + 2Fc2)/3 |
2807 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
C15H14FNO2 | V = 1222.6 (3) Å3 |
Mr = 259.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.5265 (5) Å | µ = 0.10 mm−1 |
b = 10.6652 (19) Å | T = 120 K |
c = 20.905 (4) Å | 0.26 × 0.25 × 0.14 mm |
β = 97.166 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2807 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1657 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.986 | Rint = 0.061 |
17136 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
2807 reflections | Δρmin = −0.40 e Å−3 |
173 parameters |
x | y | z | Uiso*/Ueq | ||
F7 | 0.8894 (3) | 0.36913 (15) | 0.20663 (7) | 0.0470 (5) | |
O14 | 0.4759 (3) | 0.09418 (15) | 0.43212 (8) | 0.0300 (4) | |
O21 | 0.2993 (3) | 0.38189 (14) | 0.53473 (7) | 0.0270 (4) | |
N1 | 0.4498 (3) | 0.22775 (17) | 0.42032 (9) | 0.0260 (5) | |
C2 | 0.6064 (4) | 0.2809 (2) | 0.47792 (11) | 0.0271 (5) | |
H2 | 0.6639 | 0.3666 | 0.4675 | 0.033* | |
C3 | 0.8259 (4) | 0.1900 (2) | 0.48794 (11) | 0.0307 (6) | |
H3A | 0.9721 | 0.2278 | 0.4727 | 0.037* | |
H3B | 0.8648 | 0.1670 | 0.5340 | 0.037* | |
C4 | 0.7383 (4) | 0.0755 (2) | 0.44708 (11) | 0.0287 (6) | |
H4 | 0.7748 | −0.0040 | 0.4718 | 0.034* | |
C5 | 0.8431 (4) | 0.0719 (2) | 0.38330 (11) | 0.0310 (6) | |
H5A | 1.0235 | 0.0729 | 0.3911 | 0.037* | |
H5B | 0.7912 | −0.0059 | 0.3596 | 0.037* | |
C5a | 0.7525 (4) | 0.1848 (2) | 0.34396 (11) | 0.0278 (5) | |
C6 | 0.8592 (4) | 0.2229 (2) | 0.28997 (11) | 0.0312 (6) | |
H6 | 0.9881 | 0.1757 | 0.2757 | 0.037* | |
C7 | 0.7748 (4) | 0.3299 (3) | 0.25767 (11) | 0.0338 (6) | |
C8 | 0.5828 (4) | 0.4001 (2) | 0.27423 (11) | 0.0345 (6) | |
H8 | 0.5266 | 0.4722 | 0.2501 | 0.041* | |
C9 | 0.4744 (4) | 0.3618 (2) | 0.32747 (11) | 0.0288 (6) | |
H9 | 0.3412 | 0.4079 | 0.3402 | 0.035* | |
C9a | 0.5601 (4) | 0.2563 (2) | 0.36215 (11) | 0.0263 (5) | |
C22 | 0.4728 (4) | 0.2873 (2) | 0.53541 (11) | 0.0261 (5) | |
C23 | 0.4824 (4) | 0.2226 (2) | 0.59076 (11) | 0.0309 (6) | |
H23 | 0.5853 | 0.1531 | 0.6031 | 0.037* | |
C24 | 0.3087 (4) | 0.2776 (2) | 0.62774 (11) | 0.0308 (6) | |
H24 | 0.2758 | 0.2524 | 0.6694 | 0.037* | |
C25 | 0.2004 (4) | 0.3727 (2) | 0.59183 (11) | 0.0271 (5) | |
C251 | 0.0046 (4) | 0.4629 (2) | 0.60230 (11) | 0.0321 (6) | |
H25A | −0.0712 | 0.4375 | 0.6402 | 0.048* | |
H25B | −0.1188 | 0.4638 | 0.5643 | 0.048* | |
H25C | 0.0746 | 0.5470 | 0.6093 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0255 (10) | 0.0251 (11) | 0.0275 (10) | 0.0005 (8) | 0.0036 (8) | 0.0008 (8) |
C2 | 0.0270 (12) | 0.0273 (13) | 0.0267 (12) | −0.0033 (10) | 0.0019 (9) | −0.0018 (10) |
C3 | 0.0271 (12) | 0.0340 (14) | 0.0306 (13) | −0.0011 (10) | 0.0024 (10) | −0.0035 (10) |
C4 | 0.0186 (11) | 0.0314 (13) | 0.0354 (13) | 0.0027 (10) | 0.0008 (9) | 0.0007 (10) |
C5 | 0.0268 (12) | 0.0284 (14) | 0.0375 (14) | 0.0003 (10) | 0.0028 (10) | −0.0040 (10) |
C5a | 0.0200 (11) | 0.0311 (13) | 0.0320 (13) | −0.0016 (10) | 0.0020 (9) | −0.0063 (10) |
C6 | 0.0250 (12) | 0.0409 (15) | 0.0283 (12) | 0.0003 (11) | 0.0049 (10) | −0.0042 (11) |
C7 | 0.0303 (13) | 0.0498 (17) | 0.0221 (12) | −0.0087 (12) | 0.0065 (10) | −0.0003 (11) |
F7 | 0.0449 (9) | 0.0661 (12) | 0.0318 (8) | −0.0035 (8) | 0.0123 (7) | 0.0072 (7) |
C8 | 0.0356 (14) | 0.0383 (15) | 0.0285 (13) | 0.0014 (11) | −0.0005 (10) | 0.0021 (11) |
C9 | 0.0251 (12) | 0.0354 (14) | 0.0257 (12) | 0.0033 (10) | 0.0023 (9) | −0.0030 (10) |
C9a | 0.0219 (11) | 0.0299 (13) | 0.0272 (12) | −0.0048 (9) | 0.0033 (9) | −0.0040 (9) |
O14 | 0.0250 (8) | 0.0280 (9) | 0.0375 (9) | −0.0011 (7) | 0.0053 (7) | −0.0004 (7) |
O21 | 0.0274 (8) | 0.0267 (9) | 0.0273 (9) | 0.0016 (7) | 0.0057 (6) | 0.0001 (7) |
C22 | 0.0258 (12) | 0.0227 (12) | 0.0295 (12) | −0.0005 (9) | 0.0023 (9) | −0.0024 (9) |
C23 | 0.0311 (13) | 0.0284 (13) | 0.0327 (13) | 0.0003 (10) | 0.0014 (10) | 0.0015 (10) |
C24 | 0.0375 (13) | 0.0305 (13) | 0.0256 (12) | −0.0012 (11) | 0.0091 (10) | −0.0002 (10) |
C25 | 0.0294 (12) | 0.0276 (13) | 0.0250 (12) | −0.0050 (10) | 0.0060 (9) | −0.0046 (9) |
C251 | 0.0319 (13) | 0.0318 (14) | 0.0328 (13) | −0.0004 (11) | 0.0056 (10) | −0.0028 (10) |
N1—O14 | 1.450 (2) | C6—H6 | 0.9500 |
N1—C9a | 1.459 (3) | C7—F7 | 1.372 (3) |
N1—C2 | 1.503 (3) | C7—C8 | 1.378 (3) |
C2—C22 | 1.489 (3) | C8—C9 | 1.390 (3) |
C2—C3 | 1.546 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.389 (3) |
C3—C4 | 1.534 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | O21—C25 | 1.377 (3) |
C3—H3B | 0.9900 | O21—C22 | 1.391 (3) |
C4—O14 | 1.459 (2) | C22—C23 | 1.343 (3) |
C4—C5 | 1.519 (3) | C23—C24 | 1.431 (3) |
C4—H4 | 1.0000 | C23—H23 | 0.9500 |
C5—C5a | 1.508 (3) | C24—C25 | 1.356 (3) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—C251 | 1.484 (3) |
C5a—C6 | 1.398 (3) | C251—H25A | 0.9800 |
C5a—C9a | 1.399 (3) | C251—H25B | 0.9800 |
C6—C7 | 1.377 (3) | C251—H25C | 0.9800 |
O14—N1—C9a | 107.71 (16) | F7—C7—C6 | 118.2 (2) |
O14—N1—C2 | 101.49 (15) | F7—C7—C8 | 118.3 (2) |
C9a—N1—C2 | 109.29 (17) | C6—C7—C8 | 123.5 (2) |
C22—C2—N1 | 111.71 (18) | C7—C8—C9 | 117.7 (2) |
C22—C2—C3 | 112.27 (19) | C7—C8—H8 | 121.2 |
N1—C2—C3 | 103.63 (17) | C9—C8—H8 | 121.2 |
C22—C2—H2 | 109.7 | C9a—C9—C8 | 120.2 (2) |
N1—C2—H2 | 109.7 | C9a—C9—H9 | 119.9 |
C3—C2—H2 | 109.7 | C8—C9—H9 | 119.9 |
C4—C3—C2 | 103.64 (17) | C9—C9a—C5a | 121.4 (2) |
C4—C3—H3A | 111.0 | C9—C9a—N1 | 116.97 (19) |
C2—C3—H3A | 111.0 | C5a—C9a—N1 | 121.5 (2) |
C4—C3—H3B | 111.0 | N1—O14—C4 | 104.22 (15) |
C2—C3—H3B | 111.0 | C25—O21—C22 | 106.69 (17) |
H3A—C3—H3B | 109.0 | C23—C22—O21 | 109.6 (2) |
O14—C4—C5 | 107.04 (17) | C23—C22—C2 | 134.6 (2) |
O14—C4—C3 | 104.30 (17) | O21—C22—C2 | 115.82 (19) |
C5—C4—C3 | 112.34 (19) | C22—C23—C24 | 107.3 (2) |
O14—C4—H4 | 111.0 | C22—C23—H23 | 126.3 |
C5—C4—H4 | 111.0 | C24—C23—H23 | 126.3 |
C3—C4—H4 | 111.0 | C25—C24—C23 | 106.7 (2) |
C5a—C5—C4 | 108.78 (18) | C25—C24—H24 | 126.7 |
C5a—C5—H5A | 109.9 | C23—C24—H24 | 126.7 |
C4—C5—H5A | 109.9 | C24—C25—O21 | 109.7 (2) |
C5a—C5—H5B | 109.9 | C24—C25—C251 | 133.1 (2) |
C4—C5—H5B | 109.9 | O21—C25—C251 | 117.2 (2) |
H5A—C5—H5B | 108.3 | C25—C251—H25A | 109.5 |
C6—C5a—C9a | 118.2 (2) | C25—C251—H25B | 109.5 |
C6—C5a—C5 | 121.9 (2) | H25A—C251—H25B | 109.5 |
C9a—C5a—C5 | 119.9 (2) | C25—C251—H25C | 109.5 |
C7—C6—C5a | 119.0 (2) | H25A—C251—H25C | 109.5 |
C7—C6—H6 | 120.5 | H25B—C251—H25C | 109.5 |
C5a—C6—H6 | 120.5 | ||
O14—N1—C2—C22 | −82.6 (2) | C6—C5a—C9a—N1 | −175.8 (2) |
C9a—N1—C2—C22 | 163.83 (18) | C5—C5a—C9a—N1 | 2.7 (3) |
O14—N1—C2—C3 | 38.5 (2) | O14—N1—C9a—C9 | 154.56 (18) |
C9a—N1—C2—C3 | −75.1 (2) | C2—N1—C9a—C9 | −96.0 (2) |
C22—C2—C3—C4 | 105.7 (2) | O14—N1—C9a—C5a | −28.8 (3) |
N1—C2—C3—C4 | −15.0 (2) | C2—N1—C9a—C5a | 80.7 (2) |
C2—C3—C4—O14 | −13.7 (2) | C9a—N1—O14—C4 | 66.04 (19) |
C2—C3—C4—C5 | 101.9 (2) | C2—N1—O14—C4 | −48.72 (19) |
O14—C4—C5—C5a | 50.6 (2) | C5—C4—O14—N1 | −80.3 (2) |
C3—C4—C5—C5a | −63.3 (2) | C3—C4—O14—N1 | 38.9 (2) |
C4—C5—C5a—C6 | 165.2 (2) | C25—O21—C22—C23 | −0.4 (2) |
C4—C5—C5a—C9a | −13.3 (3) | C25—O21—C22—C2 | −179.20 (17) |
C9a—C5a—C6—C7 | 1.2 (3) | N1—C2—C22—C23 | 107.0 (3) |
C5—C5a—C6—C7 | −177.3 (2) | C3—C2—C22—C23 | −8.9 (4) |
C5a—C6—C7—F7 | 177.0 (2) | N1—C2—C22—O21 | −74.5 (2) |
C5a—C6—C7—C8 | −2.5 (4) | C3—C2—C22—O21 | 169.54 (18) |
F7—C7—C8—C9 | −177.68 (19) | O21—C22—C23—C24 | −0.2 (3) |
C6—C7—C8—C9 | 1.8 (4) | C2—C22—C23—C24 | 178.3 (2) |
C7—C8—C9—C9a | 0.2 (3) | C22—C23—C24—C25 | 0.8 (3) |
C8—C9—C9a—C5a | −1.3 (3) | C23—C24—C25—O21 | −1.0 (3) |
C8—C9—C9a—N1 | 175.29 (19) | C23—C24—C25—C251 | 178.6 (2) |
C6—C5a—C9a—C9 | 0.6 (3) | C22—O21—C25—C24 | 0.9 (2) |
C5—C5a—C9a—C9 | 179.1 (2) | C22—O21—C25—C251 | −178.77 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O14i | 0.99 | 2.55 | 3.527 (3) | 169 |
Symmetry code: (i) x+1, y, z. |
C15H14FNOS | F(000) = 576 |
Mr = 275.34 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2944 reflections |
a = 9.272 (2) Å | θ = 2.9–27.5° |
b = 10.9142 (13) Å | µ = 0.25 mm−1 |
c = 12.963 (2) Å | T = 120 K |
β = 101.023 (11)° | Needle, colourless |
V = 1287.6 (4) Å3 | 0.36 × 0.19 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2944 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→14 |
Tmin = 0.914, Tmax = 0.965 | l = −16→16 |
20089 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0574P)2 + 1.162P] where P = (Fo2 + 2Fc2)/3 |
2944 reflections | (Δ/σ)max = 0.002 |
173 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C15H14FNOS | V = 1287.6 (4) Å3 |
Mr = 275.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.272 (2) Å | µ = 0.25 mm−1 |
b = 10.9142 (13) Å | T = 120 K |
c = 12.963 (2) Å | 0.36 × 0.19 × 0.14 mm |
β = 101.023 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2944 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2049 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 0.965 | Rint = 0.059 |
20089 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.65 e Å−3 |
2944 reflections | Δρmin = −0.50 e Å−3 |
173 parameters |
x | y | z | Uiso*/Ueq | ||
S21 | 0.73323 (7) | 0.36360 (7) | 0.54429 (5) | 0.0367 (2) | |
F7 | 0.67363 (18) | 0.48049 (16) | −0.15000 (12) | 0.0426 (4) | |
O14 | 0.87502 (16) | 0.34916 (15) | 0.31779 (13) | 0.0268 (4) | |
N1 | 0.7208 (2) | 0.34258 (18) | 0.26739 (15) | 0.0227 (4) | |
C2 | 0.6530 (2) | 0.4340 (2) | 0.33016 (18) | 0.0230 (5) | |
H2 | 0.5622 | 0.4678 | 0.2849 | 0.028* | |
C3 | 0.7692 (3) | 0.5373 (2) | 0.3529 (2) | 0.0295 (6) | |
H3A | 0.7372 | 0.6107 | 0.3097 | 0.035* | |
H3B | 0.7877 | 0.5607 | 0.4281 | 0.035* | |
C4 | 0.9063 (3) | 0.4801 (2) | 0.3228 (2) | 0.0290 (6) | |
H4 | 0.9954 | 0.4979 | 0.3777 | 0.035* | |
C5 | 0.9300 (3) | 0.5206 (2) | 0.2149 (2) | 0.0304 (6) | |
H5A | 0.9299 | 0.6112 | 0.2108 | 0.036* | |
H5B | 1.0262 | 0.4905 | 0.2029 | 0.036* | |
C5a | 0.8081 (3) | 0.4693 (2) | 0.13190 (19) | 0.0250 (5) | |
C6 | 0.7939 (3) | 0.5023 (2) | 0.0261 (2) | 0.0297 (6) | |
H6 | 0.8589 | 0.5602 | 0.0048 | 0.036* | |
C7 | 0.6837 (3) | 0.4489 (2) | −0.04656 (19) | 0.0304 (6) | |
C8 | 0.5844 (3) | 0.3665 (2) | −0.02092 (19) | 0.0287 (5) | |
H8 | 0.5091 | 0.3327 | −0.0733 | 0.034* | |
C9 | 0.5977 (2) | 0.3339 (2) | 0.08428 (19) | 0.0249 (5) | |
H9 | 0.5306 | 0.2774 | 0.1049 | 0.030* | |
C9a | 0.7097 (2) | 0.3845 (2) | 0.15926 (18) | 0.0224 (5) | |
C22 | 0.6115 (2) | 0.3756 (2) | 0.42537 (17) | 0.0219 (5) | |
C23 | 0.4768 (2) | 0.3294 (2) | 0.43404 (18) | 0.0227 (5) | |
C24 | 0.4746 (3) | 0.2853 (2) | 0.53732 (18) | 0.0253 (5) | |
H24 | 0.3900 | 0.2501 | 0.5569 | 0.030* | |
C25 | 0.6039 (3) | 0.2983 (2) | 0.6045 (2) | 0.0324 (6) | |
H25 | 0.6209 | 0.2741 | 0.6762 | 0.039* | |
C231 | 0.3468 (3) | 0.3223 (3) | 0.3454 (2) | 0.0369 (6) | |
H23A | 0.3433 | 0.2411 | 0.3128 | 0.055* | |
H23B | 0.3556 | 0.3852 | 0.2930 | 0.055* | |
H23C | 0.2565 | 0.3360 | 0.3727 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0188 (9) | 0.0245 (11) | 0.0243 (10) | 0.0001 (8) | 0.0030 (8) | 0.0004 (8) |
C2 | 0.0211 (11) | 0.0250 (12) | 0.0237 (12) | 0.0018 (9) | 0.0064 (9) | 0.0012 (10) |
C3 | 0.0311 (13) | 0.0265 (13) | 0.0326 (13) | −0.0057 (11) | 0.0105 (11) | −0.0025 (11) |
C4 | 0.0241 (12) | 0.0314 (13) | 0.0310 (13) | −0.0073 (10) | 0.0035 (10) | −0.0033 (11) |
C5 | 0.0241 (12) | 0.0330 (14) | 0.0361 (14) | −0.0068 (10) | 0.0112 (10) | −0.0012 (11) |
C5a | 0.0245 (12) | 0.0209 (12) | 0.0311 (13) | 0.0016 (9) | 0.0092 (10) | −0.0005 (10) |
C6 | 0.0303 (13) | 0.0267 (13) | 0.0359 (14) | 0.0038 (10) | 0.0155 (11) | 0.0054 (11) |
C7 | 0.0337 (13) | 0.0335 (14) | 0.0259 (13) | 0.0125 (11) | 0.0103 (10) | 0.0084 (11) |
F7 | 0.0466 (10) | 0.0546 (11) | 0.0279 (8) | 0.0111 (8) | 0.0102 (7) | 0.0145 (7) |
C8 | 0.0256 (12) | 0.0330 (14) | 0.0270 (12) | 0.0076 (11) | 0.0038 (10) | −0.0025 (11) |
C9 | 0.0208 (11) | 0.0251 (12) | 0.0300 (13) | 0.0016 (9) | 0.0077 (9) | −0.0001 (10) |
C9a | 0.0240 (11) | 0.0200 (12) | 0.0241 (11) | 0.0046 (9) | 0.0071 (9) | −0.0007 (9) |
O14 | 0.0184 (8) | 0.0292 (9) | 0.0318 (9) | 0.0019 (7) | 0.0028 (7) | 0.0024 (7) |
S21 | 0.0264 (3) | 0.0503 (5) | 0.0299 (3) | −0.0075 (3) | −0.0035 (2) | 0.0081 (3) |
C22 | 0.0203 (10) | 0.0225 (12) | 0.0218 (11) | 0.0004 (9) | 0.0014 (9) | −0.0005 (9) |
C23 | 0.0230 (11) | 0.0234 (12) | 0.0222 (11) | −0.0001 (9) | 0.0050 (9) | −0.0021 (9) |
C24 | 0.0266 (12) | 0.0253 (13) | 0.0257 (12) | 0.0004 (10) | 0.0098 (10) | 0.0014 (10) |
C25 | 0.0394 (14) | 0.0345 (14) | 0.0229 (12) | −0.0013 (12) | 0.0050 (11) | 0.0048 (11) |
C231 | 0.0271 (13) | 0.0483 (17) | 0.0337 (14) | −0.0077 (12) | 0.0018 (11) | 0.0093 (12) |
N1—O14 | 1.456 (2) | C6—H6 | 0.9500 |
N1—C9a | 1.459 (3) | C7—F7 | 1.370 (3) |
N1—C2 | 1.499 (3) | C7—C8 | 1.373 (4) |
C2—C22 | 1.503 (3) | C8—C9 | 1.392 (3) |
C2—C3 | 1.549 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.393 (3) |
C3—C4 | 1.533 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | S21—C25 | 1.707 (3) |
C3—H3B | 0.9900 | S21—C22 | 1.733 (2) |
C4—O14 | 1.457 (3) | C22—C23 | 1.371 (3) |
C4—C5 | 1.523 (4) | C23—C24 | 1.427 (3) |
C4—H4 | 1.0000 | C23—C231 | 1.499 (3) |
C5—C5a | 1.510 (3) | C24—C25 | 1.348 (3) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—H25 | 0.9500 |
C5a—C9a | 1.392 (3) | C231—H23A | 0.9800 |
C5a—C6 | 1.399 (3) | C231—H23B | 0.9800 |
C6—C7 | 1.379 (4) | C231—H23C | 0.9800 |
O14—N1—C9a | 107.34 (16) | F7—C7—C8 | 118.6 (2) |
O14—N1—C2 | 101.62 (16) | F7—C7—C6 | 117.7 (2) |
C9a—N1—C2 | 110.66 (17) | C8—C7—C6 | 123.7 (2) |
N1—C2—C22 | 111.31 (19) | C7—C8—C9 | 117.8 (2) |
N1—C2—C3 | 103.85 (18) | C7—C8—H8 | 121.1 |
C22—C2—C3 | 115.5 (2) | C9—C8—H8 | 121.1 |
N1—C2—H2 | 108.7 | C8—C9—C9a | 119.8 (2) |
C22—C2—H2 | 108.7 | C8—C9—H9 | 120.1 |
C3—C2—H2 | 108.7 | C9a—C9—H9 | 120.1 |
C4—C3—C2 | 103.61 (19) | C5a—C9a—C9 | 121.5 (2) |
C4—C3—H3A | 111.0 | C5a—C9a—N1 | 121.6 (2) |
C2—C3—H3A | 111.0 | C9—C9a—N1 | 116.9 (2) |
C4—C3—H3B | 111.0 | N1—O14—C4 | 103.81 (16) |
C2—C3—H3B | 111.0 | C25—S21—C22 | 92.48 (12) |
H3A—C3—H3B | 109.0 | C23—C22—C2 | 127.1 (2) |
O14—C4—C5 | 107.8 (2) | C23—C22—S21 | 110.36 (17) |
O14—C4—C3 | 104.08 (18) | C2—C22—S21 | 122.49 (16) |
C5—C4—C3 | 112.8 (2) | C22—C23—C24 | 112.2 (2) |
O14—C4—H4 | 110.6 | C22—C23—C231 | 124.6 (2) |
C5—C4—H4 | 110.6 | C24—C23—C231 | 123.2 (2) |
C3—C4—H4 | 110.6 | C25—C24—C23 | 113.6 (2) |
C5a—C5—C4 | 109.1 (2) | C25—C24—H24 | 123.2 |
C5a—C5—H5A | 109.9 | C23—C24—H24 | 123.2 |
C4—C5—H5A | 109.9 | C24—C25—S21 | 111.36 (19) |
C5a—C5—H5B | 109.9 | C24—C25—H25 | 124.3 |
C4—C5—H5B | 109.9 | S21—C25—H25 | 124.3 |
H5A—C5—H5B | 108.3 | C23—C231—H23A | 109.5 |
C9a—C5a—C6 | 118.5 (2) | C23—C231—H23B | 109.5 |
C9a—C5a—C5 | 120.1 (2) | H23A—C231—H23B | 109.5 |
C6—C5a—C5 | 121.3 (2) | C23—C231—H23C | 109.5 |
C7—C6—C5a | 118.6 (2) | H23A—C231—H23C | 109.5 |
C7—C6—H6 | 120.7 | H23B—C231—H23C | 109.5 |
C5a—C6—H6 | 120.7 | ||
O14—N1—C2—C22 | −87.67 (19) | C8—C9—C9a—N1 | −177.6 (2) |
C9a—N1—C2—C22 | 158.58 (18) | O14—N1—C9a—C5a | −29.2 (3) |
O14—N1—C2—C3 | 37.2 (2) | C2—N1—C9a—C5a | 80.9 (3) |
C9a—N1—C2—C3 | −76.6 (2) | O14—N1—C9a—C9 | 149.65 (19) |
N1—C2—C3—C4 | −12.8 (2) | C2—N1—C9a—C9 | −100.3 (2) |
C22—C2—C3—C4 | 109.3 (2) | C9a—N1—O14—C4 | 67.2 (2) |
C2—C3—C4—O14 | −16.2 (2) | C2—N1—O14—C4 | −49.0 (2) |
C2—C3—C4—C5 | 100.4 (2) | C5—C4—O14—N1 | −79.4 (2) |
O14—C4—C5—C5a | 47.2 (3) | C3—C4—O14—N1 | 40.6 (2) |
C3—C4—C5—C5a | −67.1 (3) | N1—C2—C22—C23 | −94.9 (3) |
C4—C5—C5a—C9a | −8.6 (3) | C3—C2—C22—C23 | 147.0 (2) |
C4—C5—C5a—C6 | 173.4 (2) | N1—C2—C22—S21 | 87.6 (2) |
C9a—C5a—C6—C7 | −0.3 (4) | C3—C2—C22—S21 | −30.4 (3) |
C5—C5a—C6—C7 | 177.6 (2) | C25—S21—C22—C23 | −0.3 (2) |
C5a—C6—C7—F7 | −178.7 (2) | C25—S21—C22—C2 | 177.5 (2) |
C5a—C6—C7—C8 | 1.3 (4) | C2—C22—C23—C24 | −177.6 (2) |
F7—C7—C8—C9 | 179.0 (2) | S21—C22—C23—C24 | 0.2 (3) |
C6—C7—C8—C9 | −1.0 (4) | C2—C22—C23—C231 | 4.0 (4) |
C7—C8—C9—C9a | −0.3 (3) | S21—C22—C23—C231 | −178.3 (2) |
C6—C5a—C9a—C9 | −0.9 (3) | C22—C23—C24—C25 | 0.2 (3) |
C5—C5a—C9a—C9 | −178.9 (2) | C231—C23—C24—C25 | 178.7 (2) |
C6—C5a—C9a—N1 | 177.9 (2) | C23—C24—C25—S21 | −0.5 (3) |
C5—C5a—C9a—N1 | −0.1 (3) | C22—S21—C25—C24 | 0.5 (2) |
C8—C9—C9a—C5a | 1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···Cg1i | 0.95 | 2.56 | 3.443 (3) | 154 |
Symmetry code: (i) x−1/2, −y+1/2, z+1/2. |
C15H14FNOS | F(000) = 576 |
Mr = 275.34 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2975 reflections |
a = 9.2106 (16) Å | θ = 3.0–27.5° |
b = 10.906 (2) Å | µ = 0.25 mm−1 |
c = 13.4259 (13) Å | T = 120 K |
β = 106.086 (12)° | Plate, colourless |
V = 1295.8 (4) Å3 | 0.39 × 0.24 × 0.10 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2975 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1888 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.908, Tmax = 0.975 | l = −17→17 |
20023 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.733P] where P = (Fo2 + 2Fc2)/3 |
2975 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C15H14FNOS | V = 1295.8 (4) Å3 |
Mr = 275.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2106 (16) Å | µ = 0.25 mm−1 |
b = 10.906 (2) Å | T = 120 K |
c = 13.4259 (13) Å | 0.39 × 0.24 × 0.10 mm |
β = 106.086 (12)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2975 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1888 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.975 | Rint = 0.082 |
20023 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2975 reflections | Δρmin = −0.31 e Å−3 |
173 parameters |
x | y | z | Uiso*/Ueq | ||
S21 | 0.77817 (7) | 0.65565 (6) | 0.49078 (5) | 0.02927 (17) | |
F7 | 0.13536 (16) | 0.52473 (13) | −0.12616 (10) | 0.0381 (4) | |
O14 | 0.45370 (18) | 0.63367 (14) | 0.33326 (12) | 0.0283 (4) | |
N1 | 0.5321 (2) | 0.64634 (16) | 0.25375 (14) | 0.0231 (4) | |
C2 | 0.6567 (2) | 0.5554 (2) | 0.28974 (18) | 0.0247 (5) | |
H2 | 0.6910 | 0.5277 | 0.2290 | 0.030* | |
C3 | 0.5796 (3) | 0.4466 (2) | 0.32923 (19) | 0.0295 (6) | |
H3A | 0.5604 | 0.3778 | 0.2791 | 0.035* | |
H3B | 0.6425 | 0.4168 | 0.3971 | 0.035* | |
C4 | 0.4311 (3) | 0.5017 (2) | 0.33886 (19) | 0.0306 (6) | |
H4 | 0.4136 | 0.4790 | 0.4068 | 0.037* | |
C5 | 0.2958 (3) | 0.4674 (2) | 0.24979 (18) | 0.0293 (6) | |
H5A | 0.2890 | 0.3772 | 0.2424 | 0.035* | |
H5B | 0.2019 | 0.4974 | 0.2637 | 0.035* | |
C5a | 0.3132 (2) | 0.52449 (19) | 0.15110 (18) | 0.0237 (5) | |
C6 | 0.2145 (3) | 0.4968 (2) | 0.05498 (19) | 0.0284 (5) | |
H6 | 0.1332 | 0.4414 | 0.0498 | 0.034* | |
C7 | 0.2359 (3) | 0.5505 (2) | −0.03230 (18) | 0.0280 (5) | |
C8 | 0.3531 (3) | 0.6300 (2) | −0.03024 (18) | 0.0279 (5) | |
H8 | 0.3663 | 0.6640 | −0.0923 | 0.034* | |
C9 | 0.4509 (3) | 0.6584 (2) | 0.06547 (17) | 0.0256 (5) | |
H9 | 0.5332 | 0.7126 | 0.0697 | 0.031* | |
C9a | 0.4292 (2) | 0.60785 (19) | 0.15560 (17) | 0.0227 (5) | |
C22 | 0.7885 (2) | 0.60794 (19) | 0.36990 (17) | 0.0234 (5) | |
C23 | 0.9329 (3) | 0.6163 (2) | 0.36471 (18) | 0.0280 (5) | |
H23 | 0.9626 | 0.5945 | 0.3047 | 0.034* | |
C24 | 1.0358 (3) | 0.6605 (2) | 0.45681 (18) | 0.0275 (5) | |
H24 | 1.1405 | 0.6719 | 0.4641 | 0.033* | |
C25 | 0.9704 (3) | 0.6848 (2) | 0.53327 (18) | 0.0275 (5) | |
C251 | 1.0413 (3) | 0.7310 (2) | 0.64117 (19) | 0.0372 (6) | |
H25A | 1.1513 | 0.7344 | 0.6539 | 0.056* | |
H25B | 1.0160 | 0.6756 | 0.6914 | 0.056* | |
H25C | 1.0028 | 0.8133 | 0.6486 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0211 (10) | 0.0214 (9) | 0.0285 (10) | 0.0013 (8) | 0.0096 (9) | −0.0006 (8) |
C2 | 0.0232 (12) | 0.0218 (11) | 0.0298 (13) | 0.0026 (9) | 0.0084 (11) | 0.0000 (10) |
C3 | 0.0283 (13) | 0.0219 (12) | 0.0338 (14) | −0.0032 (10) | 0.0013 (11) | 0.0033 (10) |
C4 | 0.0362 (14) | 0.0278 (12) | 0.0289 (13) | −0.0056 (11) | 0.0109 (12) | 0.0052 (10) |
C5 | 0.0245 (13) | 0.0324 (14) | 0.0328 (14) | −0.0038 (10) | 0.0107 (11) | −0.0005 (11) |
C5a | 0.0209 (12) | 0.0206 (11) | 0.0300 (13) | 0.0032 (9) | 0.0079 (11) | 0.0000 (10) |
C6 | 0.0221 (12) | 0.0272 (12) | 0.0369 (15) | −0.0002 (10) | 0.0101 (11) | −0.0042 (11) |
C7 | 0.0243 (13) | 0.0299 (12) | 0.0275 (13) | 0.0030 (10) | 0.0032 (11) | −0.0061 (11) |
F7 | 0.0353 (9) | 0.0497 (9) | 0.0275 (8) | −0.0043 (7) | 0.0055 (7) | −0.0069 (7) |
C8 | 0.0295 (13) | 0.0270 (12) | 0.0290 (13) | 0.0044 (10) | 0.0110 (11) | 0.0010 (10) |
C9 | 0.0247 (12) | 0.0212 (11) | 0.0330 (14) | 0.0013 (10) | 0.0114 (11) | 0.0013 (10) |
C9a | 0.0203 (12) | 0.0190 (10) | 0.0291 (13) | 0.0024 (9) | 0.0071 (10) | −0.0020 (10) |
O14 | 0.0296 (9) | 0.0288 (9) | 0.0295 (9) | −0.0004 (7) | 0.0133 (8) | −0.0044 (7) |
S21 | 0.0251 (3) | 0.0307 (3) | 0.0336 (3) | −0.0029 (3) | 0.0110 (3) | −0.0053 (3) |
C22 | 0.0225 (12) | 0.0198 (11) | 0.0276 (13) | 0.0010 (9) | 0.0066 (11) | 0.0011 (9) |
C23 | 0.0276 (13) | 0.0279 (12) | 0.0299 (13) | −0.0005 (10) | 0.0103 (11) | 0.0021 (10) |
C24 | 0.0202 (12) | 0.0279 (12) | 0.0338 (13) | −0.0027 (10) | 0.0062 (11) | 0.0044 (11) |
C25 | 0.0248 (13) | 0.0230 (12) | 0.0328 (13) | −0.0032 (10) | 0.0046 (11) | 0.0020 (10) |
C251 | 0.0368 (15) | 0.0356 (14) | 0.0369 (15) | −0.0039 (12) | 0.0063 (13) | −0.0052 (12) |
N1—O14 | 1.452 (2) | C6—H6 | 0.9500 |
N1—C9a | 1.456 (3) | C7—F7 | 1.370 (3) |
N1—C2 | 1.492 (3) | C7—C8 | 1.378 (3) |
C2—C22 | 1.496 (3) | C8—C9 | 1.385 (3) |
C2—C3 | 1.550 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.394 (3) |
C3—C4 | 1.532 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | S21—C22 | 1.732 (2) |
C3—H3B | 0.9900 | S21—C25 | 1.732 (2) |
C4—O14 | 1.459 (3) | C22—C23 | 1.354 (3) |
C4—C5 | 1.516 (3) | C23—C24 | 1.418 (3) |
C4—H4 | 1.0000 | C23—H23 | 0.9500 |
C5—C5a | 1.512 (3) | C24—C25 | 1.353 (3) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—C251 | 1.502 (3) |
C5a—C6 | 1.390 (3) | C251—H25A | 0.9800 |
C5a—C9a | 1.391 (3) | C251—H25B | 0.9800 |
C6—C7 | 1.372 (3) | C251—H25C | 0.9800 |
O14—N1—C9a | 107.82 (16) | F7—C7—C6 | 118.5 (2) |
O14—N1—C2 | 101.14 (15) | F7—C7—C8 | 118.2 (2) |
C9a—N1—C2 | 110.56 (16) | C6—C7—C8 | 123.2 (2) |
N1—C2—C22 | 112.13 (18) | C7—C8—C9 | 117.6 (2) |
N1—C2—C3 | 103.65 (17) | C7—C8—H8 | 121.2 |
C22—C2—C3 | 113.87 (19) | C9—C8—H8 | 121.2 |
N1—C2—H2 | 109.0 | C8—C9—C9a | 120.3 (2) |
C22—C2—H2 | 109.0 | C8—C9—H9 | 119.9 |
C3—C2—H2 | 109.0 | C9a—C9—H9 | 119.9 |
C4—C3—C2 | 103.41 (18) | C5a—C9a—C9 | 120.9 (2) |
C4—C3—H3A | 111.1 | C5a—C9a—N1 | 121.8 (2) |
C2—C3—H3A | 111.1 | C9—C9a—N1 | 117.22 (19) |
C4—C3—H3B | 111.1 | N1—O14—C4 | 103.82 (15) |
C2—C3—H3B | 111.1 | C22—S21—C25 | 92.71 (11) |
H3A—C3—H3B | 109.0 | C23—C22—C2 | 127.0 (2) |
O14—C4—C5 | 107.48 (19) | C23—C22—S21 | 109.74 (18) |
O14—C4—C3 | 103.88 (18) | C2—C22—S21 | 123.02 (16) |
C5—C4—C3 | 113.2 (2) | C22—C23—C24 | 114.0 (2) |
O14—C4—H4 | 110.7 | C22—C23—H23 | 123.0 |
C5—C4—H4 | 110.7 | C24—C23—H23 | 123.0 |
C3—C4—H4 | 110.7 | C25—C24—C23 | 113.4 (2) |
C5a—C5—C4 | 109.05 (19) | C25—C24—H24 | 123.3 |
C5a—C5—H5A | 109.9 | C23—C24—H24 | 123.3 |
C4—C5—H5A | 109.9 | C24—C25—C251 | 129.2 (2) |
C5a—C5—H5B | 109.9 | C24—C25—S21 | 110.10 (18) |
C4—C5—H5B | 109.9 | C251—C25—S21 | 120.72 (18) |
H5A—C5—H5B | 108.3 | C25—C251—H25A | 109.5 |
C6—C5a—C9a | 118.6 (2) | C25—C251—H25B | 109.5 |
C6—C5a—C5 | 121.6 (2) | H25A—C251—H25B | 109.5 |
C9a—C5a—C5 | 119.8 (2) | C25—C251—H25C | 109.5 |
C7—C6—C5a | 119.2 (2) | H25A—C251—H25C | 109.5 |
C7—C6—H6 | 120.4 | H25B—C251—H25C | 109.5 |
C5a—C6—H6 | 120.4 | ||
O14—N1—C2—C22 | −83.99 (19) | C8—C9—C9a—C5a | 2.6 (3) |
C9a—N1—C2—C22 | 162.00 (18) | C8—C9—C9a—N1 | −177.18 (19) |
O14—N1—C2—C3 | 39.26 (19) | O14—N1—C9a—C5a | −26.4 (3) |
C9a—N1—C2—C3 | −74.8 (2) | C2—N1—C9a—C5a | 83.3 (2) |
N1—C2—C3—C4 | −15.1 (2) | O14—N1—C9a—C9 | 153.33 (18) |
C22—C2—C3—C4 | 107.0 (2) | C2—N1—C9a—C9 | −97.0 (2) |
C2—C3—C4—O14 | −14.5 (2) | C9a—N1—O14—C4 | 65.9 (2) |
C2—C3—C4—C5 | 101.7 (2) | C2—N1—O14—C4 | −50.13 (19) |
O14—C4—C5—C5a | 48.2 (2) | C5—C4—O14—N1 | −80.0 (2) |
C3—C4—C5—C5a | −65.9 (2) | C3—C4—O14—N1 | 40.2 (2) |
C4—C5—C5a—C6 | 172.4 (2) | N1—C2—C22—C23 | −121.8 (2) |
C4—C5—C5a—C9a | −8.3 (3) | C3—C2—C22—C23 | 120.9 (2) |
C9a—C5a—C6—C7 | 1.2 (3) | N1—C2—C22—S21 | 64.2 (2) |
C5—C5a—C6—C7 | −179.6 (2) | C3—C2—C22—S21 | −53.1 (2) |
C5a—C6—C7—F7 | −178.34 (19) | C25—S21—C22—C23 | −0.61 (18) |
C5a—C6—C7—C8 | 1.2 (3) | C25—S21—C22—C2 | 174.32 (19) |
F7—C7—C8—C9 | 177.89 (19) | C2—C22—C23—C24 | −174.6 (2) |
C6—C7—C8—C9 | −1.6 (3) | S21—C22—C23—C24 | 0.1 (3) |
C7—C8—C9—C9a | −0.3 (3) | C22—C23—C24—C25 | 0.7 (3) |
C6—C5a—C9a—C9 | −3.0 (3) | C23—C24—C25—C251 | 179.3 (2) |
C5—C5a—C9a—C9 | 177.7 (2) | C23—C24—C25—S21 | −1.1 (3) |
C6—C5a—C9a—N1 | 176.74 (19) | C22—S21—C25—C24 | 1.00 (18) |
C5—C5a—C9a—N1 | −2.5 (3) | C22—S21—C25—C251 | −179.4 (2) |
C15H14ClNO2 | F(000) = 576 |
Mr = 275.72 | Dx = 1.396 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3017 reflections |
a = 10.2835 (13) Å | θ = 3.1–27.5° |
b = 5.4829 (3) Å | µ = 0.29 mm−1 |
c = 23.428 (2) Å | T = 120 K |
β = 96.665 (9)° | Needle, colourless |
V = 1312.0 (2) Å3 | 0.42 × 0.18 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 3017 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1902 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→7 |
Tmin = 0.889, Tmax = 0.961 | l = −30→30 |
20222 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0623P)2 + 0.6498P] where P = (Fo2 + 2Fc2)/3 |
3017 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C15H14ClNO2 | V = 1312.0 (2) Å3 |
Mr = 275.72 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.2835 (13) Å | µ = 0.29 mm−1 |
b = 5.4829 (3) Å | T = 120 K |
c = 23.428 (2) Å | 0.42 × 0.18 × 0.14 mm |
β = 96.665 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3017 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1902 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.961 | Rint = 0.073 |
20222 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.33 e Å−3 |
3017 reflections | Δρmin = −0.44 e Å−3 |
173 parameters |
x | y | z | Uiso*/Ueq | ||
O14 | 0.34374 (16) | 0.4489 (3) | 0.30724 (7) | 0.0291 (4) | |
O21 | 0.34664 (15) | 0.6791 (3) | 0.46890 (6) | 0.0289 (4) | |
N1 | 0.44200 (19) | 0.4982 (4) | 0.35536 (8) | 0.0275 (5) | |
C2 | 0.3899 (2) | 0.3569 (4) | 0.40257 (10) | 0.0273 (6) | |
H2 | 0.4640 | 0.3097 | 0.4319 | 0.033* | |
C3 | 0.3302 (2) | 0.1242 (5) | 0.37220 (10) | 0.0298 (6) | |
H3A | 0.3854 | −0.0205 | 0.3827 | 0.036* | |
H3B | 0.2408 | 0.0934 | 0.3823 | 0.036* | |
C4 | 0.3276 (2) | 0.1848 (4) | 0.30807 (10) | 0.0295 (6) | |
H4 | 0.2421 | 0.1360 | 0.2863 | 0.035* | |
C5 | 0.4406 (2) | 0.0723 (4) | 0.28161 (10) | 0.0287 (6) | |
H5A | 0.4299 | 0.1021 | 0.2396 | 0.034* | |
H5B | 0.4419 | −0.1061 | 0.2881 | 0.034* | |
C5a | 0.5680 (2) | 0.1835 (4) | 0.30853 (9) | 0.0250 (5) | |
C6 | 0.6901 (2) | 0.0847 (4) | 0.30085 (10) | 0.0264 (5) | |
H6 | 0.6954 | −0.0565 | 0.2777 | 0.032* | |
C7 | 0.8034 (2) | 0.1929 (4) | 0.32700 (10) | 0.0290 (6) | |
Cl7 | 0.95437 (6) | 0.06118 (13) | 0.31858 (3) | 0.0402 (2) | |
C8 | 0.7997 (2) | 0.4044 (5) | 0.35946 (11) | 0.0309 (6) | |
H8 | 0.8783 | 0.4796 | 0.3761 | 0.037* | |
C9 | 0.6792 (2) | 0.5027 (4) | 0.36694 (10) | 0.0292 (6) | |
H9 | 0.6749 | 0.6472 | 0.3890 | 0.035* | |
C9a | 0.5643 (2) | 0.3926 (4) | 0.34255 (10) | 0.0253 (5) | |
C22 | 0.2939 (2) | 0.5053 (4) | 0.43032 (10) | 0.0299 (6) | |
C23 | 0.1629 (3) | 0.5149 (6) | 0.42683 (12) | 0.0457 (8) | |
H23 | 0.1028 | 0.4147 | 0.4036 | 0.055* | |
C24 | 0.1308 (3) | 0.7045 (6) | 0.46471 (13) | 0.0471 (8) | |
H24 | 0.0453 | 0.7539 | 0.4714 | 0.056* | |
C25 | 0.2439 (2) | 0.7993 (5) | 0.48904 (10) | 0.0323 (6) | |
C251 | 0.2788 (3) | 1.0005 (5) | 0.53044 (11) | 0.0387 (7) | |
H25A | 0.1989 | 1.0830 | 0.5391 | 0.058* | |
H25B | 0.3354 | 1.1177 | 0.5136 | 0.058* | |
H25C | 0.3252 | 0.9338 | 0.5659 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0276 (11) | 0.0286 (11) | 0.0247 (10) | 0.0009 (9) | −0.0035 (8) | −0.0002 (9) |
C2 | 0.0315 (13) | 0.0259 (13) | 0.0238 (12) | 0.0039 (10) | −0.0002 (10) | −0.0022 (10) |
C3 | 0.0317 (14) | 0.0269 (13) | 0.0311 (13) | −0.0003 (10) | 0.0047 (10) | −0.0003 (11) |
C4 | 0.0310 (13) | 0.0253 (13) | 0.0306 (13) | −0.0029 (11) | −0.0029 (10) | −0.0021 (11) |
C5 | 0.0337 (14) | 0.0249 (13) | 0.0266 (12) | −0.0031 (11) | −0.0004 (10) | −0.0021 (10) |
C5a | 0.0309 (13) | 0.0244 (13) | 0.0198 (11) | −0.0010 (10) | 0.0026 (9) | 0.0035 (10) |
C6 | 0.0346 (14) | 0.0230 (12) | 0.0220 (11) | −0.0008 (10) | 0.0044 (10) | −0.0016 (10) |
C7 | 0.0294 (13) | 0.0318 (14) | 0.0265 (12) | 0.0025 (11) | 0.0066 (10) | 0.0030 (11) |
Cl7 | 0.0313 (4) | 0.0456 (4) | 0.0446 (4) | 0.0025 (3) | 0.0081 (3) | −0.0080 (3) |
C8 | 0.0287 (13) | 0.0311 (14) | 0.0322 (13) | −0.0039 (11) | 0.0010 (10) | −0.0024 (11) |
C9 | 0.0327 (14) | 0.0242 (13) | 0.0302 (13) | −0.0008 (10) | 0.0012 (11) | −0.0041 (10) |
C9a | 0.0284 (13) | 0.0247 (13) | 0.0226 (11) | 0.0009 (10) | 0.0020 (9) | 0.0017 (10) |
O14 | 0.0315 (9) | 0.0273 (9) | 0.0259 (9) | 0.0008 (7) | −0.0079 (7) | 0.0016 (7) |
O21 | 0.0309 (9) | 0.0309 (9) | 0.0248 (8) | 0.0034 (7) | 0.0019 (7) | −0.0008 (7) |
C22 | 0.0314 (13) | 0.0335 (14) | 0.0235 (12) | 0.0019 (11) | −0.0022 (10) | −0.0024 (11) |
C23 | 0.0291 (15) | 0.0559 (18) | 0.0498 (17) | 0.0059 (13) | −0.0047 (13) | −0.0183 (15) |
C24 | 0.0344 (15) | 0.0543 (19) | 0.0521 (17) | 0.0119 (14) | 0.0031 (13) | −0.0159 (15) |
C25 | 0.0360 (14) | 0.0355 (15) | 0.0256 (12) | 0.0105 (12) | 0.0050 (10) | −0.0011 (11) |
C251 | 0.0495 (17) | 0.0385 (16) | 0.0286 (13) | 0.0101 (13) | 0.0063 (12) | −0.0020 (12) |
N1—C9a | 1.447 (3) | C6—H6 | 0.9500 |
N1—O14 | 1.449 (2) | C7—C8 | 1.389 (3) |
N1—C2 | 1.499 (3) | C7—Cl7 | 1.744 (2) |
C2—C22 | 1.486 (3) | C8—C9 | 1.381 (4) |
C2—C3 | 1.552 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.390 (3) |
C3—C4 | 1.536 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | O21—C25 | 1.375 (3) |
C3—H3B | 0.9900 | O21—C22 | 1.380 (3) |
C4—O14 | 1.458 (3) | C22—C23 | 1.341 (4) |
C4—C5 | 1.510 (3) | C23—C24 | 1.430 (4) |
C4—H4 | 1.0000 | C23—H23 | 0.9500 |
C5—C5a | 1.515 (3) | C24—C25 | 1.339 (4) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—C251 | 1.485 (3) |
C5a—C6 | 1.399 (3) | C251—H25A | 0.9800 |
C5a—C9a | 1.399 (3) | C251—H25B | 0.9800 |
C6—C7 | 1.385 (3) | C251—H25C | 0.9800 |
C9a—N1—O14 | 107.95 (17) | C6—C7—C8 | 121.6 (2) |
C9a—N1—C2 | 109.85 (18) | C6—C7—Cl7 | 119.11 (19) |
O14—N1—C2 | 101.58 (16) | C8—C7—Cl7 | 119.26 (19) |
C22—C2—N1 | 110.6 (2) | C9—C8—C7 | 118.5 (2) |
C22—C2—C3 | 113.8 (2) | C9—C8—H8 | 120.7 |
N1—C2—C3 | 104.07 (18) | C7—C8—H8 | 120.7 |
C22—C2—H2 | 109.4 | C8—C9—C9a | 120.7 (2) |
N1—C2—H2 | 109.4 | C8—C9—H9 | 119.6 |
C3—C2—H2 | 109.4 | C9a—C9—H9 | 119.6 |
C4—C3—C2 | 103.37 (19) | C9—C9a—C5a | 120.8 (2) |
C4—C3—H3A | 111.1 | C9—C9a—N1 | 117.3 (2) |
C2—C3—H3A | 111.1 | C5a—C9a—N1 | 121.9 (2) |
C4—C3—H3B | 111.1 | N1—O14—C4 | 104.19 (16) |
C2—C3—H3B | 111.1 | C25—O21—C22 | 107.26 (19) |
H3A—C3—H3B | 109.1 | C23—C22—O21 | 109.2 (2) |
O14—C4—C5 | 107.8 (2) | C23—C22—C2 | 135.1 (2) |
O14—C4—C3 | 103.82 (18) | O21—C22—C2 | 115.7 (2) |
C5—C4—C3 | 112.7 (2) | C22—C23—C24 | 107.1 (2) |
O14—C4—H4 | 110.7 | C22—C23—H23 | 126.5 |
C5—C4—H4 | 110.7 | C24—C23—H23 | 126.5 |
C3—C4—H4 | 110.7 | C25—C24—C23 | 107.1 (2) |
C4—C5—C5a | 109.52 (19) | C25—C24—H24 | 126.4 |
C4—C5—H5A | 109.8 | C23—C24—H24 | 126.4 |
C5a—C5—H5A | 109.8 | C24—C25—O21 | 109.4 (2) |
C4—C5—H5B | 109.8 | C24—C25—C251 | 134.3 (2) |
C5a—C5—H5B | 109.8 | O21—C25—C251 | 116.3 (2) |
H5A—C5—H5B | 108.2 | C25—C251—H25A | 109.5 |
C6—C5a—C9a | 118.4 (2) | C25—C251—H25B | 109.5 |
C6—C5a—C5 | 122.5 (2) | H25A—C251—H25B | 109.5 |
C9a—C5a—C5 | 119.2 (2) | C25—C251—H25C | 109.5 |
C7—C6—C5a | 119.9 (2) | H25A—C251—H25C | 109.5 |
C7—C6—H6 | 120.0 | H25B—C251—H25C | 109.5 |
C5a—C6—H6 | 120.0 | ||
C9a—N1—C2—C22 | 160.05 (19) | C6—C5a—C9a—N1 | −176.4 (2) |
O14—N1—C2—C22 | −85.8 (2) | C5—C5a—C9a—N1 | 3.4 (3) |
C9a—N1—C2—C3 | −77.4 (2) | O14—N1—C9a—C9 | 151.4 (2) |
O14—N1—C2—C3 | 36.7 (2) | C2—N1—C9a—C9 | −98.6 (2) |
C22—C2—C3—C4 | 108.3 (2) | O14—N1—C9a—C5a | −30.6 (3) |
N1—C2—C3—C4 | −12.2 (2) | C2—N1—C9a—C5a | 79.4 (2) |
C2—C3—C4—O14 | −16.7 (2) | C9a—N1—O14—C4 | 66.5 (2) |
C2—C3—C4—C5 | 99.8 (2) | C2—N1—O14—C4 | −49.0 (2) |
O14—C4—C5—C5a | 48.8 (2) | C5—C4—O14—N1 | −78.8 (2) |
C3—C4—C5—C5a | −65.2 (3) | C3—C4—O14—N1 | 41.0 (2) |
C4—C5—C5a—C6 | 167.6 (2) | C25—O21—C22—C23 | −0.5 (3) |
C4—C5—C5a—C9a | −12.2 (3) | C25—O21—C22—C2 | 178.9 (2) |
C9a—C5a—C6—C7 | 0.5 (3) | N1—C2—C22—C23 | 101.1 (4) |
C5—C5a—C6—C7 | −179.4 (2) | C3—C2—C22—C23 | −15.6 (4) |
C5a—C6—C7—C8 | −2.3 (4) | N1—C2—C22—O21 | −78.1 (2) |
C5a—C6—C7—Cl7 | 178.08 (17) | C3—C2—C22—O21 | 165.18 (19) |
C6—C7—C8—C9 | 2.1 (4) | O21—C22—C23—C24 | 0.3 (3) |
Cl7—C7—C8—C9 | −178.33 (19) | C2—C22—C23—C24 | −179.0 (3) |
C7—C8—C9—C9a | 0.0 (4) | C22—C23—C24—C25 | 0.0 (3) |
C8—C9—C9a—C5a | −1.8 (4) | C23—C24—C25—O21 | −0.3 (3) |
C8—C9—C9a—N1 | 176.2 (2) | C23—C24—C25—C251 | 178.4 (3) |
C6—C5a—C9a—C9 | 1.5 (3) | C22—O21—C25—C24 | 0.5 (3) |
C5—C5a—C9a—C9 | −178.6 (2) | C22—O21—C25—C251 | −178.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O14i | 1.00 | 2.49 | 3.312 (3) | 140 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
C16H14F3NO3 | Z = 2 |
Mr = 325.28 | F(000) = 336 |
Triclinic, P1 | Dx = 1.501 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.5088 (6) Å | Cell parameters from 3299 reflections |
b = 10.7619 (17) Å | θ = 3.1–27.5° |
c = 13.1398 (19) Å | µ = 0.13 mm−1 |
α = 110.011 (10)° | T = 120 K |
β = 98.797 (10)° | Needle, colourless |
γ = 92.271 (12)° | 0.41 × 0.19 × 0.08 mm |
V = 719.80 (18) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3299 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1690 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.111 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −6→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.949, Tmax = 0.990 | l = −17→17 |
21281 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0626P)2 + 0.2269P] where P = (Fo2 + 2Fc2)/3 |
3299 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C16H14F3NO3 | γ = 92.271 (12)° |
Mr = 325.28 | V = 719.80 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.5088 (6) Å | Mo Kα radiation |
b = 10.7619 (17) Å | µ = 0.13 mm−1 |
c = 13.1398 (19) Å | T = 120 K |
α = 110.011 (10)° | 0.41 × 0.19 × 0.08 mm |
β = 98.797 (10)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3299 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1690 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.990 | Rint = 0.111 |
21281 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.26 e Å−3 |
3299 reflections | Δρmin = −0.31 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
F1 | 0.9339 (3) | 0.22573 (19) | −0.11911 (14) | 0.0515 (5) | |
F2 | 0.9163 (4) | 0.35443 (18) | 0.04447 (15) | 0.0609 (6) | |
F3 | 0.5900 (4) | 0.2905 (3) | −0.07717 (17) | 0.0731 (7) | |
O14 | 0.4590 (3) | 0.04233 (17) | 0.39016 (14) | 0.0258 (4) | |
O21 | 0.3182 (3) | 0.40634 (16) | 0.56232 (13) | 0.0243 (4) | |
O71 | 0.7675 (4) | 0.14349 (19) | −0.01534 (15) | 0.0365 (5) | |
N1 | 0.4265 (4) | 0.1666 (2) | 0.37127 (17) | 0.0239 (5) | |
C2 | 0.6028 (5) | 0.2625 (3) | 0.4668 (2) | 0.0247 (6) | |
H2 | 0.6606 | 0.3386 | 0.4464 | 0.030* | |
C3 | 0.8230 (5) | 0.1821 (3) | 0.4833 (2) | 0.0294 (6) | |
H3A | 0.9690 | 0.2124 | 0.4593 | 0.035* | |
H3B | 0.8683 | 0.1904 | 0.5614 | 0.035* | |
C4 | 0.7259 (4) | 0.0393 (3) | 0.4108 (2) | 0.0261 (6) | |
H4 | 0.7717 | −0.0234 | 0.4503 | 0.031* | |
C5 | 0.8106 (5) | −0.0038 (3) | 0.3005 (2) | 0.0271 (6) | |
H5A | 0.9929 | 0.0097 | 0.3120 | 0.033* | |
H5B | 0.7588 | −0.0996 | 0.2602 | 0.033* | |
C5a | 0.6997 (4) | 0.0761 (2) | 0.2337 (2) | 0.0238 (6) | |
C6 | 0.7803 (5) | 0.0758 (3) | 0.1387 (2) | 0.0267 (6) | |
H6 | 0.9078 | 0.0232 | 0.1129 | 0.032* | |
C7 | 0.6738 (5) | 0.1528 (3) | 0.0817 (2) | 0.0286 (6) | |
C8 | 0.4829 (5) | 0.2280 (3) | 0.1143 (2) | 0.0296 (6) | |
H8 | 0.4077 | 0.2774 | 0.0725 | 0.036* | |
C9 | 0.4049 (5) | 0.2288 (3) | 0.2099 (2) | 0.0288 (6) | |
H9 | 0.2756 | 0.2807 | 0.2347 | 0.035* | |
C9a | 0.5117 (4) | 0.1556 (2) | 0.2697 (2) | 0.0235 (6) | |
C22 | 0.4840 (5) | 0.3140 (2) | 0.5655 (2) | 0.0234 (6) | |
C23 | 0.4977 (5) | 0.2925 (3) | 0.6616 (2) | 0.0288 (6) | |
H23 | 0.5991 | 0.2344 | 0.6850 | 0.035* | |
C24 | 0.3308 (5) | 0.3735 (3) | 0.7216 (2) | 0.0295 (6) | |
H24 | 0.2997 | 0.3794 | 0.7922 | 0.035* | |
C25 | 0.2260 (5) | 0.4400 (2) | 0.6588 (2) | 0.0234 (6) | |
C71 | 0.7994 (6) | 0.2516 (3) | −0.0398 (2) | 0.0367 (7) | |
C251 | 0.0376 (5) | 0.5375 (3) | 0.6731 (2) | 0.0283 (6) | |
H25A | 0.1200 | 0.6275 | 0.6951 | 0.042* | |
H25B | −0.0535 | 0.5321 | 0.7302 | 0.042* | |
H25C | −0.0774 | 0.5171 | 0.6035 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0231 (12) | 0.0208 (12) | 0.0271 (12) | 0.0019 (9) | 0.0046 (9) | 0.0075 (10) |
C2 | 0.0252 (14) | 0.0217 (14) | 0.0250 (14) | −0.0005 (11) | 0.0059 (11) | 0.0051 (11) |
C3 | 0.0244 (14) | 0.0311 (16) | 0.0296 (15) | 0.0031 (12) | 0.0059 (12) | 0.0063 (13) |
C4 | 0.0196 (14) | 0.0286 (15) | 0.0310 (15) | 0.0052 (11) | 0.0050 (11) | 0.0114 (13) |
C5 | 0.0241 (14) | 0.0256 (15) | 0.0325 (16) | 0.0060 (11) | 0.0088 (12) | 0.0094 (13) |
C5a | 0.0190 (13) | 0.0206 (14) | 0.0285 (15) | −0.0005 (11) | 0.0027 (11) | 0.0054 (12) |
C6 | 0.0243 (14) | 0.0255 (15) | 0.0288 (15) | 0.0028 (11) | 0.0086 (12) | 0.0063 (12) |
C7 | 0.0326 (16) | 0.0321 (16) | 0.0198 (14) | 0.0020 (12) | 0.0089 (12) | 0.0059 (12) |
C8 | 0.0315 (16) | 0.0334 (16) | 0.0249 (15) | 0.0067 (12) | 0.0038 (12) | 0.0115 (13) |
C9 | 0.0250 (14) | 0.0299 (16) | 0.0290 (15) | 0.0068 (12) | 0.0047 (12) | 0.0069 (13) |
C9a | 0.0230 (14) | 0.0215 (14) | 0.0247 (14) | 0.0016 (11) | 0.0059 (11) | 0.0058 (11) |
O14 | 0.0243 (10) | 0.0224 (10) | 0.0323 (11) | 0.0020 (8) | 0.0067 (8) | 0.0109 (8) |
O71 | 0.0485 (13) | 0.0350 (12) | 0.0302 (11) | 0.0095 (10) | 0.0179 (9) | 0.0117 (10) |
C71 | 0.0435 (19) | 0.044 (2) | 0.0279 (16) | 0.0147 (15) | 0.0131 (14) | 0.0157 (15) |
F1 | 0.0661 (13) | 0.0627 (13) | 0.0422 (11) | 0.0236 (10) | 0.0312 (10) | 0.0282 (10) |
F2 | 0.0877 (15) | 0.0456 (12) | 0.0470 (12) | −0.0127 (11) | 0.0259 (11) | 0.0095 (10) |
F3 | 0.0667 (14) | 0.127 (2) | 0.0631 (14) | 0.0527 (13) | 0.0282 (11) | 0.0691 (14) |
O21 | 0.0288 (10) | 0.0222 (10) | 0.0216 (10) | 0.0041 (8) | 0.0061 (8) | 0.0067 (8) |
C22 | 0.0234 (14) | 0.0193 (14) | 0.0282 (15) | 0.0037 (11) | 0.0052 (11) | 0.0087 (12) |
C23 | 0.0357 (16) | 0.0247 (15) | 0.0273 (15) | 0.0049 (12) | 0.0050 (12) | 0.0106 (12) |
C24 | 0.0369 (16) | 0.0306 (16) | 0.0229 (14) | 0.0065 (12) | 0.0090 (12) | 0.0100 (12) |
C25 | 0.0273 (14) | 0.0198 (14) | 0.0210 (13) | −0.0006 (11) | 0.0078 (11) | 0.0033 (11) |
C251 | 0.0302 (15) | 0.0261 (15) | 0.0277 (15) | 0.0043 (12) | 0.0070 (12) | 0.0075 (12) |
N1—C9a | 1.450 (3) | C7—O71 | 1.421 (3) |
N1—O14 | 1.454 (3) | C8—C9 | 1.386 (4) |
N1—C2 | 1.499 (3) | C8—H8 | 0.9500 |
C2—C22 | 1.487 (3) | C9—C9a | 1.380 (4) |
C2—C3 | 1.549 (4) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | O71—C71 | 1.321 (3) |
C3—C4 | 1.527 (4) | C71—F3 | 1.323 (3) |
C3—H3A | 0.9900 | C71—F2 | 1.324 (3) |
C3—H3B | 0.9900 | C71—F1 | 1.329 (3) |
C4—O14 | 1.457 (3) | O21—C25 | 1.376 (3) |
C4—C5 | 1.517 (4) | O21—C22 | 1.383 (3) |
C4—H4 | 1.0000 | C22—C23 | 1.352 (4) |
C5—C5a | 1.508 (4) | C23—C24 | 1.429 (4) |
C5—H5A | 0.9900 | C23—H23 | 0.9500 |
C5—H5B | 0.9900 | C24—C25 | 1.348 (4) |
C5a—C6 | 1.387 (4) | C24—H24 | 0.9500 |
C5a—C9a | 1.405 (3) | C25—C251 | 1.491 (3) |
C6—C7 | 1.386 (4) | C251—H25A | 0.9800 |
C6—H6 | 0.9500 | C251—H25B | 0.9800 |
C7—C8 | 1.382 (4) | C251—H25C | 0.9800 |
C9a—N1—O14 | 107.84 (18) | C7—C8—C9 | 117.7 (2) |
C9a—N1—C2 | 109.50 (19) | C7—C8—H8 | 121.1 |
O14—N1—C2 | 101.50 (18) | C9—C8—H8 | 121.1 |
C22—C2—N1 | 111.2 (2) | C9a—C9—C8 | 121.2 (2) |
C22—C2—C3 | 113.5 (2) | C9a—C9—H9 | 119.4 |
N1—C2—C3 | 104.3 (2) | C8—C9—H9 | 119.4 |
C22—C2—H2 | 109.3 | C9—C9a—C5a | 120.5 (2) |
N1—C2—H2 | 109.3 | C9—C9a—N1 | 117.6 (2) |
C3—C2—H2 | 109.3 | C5a—C9a—N1 | 121.8 (2) |
C4—C3—C2 | 103.6 (2) | N1—O14—C4 | 104.10 (17) |
C4—C3—H3A | 111.0 | C71—O71—C7 | 119.2 (2) |
C2—C3—H3A | 111.0 | O71—C71—F3 | 113.3 (3) |
C4—C3—H3B | 111.0 | O71—C71—F2 | 113.2 (2) |
C2—C3—H3B | 111.0 | F3—C71—F2 | 107.1 (3) |
H3A—C3—H3B | 109.0 | O71—C71—F1 | 108.5 (2) |
O14—C4—C5 | 107.6 (2) | F3—C71—F1 | 106.9 (2) |
O14—C4—C3 | 103.99 (19) | F2—C71—F1 | 107.6 (3) |
C5—C4—C3 | 112.8 (2) | C25—O21—C22 | 106.90 (19) |
O14—C4—H4 | 110.7 | C23—C22—O21 | 109.3 (2) |
C5—C4—H4 | 110.7 | C23—C22—C2 | 135.2 (2) |
C3—C4—H4 | 110.7 | O21—C22—C2 | 115.5 (2) |
C5a—C5—C4 | 109.8 (2) | C22—C23—C24 | 107.1 (2) |
C5a—C5—H5A | 109.7 | C22—C23—H23 | 126.5 |
C4—C5—H5A | 109.7 | C24—C23—H23 | 126.5 |
C5a—C5—H5B | 109.7 | C25—C24—C23 | 106.9 (2) |
C4—C5—H5B | 109.7 | C25—C24—H24 | 126.6 |
H5A—C5—H5B | 108.2 | C23—C24—H24 | 126.6 |
C6—C5a—C9a | 118.6 (2) | C24—C25—O21 | 109.9 (2) |
C6—C5a—C5 | 122.2 (2) | C24—C25—C251 | 133.5 (2) |
C9a—C5a—C5 | 119.2 (2) | O21—C25—C251 | 116.6 (2) |
C7—C6—C5a | 119.6 (2) | C25—C251—H25A | 109.5 |
C7—C6—H6 | 120.2 | C25—C251—H25B | 109.5 |
C5a—C6—H6 | 120.2 | H25A—C251—H25B | 109.5 |
C8—C7—C6 | 122.3 (2) | C25—C251—H25C | 109.5 |
C8—C7—O71 | 122.7 (2) | H25A—C251—H25C | 109.5 |
C6—C7—O71 | 114.9 (2) | H25B—C251—H25C | 109.5 |
C9a—N1—C2—C22 | 159.6 (2) | C2—N1—C9a—C9 | −98.8 (3) |
O14—N1—C2—C22 | −86.6 (2) | O14—N1—C9a—C5a | −29.8 (3) |
C9a—N1—C2—C3 | −77.8 (2) | C2—N1—C9a—C5a | 79.9 (3) |
O14—N1—C2—C3 | 36.0 (2) | C9a—N1—O14—C4 | 66.7 (2) |
C22—C2—C3—C4 | 109.6 (2) | C2—N1—O14—C4 | −48.4 (2) |
N1—C2—C3—C4 | −11.6 (3) | C5—C4—O14—N1 | −78.9 (2) |
C2—C3—C4—O14 | −17.1 (3) | C3—C4—O14—N1 | 41.0 (2) |
C2—C3—C4—C5 | 99.2 (2) | C8—C7—O71—C71 | 41.8 (4) |
O14—C4—C5—C5a | 48.5 (3) | C6—C7—O71—C71 | −141.1 (3) |
C3—C4—C5—C5a | −65.7 (3) | C7—O71—C71—F3 | −74.3 (3) |
C4—C5—C5a—C6 | 167.7 (2) | C7—O71—C71—F2 | 47.8 (3) |
C4—C5—C5a—C9a | −11.1 (3) | C7—O71—C71—F1 | 167.2 (2) |
C9a—C5a—C6—C7 | −0.3 (4) | C25—O21—C22—C23 | −1.0 (3) |
C5—C5a—C6—C7 | −179.1 (2) | C25—O21—C22—C2 | 179.1 (2) |
C5a—C6—C7—C8 | −1.9 (4) | N1—C2—C22—C23 | 105.6 (3) |
C5a—C6—C7—O71 | −179.0 (2) | C3—C2—C22—C23 | −11.6 (4) |
C6—C7—C8—C9 | 2.5 (4) | N1—C2—C22—O21 | −74.4 (3) |
O71—C7—C8—C9 | 179.4 (2) | C3—C2—C22—O21 | 168.4 (2) |
C7—C8—C9—C9a | −0.9 (4) | O21—C22—C23—C24 | 0.7 (3) |
C8—C9—C9a—C5a | −1.3 (4) | C2—C22—C23—C24 | −179.3 (3) |
C8—C9—C9a—N1 | 177.4 (2) | C22—C23—C24—C25 | −0.2 (3) |
C6—C5a—C9a—C9 | 1.9 (4) | C23—C24—C25—O21 | −0.4 (3) |
C5—C5a—C9a—C9 | −179.3 (2) | C23—C24—C25—C251 | 179.2 (3) |
C6—C5a—C9a—N1 | −176.7 (2) | C22—O21—C25—C24 | 0.8 (3) |
C5—C5a—C9a—N1 | 2.1 (4) | C22—O21—C25—C251 | −178.8 (2) |
O14—N1—C9a—C9 | 151.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O14i | 0.99 | 2.58 | 3.545 (3) | 165 |
Symmetry code: (i) x+1, y, z. |
C16H14F3NO2S | F(000) = 704 |
Mr = 341.35 | Dx = 1.555 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3348 reflections |
a = 16.234 (3) Å | θ = 2.6–27.5° |
b = 5.6113 (5) Å | µ = 0.26 mm−1 |
c = 16.665 (3) Å | T = 120 K |
β = 106.143 (14)° | Block, colourless |
V = 1458.2 (4) Å3 | 0.38 × 0.32 × 0.24 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 3348 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2493 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −7→7 |
Tmin = 0.906, Tmax = 0.939 | l = −21→21 |
21849 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0464P)2 + 1.2783P] where P = (Fo2 + 2Fc2)/3 |
3348 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
C16H14F3NO2S | V = 1458.2 (4) Å3 |
Mr = 341.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.234 (3) Å | µ = 0.26 mm−1 |
b = 5.6113 (5) Å | T = 120 K |
c = 16.665 (3) Å | 0.38 × 0.32 × 0.24 mm |
β = 106.143 (14)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3348 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2493 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.939 | Rint = 0.070 |
21849 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.30 e Å−3 |
3348 reflections | Δρmin = −0.42 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
S21 | 0.41310 (4) | 0.35094 (11) | 0.92562 (4) | 0.03043 (17) | |
F1 | 0.01593 (9) | 1.1704 (3) | 0.33237 (10) | 0.0460 (4) | |
F2 | −0.00757 (11) | 0.8241 (3) | 0.37535 (11) | 0.0636 (6) | |
F3 | 0.10805 (11) | 0.8884 (3) | 0.34085 (10) | 0.0501 (4) | |
O14 | 0.39200 (9) | 0.4578 (3) | 0.67877 (9) | 0.0233 (3) | |
O71 | 0.09158 (10) | 1.0632 (3) | 0.45501 (10) | 0.0324 (4) | |
N1 | 0.30547 (11) | 0.4484 (3) | 0.68755 (11) | 0.0218 (4) | |
C2 | 0.31597 (14) | 0.5535 (4) | 0.77282 (13) | 0.0237 (4) | |
H2 | 0.2631 | 0.6467 | 0.7715 | 0.028* | |
C3 | 0.39199 (14) | 0.7315 (4) | 0.78423 (14) | 0.0269 (5) | |
H3A | 0.3729 | 0.8975 | 0.7884 | 0.032* | |
H3B | 0.4388 | 0.6932 | 0.8349 | 0.032* | |
C4 | 0.42139 (14) | 0.6969 (4) | 0.70506 (13) | 0.0234 (4) | |
H4 | 0.4853 | 0.7061 | 0.7187 | 0.028* | |
C5 | 0.38013 (13) | 0.8682 (4) | 0.63472 (14) | 0.0233 (4) | |
H5A | 0.3867 | 1.0337 | 0.6562 | 0.028* | |
H5B | 0.4094 | 0.8559 | 0.5901 | 0.028* | |
C5a | 0.28585 (13) | 0.8114 (4) | 0.59901 (13) | 0.0226 (4) | |
C6 | 0.23136 (13) | 0.9575 (4) | 0.53963 (13) | 0.0240 (4) | |
H6 | 0.2530 | 1.0957 | 0.5194 | 0.029* | |
C7 | 0.14545 (14) | 0.8985 (4) | 0.51059 (14) | 0.0267 (5) | |
C8 | 0.11120 (15) | 0.6989 (4) | 0.53724 (15) | 0.0308 (5) | |
H8 | 0.0517 | 0.6649 | 0.5173 | 0.037* | |
C9 | 0.16605 (14) | 0.5487 (4) | 0.59399 (14) | 0.0283 (5) | |
H9 | 0.1445 | 0.4066 | 0.6117 | 0.034* | |
C9a | 0.25238 (13) | 0.6061 (4) | 0.62495 (13) | 0.0223 (4) | |
C22 | 0.32612 (13) | 0.3607 (4) | 0.83779 (13) | 0.0231 (4) | |
C23 | 0.26886 (14) | 0.1832 (4) | 0.84007 (14) | 0.0255 (5) | |
C24 | 0.29619 (16) | 0.0410 (4) | 0.91387 (14) | 0.0306 (5) | |
H24 | 0.2639 | −0.0887 | 0.9258 | 0.037* | |
C25 | 0.37292 (16) | 0.1100 (5) | 0.96509 (15) | 0.0327 (5) | |
H25 | 0.4008 | 0.0342 | 1.0164 | 0.039* | |
C71 | 0.05325 (16) | 0.9854 (5) | 0.37774 (16) | 0.0360 (6) | |
C231 | 0.18665 (15) | 0.1382 (4) | 0.77280 (15) | 0.0317 (5) | |
H23A | 0.1996 | 0.0625 | 0.7247 | 0.048* | |
H23B | 0.1572 | 0.2899 | 0.7554 | 0.048* | |
H23C | 0.1497 | 0.0330 | 0.7945 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0215 (9) | 0.0197 (9) | 0.0234 (9) | −0.0004 (7) | 0.0050 (7) | 0.0004 (7) |
C2 | 0.0259 (11) | 0.0211 (10) | 0.0237 (11) | −0.0005 (9) | 0.0062 (9) | −0.0023 (9) |
C3 | 0.0306 (11) | 0.0242 (11) | 0.0259 (11) | −0.0048 (9) | 0.0078 (9) | −0.0050 (9) |
C4 | 0.0227 (10) | 0.0187 (10) | 0.0275 (11) | −0.0027 (8) | 0.0050 (8) | −0.0010 (8) |
C5 | 0.0229 (10) | 0.0182 (10) | 0.0285 (11) | −0.0023 (8) | 0.0064 (9) | 0.0010 (9) |
C5a | 0.0236 (10) | 0.0200 (10) | 0.0237 (10) | −0.0005 (8) | 0.0059 (8) | −0.0028 (8) |
C6 | 0.0250 (10) | 0.0196 (10) | 0.0273 (11) | 0.0008 (9) | 0.0072 (9) | 0.0003 (9) |
C7 | 0.0275 (11) | 0.0261 (11) | 0.0240 (11) | 0.0042 (9) | 0.0029 (9) | 0.0023 (9) |
C8 | 0.0247 (11) | 0.0321 (13) | 0.0315 (12) | −0.0042 (10) | 0.0011 (9) | 0.0008 (10) |
C9 | 0.0282 (11) | 0.0264 (11) | 0.0274 (11) | −0.0067 (9) | 0.0027 (9) | 0.0018 (9) |
C9a | 0.0248 (10) | 0.0195 (10) | 0.0206 (10) | 0.0002 (8) | 0.0031 (8) | −0.0015 (8) |
O14 | 0.0233 (7) | 0.0184 (7) | 0.0277 (8) | 0.0006 (6) | 0.0061 (6) | −0.0031 (6) |
O71 | 0.0294 (8) | 0.0315 (9) | 0.0316 (9) | 0.0057 (7) | 0.0005 (7) | 0.0047 (7) |
C71 | 0.0326 (13) | 0.0377 (14) | 0.0333 (13) | −0.0030 (11) | 0.0018 (10) | 0.0092 (11) |
F1 | 0.0378 (8) | 0.0546 (10) | 0.0398 (9) | 0.0105 (7) | 0.0013 (7) | 0.0198 (7) |
F2 | 0.0493 (10) | 0.0755 (13) | 0.0484 (10) | −0.0325 (9) | −0.0158 (8) | 0.0236 (9) |
F3 | 0.0643 (11) | 0.0499 (10) | 0.0364 (8) | 0.0133 (8) | 0.0143 (8) | 0.0053 (7) |
S21 | 0.0280 (3) | 0.0382 (3) | 0.0228 (3) | 0.0005 (3) | 0.0032 (2) | 0.0009 (2) |
C22 | 0.0236 (10) | 0.0229 (10) | 0.0225 (10) | 0.0019 (9) | 0.0060 (8) | −0.0010 (9) |
C23 | 0.0269 (11) | 0.0241 (11) | 0.0270 (11) | 0.0023 (9) | 0.0097 (9) | −0.0003 (9) |
C24 | 0.0383 (13) | 0.0286 (12) | 0.0280 (12) | 0.0034 (10) | 0.0145 (10) | 0.0034 (10) |
C25 | 0.0376 (13) | 0.0358 (13) | 0.0249 (11) | 0.0082 (11) | 0.0091 (10) | 0.0041 (10) |
C231 | 0.0300 (12) | 0.0293 (12) | 0.0345 (13) | −0.0052 (10) | 0.0070 (10) | 0.0022 (10) |
N1—O14 | 1.453 (2) | C7—O71 | 1.424 (3) |
N1—C9a | 1.454 (3) | C8—C9 | 1.389 (3) |
N1—C2 | 1.504 (3) | C8—H8 | 0.9500 |
C2—C22 | 1.507 (3) | C9—C9a | 1.390 (3) |
C2—C3 | 1.558 (3) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | O71—C71 | 1.338 (3) |
C3—C4 | 1.535 (3) | C71—F1 | 1.327 (3) |
C3—H3A | 0.9900 | C71—F3 | 1.330 (3) |
C3—H3B | 0.9900 | C71—F2 | 1.332 (3) |
C4—O14 | 1.450 (2) | S21—C25 | 1.710 (3) |
C4—C5 | 1.520 (3) | S21—C22 | 1.729 (2) |
C4—H4 | 1.0000 | C22—C23 | 1.370 (3) |
C5—C5a | 1.514 (3) | C23—C24 | 1.429 (3) |
C5—H5A | 0.9900 | C23—C231 | 1.507 (3) |
C5—H5B | 0.9900 | C24—C25 | 1.356 (3) |
C5a—C9a | 1.393 (3) | C24—H24 | 0.9500 |
C5a—C6 | 1.396 (3) | C25—H25 | 0.9500 |
C6—C7 | 1.383 (3) | C231—H23A | 0.9800 |
C6—H6 | 0.9500 | C231—H23B | 0.9800 |
C7—C8 | 1.378 (3) | C231—H23C | 0.9800 |
O14—N1—C9a | 107.61 (15) | C7—C8—C9 | 118.2 (2) |
O14—N1—C2 | 102.84 (14) | C7—C8—H8 | 120.9 |
C9a—N1—C2 | 109.17 (16) | C9—C8—H8 | 120.9 |
N1—C2—C22 | 111.01 (17) | C8—C9—C9a | 120.1 (2) |
N1—C2—C3 | 104.15 (16) | C8—C9—H9 | 120.0 |
C22—C2—C3 | 116.62 (18) | C9a—C9—H9 | 120.0 |
N1—C2—H2 | 108.2 | C9—C9a—C5a | 121.1 (2) |
C22—C2—H2 | 108.2 | C9—C9a—N1 | 117.45 (19) |
C3—C2—H2 | 108.2 | C5a—C9a—N1 | 121.42 (18) |
C4—C3—C2 | 103.83 (17) | C4—O14—N1 | 104.42 (14) |
C4—C3—H3A | 111.0 | C71—O71—C7 | 116.85 (19) |
C2—C3—H3A | 111.0 | F1—C71—F3 | 108.4 (2) |
C4—C3—H3B | 111.0 | F1—C71—F2 | 107.3 (2) |
C2—C3—H3B | 111.0 | F3—C71—F2 | 107.1 (2) |
H3A—C3—H3B | 109.0 | F1—C71—O71 | 108.0 (2) |
O14—C4—C5 | 108.33 (17) | F3—C71—O71 | 112.7 (2) |
O14—C4—C3 | 102.82 (17) | F2—C71—O71 | 113.1 (2) |
C5—C4—C3 | 114.04 (18) | C25—S21—C22 | 92.38 (11) |
O14—C4—H4 | 110.5 | C23—C22—C2 | 127.0 (2) |
C5—C4—H4 | 110.5 | C23—C22—S21 | 110.75 (17) |
C3—C4—H4 | 110.5 | C2—C22—S21 | 122.09 (16) |
C5a—C5—C4 | 110.53 (17) | C22—C23—C24 | 112.3 (2) |
C5a—C5—H5A | 109.5 | C22—C23—C231 | 124.7 (2) |
C4—C5—H5A | 109.5 | C24—C23—C231 | 123.1 (2) |
C5a—C5—H5B | 109.5 | C25—C24—C23 | 113.2 (2) |
C4—C5—H5B | 109.5 | C25—C24—H24 | 123.4 |
H5A—C5—H5B | 108.1 | C23—C24—H24 | 123.4 |
C9a—C5a—C6 | 118.75 (19) | C24—C25—S21 | 111.44 (18) |
C9a—C5a—C5 | 119.43 (19) | C24—C25—H25 | 124.3 |
C6—C5a—C5 | 121.82 (19) | S21—C25—H25 | 124.3 |
C7—C6—C5a | 119.1 (2) | C23—C231—H23A | 109.5 |
C7—C6—H6 | 120.5 | C23—C231—H23B | 109.5 |
C5a—C6—H6 | 120.5 | H23A—C231—H23B | 109.5 |
C8—C7—C6 | 122.7 (2) | C23—C231—H23C | 109.5 |
C8—C7—O71 | 120.5 (2) | H23A—C231—H23C | 109.5 |
C6—C7—O71 | 116.7 (2) | H23B—C231—H23C | 109.5 |
O14—N1—C2—C22 | −96.50 (18) | C2—N1—C9a—C9 | −98.8 (2) |
C9a—N1—C2—C22 | 149.43 (17) | O14—N1—C9a—C5a | −31.9 (2) |
O14—N1—C2—C3 | 29.79 (19) | C2—N1—C9a—C5a | 79.0 (2) |
C9a—N1—C2—C3 | −84.3 (2) | C5—C4—O14—N1 | −76.87 (19) |
N1—C2—C3—C4 | −3.6 (2) | C3—C4—O14—N1 | 44.16 (19) |
C22—C2—C3—C4 | 119.1 (2) | C9a—N1—O14—C4 | 68.27 (18) |
C2—C3—C4—O14 | −23.8 (2) | C2—N1—O14—C4 | −46.93 (18) |
C2—C3—C4—C5 | 93.2 (2) | C8—C7—O71—C71 | −66.6 (3) |
O14—C4—C5—C5a | 44.4 (2) | C6—C7—O71—C71 | 117.3 (2) |
C3—C4—C5—C5a | −69.4 (2) | C7—O71—C71—F1 | −171.56 (18) |
C4—C5—C5a—C9a | −7.7 (3) | C7—O71—C71—F3 | −51.9 (3) |
C4—C5—C5a—C6 | 173.21 (19) | C7—O71—C71—F2 | 69.8 (3) |
C9a—C5a—C6—C7 | 2.2 (3) | N1—C2—C22—C23 | −59.9 (3) |
C5—C5a—C6—C7 | −178.7 (2) | C3—C2—C22—C23 | −178.9 (2) |
C5a—C6—C7—C8 | −0.7 (3) | N1—C2—C22—S21 | 124.53 (17) |
C5a—C6—C7—O71 | 175.31 (19) | C3—C2—C22—S21 | 5.5 (3) |
C6—C7—C8—C9 | −1.7 (4) | C25—S21—C22—C23 | 0.06 (18) |
O71—C7—C8—C9 | −177.5 (2) | C25—S21—C22—C2 | 176.31 (18) |
C7—C8—C9—C9a | 2.5 (4) | C2—C22—C23—C24 | −175.7 (2) |
C8—C9—C9a—C5a | −1.1 (3) | S21—C22—C23—C24 | 0.3 (2) |
C8—C9—C9a—N1 | 176.7 (2) | C2—C22—C23—C231 | 4.9 (4) |
C6—C5a—C9a—C9 | −1.3 (3) | S21—C22—C23—C231 | −179.03 (18) |
C5—C5a—C9a—C9 | 179.6 (2) | C22—C23—C24—C25 | −0.7 (3) |
C6—C5a—C9a—N1 | −179.03 (19) | C231—C23—C24—C25 | 178.7 (2) |
C5—C5a—C9a—N1 | 1.9 (3) | C23—C24—C25—S21 | 0.7 (3) |
O14—N1—C9a—C9 | 150.29 (19) | C22—S21—C25—C24 | −0.44 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O14i | 0.99 | 2.41 | 3.383 (3) | 168 |
C3—H3A···Cg2i | 0.99 | 2.70 | 3.533 (3) | 142 |
Symmetry code: (i) x, y+1, z. |
C15H11F3N2O5 | F(000) = 728 |
Mr = 356.26 | Dx = 1.610 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3380 reflections |
a = 20.4120 (15) Å | θ = 3.0–27.5° |
b = 7.3690 (18) Å | µ = 0.15 mm−1 |
c = 10.035 (3) Å | T = 120 K |
β = 103.091 (15)° | Block, pale yellow |
V = 1470.2 (6) Å3 | 0.26 × 0.25 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2743 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1634 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 3.0° |
ϕ and ω scans | h = −24→24 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.963, Tmax = 0.980 | l = −12→12 |
18612 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0863P)2 + 1.0699P] where P = (Fo2 + 2Fc2)/3 |
2743 reflections | (Δ/σ)max = 0.001 |
226 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C15H11F3N2O5 | V = 1470.2 (6) Å3 |
Mr = 356.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.4120 (15) Å | µ = 0.15 mm−1 |
b = 7.3690 (18) Å | T = 120 K |
c = 10.035 (3) Å | 0.26 × 0.25 × 0.14 mm |
β = 103.091 (15)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2743 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1634 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.980 | Rint = 0.081 |
18612 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.31 e Å−3 |
2743 reflections | Δρmin = −0.32 e Å−3 |
226 parameters |
x | y | z | Uiso*/Ueq | ||
F1 | 0.01000 (12) | 0.1560 (3) | 0.7817 (2) | 0.0611 (7) | |
F2 | 0.07503 (12) | 0.0187 (3) | 0.6750 (3) | 0.0639 (8) | |
F3 | 0.00887 (12) | 0.2265 (4) | 0.5746 (3) | 0.0690 (8) | |
O14 | 0.24772 (12) | 0.6455 (3) | 0.3307 (2) | 0.0353 (6) | |
O21 | 0.44541 (11) | 0.7397 (3) | 0.5260 (2) | 0.0336 (6) | |
O51 | 0.59492 (13) | 0.8004 (3) | 0.4230 (3) | 0.0439 (7) | |
O52 | 0.56407 (12) | 0.8959 (3) | 0.6051 (3) | 0.0416 (7) | |
O71 | 0.09501 (12) | 0.3048 (3) | 0.7434 (2) | 0.0377 (6) | |
N1 | 0.27937 (14) | 0.5196 (4) | 0.4377 (3) | 0.0326 (7) | |
N25 | 0.55395 (15) | 0.8132 (4) | 0.4958 (3) | 0.0356 (8) | |
C2 | 0.33194 (17) | 0.6361 (5) | 0.5242 (3) | 0.0325 (8) | |
H2 | 0.3451 | 0.5875 | 0.6196 | 0.039* | |
C3 | 0.29723 (17) | 0.8236 (5) | 0.5223 (4) | 0.0327 (8) | |
H3A | 0.2850 | 0.8483 | 0.6105 | 0.039* | |
H3B | 0.3268 | 0.9222 | 0.5033 | 0.039* | |
C4 | 0.23388 (18) | 0.8055 (5) | 0.4051 (4) | 0.0345 (9) | |
H4 | 0.2281 | 0.9151 | 0.3449 | 0.041* | |
C5 | 0.16989 (17) | 0.7652 (5) | 0.4518 (4) | 0.0349 (9) | |
H5A | 0.1310 | 0.7665 | 0.3722 | 0.042* | |
H5B | 0.1625 | 0.8596 | 0.5171 | 0.042* | |
C5a | 0.17550 (17) | 0.5794 (5) | 0.5206 (3) | 0.0308 (8) | |
C6 | 0.12920 (17) | 0.5190 (5) | 0.5933 (3) | 0.0313 (8) | |
H6 | 0.0908 | 0.5901 | 0.5968 | 0.038* | |
C7 | 0.13973 (17) | 0.3538 (5) | 0.6606 (3) | 0.0334 (8) | |
C8 | 0.19444 (18) | 0.2448 (5) | 0.6571 (4) | 0.0358 (9) | |
H8 | 0.2010 | 0.1331 | 0.7055 | 0.043* | |
C9 | 0.23916 (17) | 0.3016 (5) | 0.5820 (4) | 0.0341 (9) | |
H9 | 0.2765 | 0.2274 | 0.5766 | 0.041* | |
C9a | 0.22985 (17) | 0.4677 (5) | 0.5137 (3) | 0.0312 (8) | |
C22 | 0.39078 (17) | 0.6375 (5) | 0.4589 (3) | 0.0324 (8) | |
C23 | 0.40413 (17) | 0.5620 (5) | 0.3450 (4) | 0.0341 (9) | |
H23 | 0.3748 | 0.4858 | 0.2820 | 0.041* | |
C24 | 0.46951 (17) | 0.6165 (5) | 0.3362 (4) | 0.0347 (9) | |
H24 | 0.4927 | 0.5860 | 0.2673 | 0.042* | |
C25 | 0.49149 (17) | 0.7212 (5) | 0.4473 (4) | 0.0323 (8) | |
C71 | 0.04820 (19) | 0.1791 (6) | 0.6939 (4) | 0.0414 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0381 (16) | 0.0219 (17) | 0.0384 (16) | −0.0004 (13) | 0.0101 (14) | 0.0005 (14) |
C2 | 0.040 (2) | 0.023 (2) | 0.0355 (19) | −0.0009 (16) | 0.0104 (16) | −0.0024 (16) |
C3 | 0.0363 (19) | 0.023 (2) | 0.043 (2) | −0.0019 (15) | 0.0164 (16) | −0.0064 (16) |
C4 | 0.044 (2) | 0.019 (2) | 0.041 (2) | 0.0012 (16) | 0.0127 (17) | −0.0002 (16) |
C5 | 0.038 (2) | 0.023 (2) | 0.043 (2) | 0.0021 (15) | 0.0065 (17) | −0.0008 (16) |
C5a | 0.0381 (19) | 0.020 (2) | 0.0328 (19) | −0.0003 (15) | 0.0050 (16) | −0.0033 (15) |
C6 | 0.0323 (18) | 0.025 (2) | 0.0359 (19) | 0.0025 (15) | 0.0072 (16) | −0.0003 (16) |
C7 | 0.0366 (19) | 0.029 (2) | 0.0374 (19) | −0.0047 (16) | 0.0134 (16) | −0.0017 (16) |
C8 | 0.042 (2) | 0.020 (2) | 0.046 (2) | −0.0010 (16) | 0.0100 (18) | 0.0036 (16) |
C9 | 0.0337 (19) | 0.021 (2) | 0.048 (2) | −0.0006 (16) | 0.0102 (17) | 0.0006 (17) |
C9a | 0.0338 (19) | 0.024 (2) | 0.038 (2) | −0.0030 (15) | 0.0123 (16) | −0.0020 (16) |
O14 | 0.0436 (14) | 0.0282 (14) | 0.0350 (13) | 0.0004 (11) | 0.0109 (11) | 0.0015 (11) |
O71 | 0.0417 (14) | 0.0325 (16) | 0.0417 (14) | −0.0073 (12) | 0.0154 (12) | −0.0029 (12) |
C71 | 0.037 (2) | 0.039 (3) | 0.051 (2) | −0.0023 (18) | 0.014 (2) | 0.0023 (19) |
F1 | 0.0588 (15) | 0.0574 (17) | 0.0775 (17) | −0.0142 (12) | 0.0373 (14) | 0.0040 (13) |
F2 | 0.0583 (15) | 0.0304 (15) | 0.111 (2) | −0.0096 (12) | 0.0353 (15) | −0.0079 (13) |
F3 | 0.0505 (15) | 0.080 (2) | 0.0691 (17) | −0.0183 (13) | −0.0029 (13) | 0.0198 (15) |
O21 | 0.0356 (14) | 0.0246 (14) | 0.0420 (14) | −0.0027 (11) | 0.0119 (12) | −0.0017 (11) |
C22 | 0.0335 (19) | 0.022 (2) | 0.040 (2) | 0.0015 (15) | 0.0054 (16) | 0.0046 (16) |
C23 | 0.038 (2) | 0.028 (2) | 0.038 (2) | 0.0045 (16) | 0.0110 (17) | 0.0038 (16) |
C24 | 0.039 (2) | 0.029 (2) | 0.039 (2) | 0.0055 (17) | 0.0154 (17) | 0.0045 (17) |
C25 | 0.0326 (19) | 0.024 (2) | 0.043 (2) | 0.0018 (16) | 0.0144 (17) | 0.0054 (17) |
N25 | 0.0407 (18) | 0.0216 (18) | 0.0469 (19) | 0.0005 (14) | 0.0150 (16) | 0.0052 (15) |
O51 | 0.0439 (15) | 0.0365 (16) | 0.0590 (17) | 0.0006 (12) | 0.0277 (14) | 0.0052 (13) |
O52 | 0.0485 (16) | 0.0276 (15) | 0.0506 (16) | −0.0044 (12) | 0.0153 (13) | −0.0031 (13) |
N1—C9a | 1.449 (4) | C7—O71 | 1.414 (4) |
N1—O14 | 1.455 (4) | C8—C9 | 1.374 (5) |
N1—C2 | 1.490 (4) | C8—H8 | 0.9500 |
C2—C22 | 1.493 (5) | C9—C9a | 1.395 (5) |
C2—C3 | 1.551 (5) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | O71—C71 | 1.342 (4) |
C3—C4 | 1.544 (5) | C71—F1 | 1.313 (4) |
C3—H3A | 0.9900 | C71—F3 | 1.329 (4) |
C3—H3B | 0.9900 | C71—F2 | 1.334 (4) |
C4—O14 | 1.457 (4) | O21—C25 | 1.365 (4) |
C4—C5 | 1.514 (5) | O21—C22 | 1.387 (4) |
C4—H4 | 1.0000 | C22—C23 | 1.353 (5) |
C5—C5a | 1.526 (5) | C23—C24 | 1.415 (5) |
C5—H5A | 0.9900 | C23—H23 | 0.9500 |
C5—H5B | 0.9900 | C24—C25 | 1.346 (5) |
C5a—C6 | 1.392 (5) | C24—H24 | 0.9500 |
C5a—C9a | 1.396 (5) | C25—N25 | 1.429 (5) |
C6—C7 | 1.385 (5) | N25—O52 | 1.231 (4) |
C6—H6 | 0.9500 | N25—O51 | 1.232 (4) |
C7—C8 | 1.383 (5) | ||
C9a—N1—O14 | 108.1 (2) | C6—C7—O71 | 117.5 (3) |
C9a—N1—C2 | 110.0 (2) | C9—C8—C7 | 118.6 (3) |
O14—N1—C2 | 101.7 (2) | C9—C8—H8 | 120.7 |
N1—C2—C22 | 107.1 (3) | C7—C8—H8 | 120.7 |
N1—C2—C3 | 103.9 (3) | C8—C9—C9a | 120.2 (3) |
C22—C2—C3 | 113.5 (3) | C8—C9—H9 | 119.9 |
N1—C2—H2 | 110.7 | C9a—C9—H9 | 119.9 |
C22—C2—H2 | 110.7 | C9—C9a—C5a | 121.0 (3) |
C3—C2—H2 | 110.7 | C9—C9a—N1 | 117.2 (3) |
C4—C3—C2 | 103.5 (3) | C5a—C9a—N1 | 121.8 (3) |
C4—C3—H3A | 111.1 | N1—O14—C4 | 104.1 (2) |
C2—C3—H3A | 111.1 | C71—O71—C7 | 117.3 (3) |
C4—C3—H3B | 111.1 | F1—C71—F3 | 108.0 (3) |
C2—C3—H3B | 111.1 | F1—C71—F2 | 107.8 (3) |
H3A—C3—H3B | 109.0 | F3—C71—F2 | 106.7 (3) |
O14—C4—C5 | 106.3 (3) | F1—C71—O71 | 108.8 (3) |
O14—C4—C3 | 103.5 (3) | F3—C71—O71 | 112.7 (3) |
C5—C4—C3 | 114.5 (3) | F2—C71—O71 | 112.5 (3) |
O14—C4—H4 | 110.7 | C25—O21—C22 | 104.4 (3) |
C5—C4—H4 | 110.7 | C23—C22—O21 | 109.9 (3) |
C3—C4—H4 | 110.7 | C23—C22—C2 | 134.7 (3) |
C4—C5—C5a | 109.5 (3) | O21—C22—C2 | 115.4 (3) |
C4—C5—H5A | 109.8 | C22—C23—C24 | 108.0 (3) |
C5a—C5—H5A | 109.8 | C22—C23—H23 | 126.0 |
C4—C5—H5B | 109.8 | C24—C23—H23 | 126.0 |
C5a—C5—H5B | 109.8 | C25—C24—C23 | 104.7 (3) |
H5A—C5—H5B | 108.2 | C25—C24—H24 | 127.7 |
C6—C5a—C9a | 118.6 (3) | C23—C24—H24 | 127.7 |
C6—C5a—C5 | 122.3 (3) | C24—C25—O21 | 113.1 (3) |
C9a—C5a—C5 | 119.1 (3) | C24—C25—N25 | 131.2 (3) |
C7—C6—C5a | 119.2 (3) | O21—C25—N25 | 115.7 (3) |
C7—C6—H6 | 120.4 | O52—N25—O51 | 124.5 (3) |
C5a—C6—H6 | 120.4 | O52—N25—C25 | 119.7 (3) |
C8—C7—C6 | 122.4 (3) | O51—N25—C25 | 115.8 (3) |
C8—C7—O71 | 120.0 (3) | ||
C9a—N1—C2—C22 | 163.0 (3) | C2—N1—C9a—C5a | 84.7 (4) |
O14—N1—C2—C22 | −82.6 (3) | C9a—N1—O14—C4 | 66.3 (3) |
C9a—N1—C2—C3 | −76.6 (3) | C2—N1—O14—C4 | −49.5 (3) |
O14—N1—C2—C3 | 37.8 (3) | C5—C4—O14—N1 | −80.6 (3) |
N1—C2—C3—C4 | −13.5 (3) | C3—C4—O14—N1 | 40.3 (3) |
C22—C2—C3—C4 | 102.4 (3) | C8—C7—O71—C71 | −80.4 (4) |
C2—C3—C4—O14 | −15.6 (3) | C6—C7—O71—C71 | 104.3 (4) |
C2—C3—C4—C5 | 99.7 (3) | C7—O71—C71—F1 | −177.7 (3) |
O14—C4—C5—C5a | 49.2 (4) | C7—O71—C71—F3 | −57.9 (4) |
C3—C4—C5—C5a | −64.5 (4) | C7—O71—C71—F2 | 62.9 (4) |
C4—C5—C5a—C6 | 169.2 (3) | C25—O21—C22—C23 | −0.1 (4) |
C4—C5—C5a—C9a | −9.1 (4) | C25—O21—C22—C2 | −179.5 (3) |
C9a—C5a—C6—C7 | 2.4 (5) | N1—C2—C22—C23 | 1.1 (5) |
C5—C5a—C6—C7 | −175.9 (3) | C3—C2—C22—C23 | −112.9 (4) |
C5a—C6—C7—C8 | −0.8 (5) | N1—C2—C22—O21 | −179.8 (3) |
C5a—C6—C7—O71 | 174.4 (3) | C3—C2—C22—O21 | 66.2 (4) |
C6—C7—C8—C9 | −1.2 (5) | O21—C22—C23—C24 | −0.2 (4) |
O71—C7—C8—C9 | −176.2 (3) | C2—C22—C23—C24 | 178.9 (4) |
C7—C8—C9—C9a | 1.4 (5) | C22—C23—C24—C25 | 0.5 (4) |
C8—C9—C9a—C5a | 0.3 (5) | C23—C24—C25—O21 | −0.6 (4) |
C8—C9—C9a—N1 | 179.4 (3) | C23—C24—C25—N25 | 179.0 (3) |
C6—C5a—C9a—C9 | −2.2 (5) | C22—O21—C25—C24 | 0.4 (4) |
C5—C5a—C9a—C9 | 176.1 (3) | C22—O21—C25—N25 | −179.2 (3) |
C6—C5a—C9a—N1 | 178.7 (3) | C24—C25—N25—O52 | −176.7 (4) |
C5—C5a—C9a—N1 | −2.9 (5) | O21—C25—N25—O52 | 2.8 (5) |
O14—N1—C9a—C9 | 155.4 (3) | C24—C25—N25—O51 | 2.2 (5) |
C2—N1—C9a—C9 | −94.3 (4) | O21—C25—N25—O51 | −178.2 (3) |
O14—N1—C9a—C5a | −25.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O14i | 0.99 | 2.50 | 3.474 (4) | 170 |
C3—H3B···O51ii | 0.99 | 2.60 | 3.504 (5) | 152 |
C8—H8···O14iii | 0.95 | 2.48 | 3.411 (4) | 166 |
C24—H24···O52iv | 0.95 | 2.42 | 3.338 (5) | 162 |
C4—H4···Cg1iii | 1.00 | 2.84 | 3.749 (4) | 152 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, −y+3/2, z−1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C14H12N2O4 | C15H15FN2O | C15H14FNO2 | C15H14FNOS |
Mr | 272.26 | 258.29 | 259.27 | 275.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 7.2248 (5), 18.1447 (19), 9.4504 (8) | 27.141 (4), 5.4082 (7), 17.2849 (18) | 5.5265 (5), 10.6652 (19), 20.905 (4) | 9.272 (2), 10.9142 (13), 12.963 (2) |
α, β, γ (°) | 90, 94.279 (6), 90 | 90, 103.275 (9), 90 | 90, 97.166 (11), 90 | 90, 101.023 (11), 90 |
V (Å3) | 1235.42 (19) | 2469.3 (6) | 1222.6 (3) | 1287.6 (4) |
Z | 4 | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.10 | 0.10 | 0.25 |
Crystal size (mm) | 0.38 × 0.27 × 0.22 | 0.41 × 0.27 × 0.10 | 0.26 × 0.25 × 0.14 | 0.36 × 0.19 × 0.14 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.960, 0.976 | 0.961, 0.990 | 0.974, 0.986 | 0.914, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18226, 2835, 1868 | 21463, 2824, 1511 | 17136, 2807, 1657 | 20089, 2944, 2049 |
Rint | 0.047 | 0.092 | 0.061 | 0.059 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.139, 1.05 | 0.053, 0.148, 1.05 | 0.058, 0.175, 1.06 | 0.050, 0.135, 1.03 |
No. of reflections | 2835 | 2824 | 2807 | 2944 |
No. of parameters | 181 | 173 | 173 | 173 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.29 | 0.28, −0.23 | 0.29, −0.40 | 0.65, −0.50 |
(V) | (VI) | (VII) | (VIII) | |
Crystal data | ||||
Chemical formula | C15H14FNOS | C15H14ClNO2 | C16H14F3NO3 | C16H14F3NO2S |
Mr | 275.34 | 275.72 | 325.28 | 341.35 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 9.2106 (16), 10.906 (2), 13.4259 (13) | 10.2835 (13), 5.4829 (3), 23.428 (2) | 5.5088 (6), 10.7619 (17), 13.1398 (19) | 16.234 (3), 5.6113 (5), 16.665 (3) |
α, β, γ (°) | 90, 106.086 (12), 90 | 90, 96.665 (9), 90 | 110.011 (10), 98.797 (10), 92.271 (12) | 90, 106.143 (14), 90 |
V (Å3) | 1295.8 (4) | 1312.0 (2) | 719.80 (18) | 1458.2 (4) |
Z | 4 | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.29 | 0.13 | 0.26 |
Crystal size (mm) | 0.39 × 0.24 × 0.10 | 0.42 × 0.18 × 0.14 | 0.41 × 0.19 × 0.08 | 0.38 × 0.32 × 0.24 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.908, 0.975 | 0.889, 0.961 | 0.949, 0.990 | 0.906, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20023, 2975, 1888 | 20222, 3017, 1902 | 21281, 3299, 1690 | 21849, 3348, 2493 |
Rint | 0.082 | 0.073 | 0.111 | 0.070 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.106, 1.03 | 0.052, 0.143, 1.07 | 0.056, 0.147, 1.01 | 0.048, 0.128, 1.11 |
No. of reflections | 2975 | 3017 | 3299 | 3348 |
No. of parameters | 173 | 173 | 209 | 209 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.31 | 0.33, −0.44 | 0.26, −0.31 | 0.30, −0.42 |
(IX) | |
Crystal data | |
Chemical formula | C15H11F3N2O5 |
Mr | 356.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 20.4120 (15), 7.3690 (18), 10.035 (3) |
α, β, γ (°) | 90, 103.091 (15), 90 |
V (Å3) | 1470.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.26 × 0.25 × 0.14 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.963, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18612, 2743, 1634 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.607 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.183, 1.07 |
No. of reflections | 2743 |
No. of parameters | 226 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.32 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(a) | Five-membered rings | ||
Compound | Q2 | ϕ2 | |
(I) | 0.444 (2) | 13.3 (3) | |
(II) | 0.445 (2) | 16.9 (3) | |
(III) | 0.444 (2) | 19.5 (3) | |
(IV) | 0.447 (2) | 16.2 (3) | |
(V) | 0.457 (2) | 18.8 (3) | |
(VI) | 0.446 (2) | 15.4 (3) | |
(VII) | 0.443 (3) | 14.7 (4) | |
(VIII) | 0.434 (2) | 4.5 (3) | |
(IX) | 0.448 (2) | 17.0 (3) | |
(b) | Six-membered rings | ||
Compound | Q | θ | ϕ |
(I) | 0.607 (2) | 130.0 (2) | 164.7 (2) |
(II) | 0.616 (2) | 129.7 (2) | 166.3 (3) |
(III) | 0.617 (2) | 130.5 (2) | 162.3 (3) |
(IV) | 0.621 (2) | 128.2 (2) | 166.3 (3) |
(V) | 0.625 (2) | 127.0 (2) | 163.9 (2) |
(VI) | 0.609 (2) | 130.6 (2) | 165.0 (3) |
(VII) | 0.613 (2) | 129.6 (2) | 165.2 (3) |
(VIII) | 0.606 (2) | 128.8 (2) | 170.1 (3) |
(IX) | 0.627 (4) | 126.8 (4) | 162.5 (5) |
(c) | Seven-membered rings | ||
Compound | Q | ϕ2 | ϕ3 |
(I) | 1.126 (2) | 16.62 (11) | 300.6 (4) |
(II) | 1.123 (2) | 16.61 (12) | 297.8 (4) |
(III) | 1.143 (2) | 14.76 (12) | 297.8 (4) |
(IV) | 1.111 (2) | 16.39 (13) | 298.8 (4) |
(V) | 1.108 (2) | 14.36 (13) | 297.6 (4) |
(VI) | 1.132 (2) | 16.55 (12) | 298.8 (4) |
(VII) | 1.125 (2) | 16.77 (15) | 300.2 (5) |
(VIII) | 1.109 (2) | 21.02 (13) | 306.8 (4) |
(IX) | 1.117 (4) | 14.4 (2) | 299.0 (7) |
Ring-puckering angles in the five-membered rings refer to the atom sequence O14—N1—C2—C3—C4. Ring-puckering angles in the six-membered rings refer to the atom sequence O14—N1—C9a—C5a—C5—C4. Ring-puckering angles in the seven-membered rings refer to the atom sequence N1—C2—C3—C4—C5—C5a—C9a. |
D—H···A | D—H | H···A | D···A | D—H···A |
(I) | ||||
C24—H24···O51i | 0.95 | 2.45 | 3.359 (3) | 161 |
C5—H5B···Cg1a,ii | 0.99 | 2.66 | 3.458 (2) | 138 |
(II) | ||||
C5—H5A···O14iii | 0.99 | 2.58 | 3.530 (3) | 161 |
C25—H25···Cg1a,iv | 0.95 | 2.81 | 3.654 (2) | 149 |
(III) | ||||
C5—H5A···O14v | 0.99 | 2.55 | 3.527 (3) | 169 |
(IV) | ||||
C24—H24···Cg1a,vi | 0.95 | 2.56 | 3.443 (3) | 154 |
(VI) | ||||
C4—H4···O14vii | 1.00 | 2.49 | 3.312 (3) | 140 |
(VII) | ||||
C5—H5A···O14v | 0.99 | 2.58 | 3.545 (3) | 165 |
(VIII) | ||||
C5—H5A···O14viii | 0.99 | 2.41 | 3.383 (3) | 168 |
C3—H3A···Cg2b,viii | 0.99 | 2.70 | 3.533 (3) | 142 |
(IX) | ||||
C3—H3A···O51ix | 0.99 | 2.59 | 3.502 (5) | 153 |
C3—H3B···O14x | 0.99 | 2.50 | 3.475 (5) | 170 |
C8—H8···O14xi | 0.95 | 2.48 | 3.412 (6) | 165 |
C24—H24···O52ii | 0.95 | 2.42 | 3.340 (6) | 162 |
C4—H4···Cg1a,ii | 1.00 | 2.84 | 3.751 (5) | 152 |
Notes: (a) Cg1 represents the centroid of the C5a/C6–C9/C9a ring; (b) Cg2 represents the centroid of the S21/C22–C25 ring. Symmetry codes: (i) -x, -y + 1, -z; (ii) x, -y + 3/2, z - 1/2; (iii) x, y - 1, z; (iv) x, -y + 2, z - 1/2; (v) x + 1, y, z; (vi) x - 1/2, -y + 1/2, z + 1/2; (vii) -x + 1/2, y - 1/2, -z + 1/2; (viii) x, y + 1, z; (ix) -x + 1, -y + 2, -z + 1; (x) x, -y + 3/2, z + 1/2; (xi) x, -y + 1/2, z + 1/2. |
We report here the molecular and supramolecular structures of nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents, compounds (I)–(IX) (Fig. 1 and Scheme 1), and we compare these with some related compounds whose structures were reported recently, (X)–(XII) (Blanco et al., 2008) and (XIII)–(XV) (Blanco et al., 2009) (Scheme 2). The work reported here continues our structural study of this class of epoxybenzazepines (Acosta et al., 2008; Blanco et al., 2008, 2009; Gómez et al., 2008, 2009), which is itself associated with a synthetic programme to identify structurally novel antiparasitic agents having new modes of action against both Trypanosoma cruzi and Leishmania chagasi (Gómez et al., 2008; Yépez et al., 2006; Gómez-Ayala et al., 2010). Compounds (I)–(IX) were all prepared by appropriate modification of the procedure previously reported by Acosta et al. (2008).
The molecular constitutions of (I)–(XV) differ in just two respects: the identity of the simple substituent at position 7 (cf. Fig. 1) and the nature of the heterocyclic substituent at position 2. Of the compounds newly reported here, (II)–(V), along with the previously reported (X) and (XI) (Blanco et al., 2008), all carry a fluoro substituent at position 7, and (VI), along with (XIII) and (XV) (Blanco et al., 2009), has a chloro substituent at this position, while (VII)–(IX), and (XII) (Blanco et al., 2008) all have a trifluoromethoxy substituent at position 7. The substituents at position 2 comprise a variety of simply substituted furan units in (I), (III), (VI), (VII), (IX) and (X), or thienyl units, in (IV), (V), (VIII) and (XI)–(XV), with a substituted pyrrole unit in (II). Compounds (I)–(IX) all crystallize in centrosymmetric space groups, with Z' = 1. The molecules contain two stereogenic centres, at atoms C2 and C4, and the reference molecules in (I)–(IX) were all selected to have the R configuration at atom C2 and, on this basis, the configuration at atom C4 is always S in the reference molecules. The space groups for (I)–(IX) indicate that these compounds all crystallize as true racemates with configurations (2RS,4SR). By contrast, (X) crystallizes with Z' = 2 in the centrosymmetric space group P21/c, while (XII) crystallizes in the Sohnke space group P21 with Z' = 1 as a single enantiomorph, having configuration (2S,4R) in the crystal selected for data collection (Blanco et al., 2008).
The shapes of the heterobicyclic ring systems in (I)–(VIII) [(VII)?] and (IX) are all very similar, as indicated by the ring-puckering parameters (Cremer & Pople, 1975), although (VIII) differs somewhat (Table 1). In each of (I)–(VII) and (IX), the five-membered ring adopts a half-chair conformation, for which the idealized value of the puckering angle ϕ is (36k + 18)°, where k represents an integer. On the other hand, this ring in (VIII) adopts a conformation close to an envelope form, folded across the line N1···C4, where the ideal value of ϕ is (36k)°. The six-membered rings all adopt conformations intermediate between a half-chair form, where the idealized values of the puckering angles are θ = 129.2° and ϕ = (60k + 30)°, and an envelope form, where the idealized values are θ = 125.3° and ϕ = (60k)°, where k represents an integer in each case.
The supramolecular assembly in (I)–(IX) is dominated by C—H···O and C—H···π(arene) hydrogen bonds, although a C—H···π(thienyl) interaction is present in the structure of (VIII) (Table 2). The criteria for acceptance of such intermolecular interactions as structurally significant may be simply stated: (i) C—H···O contacts have been discounted if the C—H···O angle is significantly less than 140° (cf. Wood et al., 2009); (ii) C—H···π contacts have been discounted if the H···(ring centroid) distance exceeds 2.90 Å; (iii) all contacts involving methyl C—H bonds have been discounted; and (iv) C—H···F contacts have all been discounted (Howard et al., 1996; Brammer et al., 2001; Thallypally & Nangia, 2001). In addition, we may note here that none of the structures of (I)–(IX) exhibits any aromatic π–π stacking interactions.
Subject to the criteria enumerated above, it is then convenient to discuss the supramolecular assembly of (I)–(IX) in order of increasing complexity, and then briefly to compare these supramolecular structures with those of the related compounds, (X)–(XII) (Blanco et al., 2008).
There are no direction-specific intermolecular interactions of any kind in the structure of (IV), so that this structure may be regarded as zero-dimensional, built from essentially isolated molecules. In each of (III) and (VII), which carry the same heterocyclic substituent but different substituents at position 7 (see Scheme 1), a single rather long but almost linear C—H···O hydrogen bond links molecules related by translation into C(4) (Bernstein et al., 1995) chains running parallel to the [100] direction (Figs. 2 and 3). Two such chains, related to one another by inversion, pass through each unit cell in (VII), but there are four chains passing through each unit cell in (III) (Fig. 4).
In the structure of (VI), the molecules are again linked into a chain by a single C—H···O hydrogen bond (Table 2), but now the chain is of C(3) type running parallel to the [010] direction, and the component molecules are related by a 21 screw axis (Fig. 5). The chains in (IV) are built from a single C—H···π(arene) hydrogen bond linking molecules related by an n-glide plane, such that the chain is parallel to the [101] direction (Fig. 6). In the structure of (VIII), molecules related by translation along [010] are linked into C(4) chains by a C—H···O hydrogen bond (Fig. 7), exactly analogous to the chain formation in (III) and (VII). However, the action of the C—H···O hydrogen bond in (VIII) is modestly augmented by a C—H···π(thienyl) contact, so that the hydrogen-bonded assembly here should more properly be regarded as a chain of rings. Thus, for each of (III), (IV), (VI), (VII) and (VIII), the supramolecular assembly takes the form of a one-dimensional hydrogen-bonded structure, with simple chains in the first four of these compounds and a chain of rings in (VIII).
The hydrogen-bonded supramolecular assembly in each of (I) and (II) is two-dimensional and, in each case, the sheet structure is built from a combination of one C—H···O hydrogen bond and one C—H···.π(arene) hydrogen bond. However, except for the π(arene) acceptor, the donors and acceptors all differ (Table 2), so that the construction of the sheet is also different in the two compounds.
The formation of the sheet structure in (II) is readily analysed in terms of two one-dimensional substructures, each in the form of a simple chain involving just one type of hydrogen bond. Molecules of (II) related by translation are linked by a C—H···O hydrogen bond to form a C(4) chain running parallel to the [010] direction, analogous to the C(4) chains in (III) and (VII). In addition, molecules of (II) related by a c-glide plane are linked by a C—H···π(arene) hydrogen bond into a chain running parallel to the [001] direction. The combination of these two simple chain motifs generates a sheet lying parallel to (100) and containing just one type of ring (Fig. 8).
In the structure of (I), by contrast, a C—H···O hydrogen bond links pairs of molecules which are related by inversion to form a cyclic centrosymmetric dimeric unit characterized by an R22(10) motif. This dimeric unit is centred across (0, 1/2, 0) and it may conveniently be regarded as the basic building block in the formation of the sheet structure of (I). The dimer centred across (0, 1/2, 0) is directly linked by a C—H···π(arene) hydrogen bond to four further such dimers, centred respectively across (0, 0, 1/2), (0, 0, -1/2), (0, 1, 1/2) and (0, 1, -1/2), so forming a sheet lying parallel to (100) and containing two types of ring, both of them centrosymmetric (Fig. 9).
The sheet structure of (IX) is considerably more complex than those in (I) and (II) as five independent hydrogen bonds are involved, four of C—H···O type and one of C—H···π(arene) type (Table 2). However, the essential features of the sheet formation can be conveniently, although not uniquely, analysed in terms of just three of the C—H···O hydrogen bonds. Just as for (I), so too for (IX), a cyclic centrosymmetric dimer unit can be regarded as the basic building block for the sheet structure, but in the structure of (IX) the dimer motif is of R22(16) type (Fig. 10), as opposed to the R22(10) motif in (I). This reference dimer is centred across (1/2, 1, 1/2) and the C—H···O hydrogen bond which involves atom H3B (Table 2) links this dimer directly to the four similar dimer units centred across (1/2, 1/2, 1), (1/2, 1/2, 0), (1/2, 3/2, 1) and (1/2, 3/2, 0) (Fig. 11). In addition, the same reference dimer across (1/2, 1, 1/2) is linked by the C—H···O hydrogen bond involving atom H8 to four further dimeric units, centred across (1/2, -1/2, 1), (1/2, -1/2, 0), (1/2, 5/2, 1) and (1/2, 5/2, 0) (Fig. 12). These interactions in combination give rise to a complex sheet lying parallel to (100). The remaining two hydrogen bonds both lie within the sheet, so that they serve to augment its strength and increase its complexity, but they do not influence the overall dimensionality of the hydrogen-bonded assembly.
We briefly compare here the structures of (X)–(XV) (Blanco et al., 2008, 2009) with those of (I)–(IX). In the structure of (X), which crystallizes with Z' = 2, a combination of one C—H···N hydrogen bond and three C—H···O hydrogen bonds links the molecules into a chain of edge-fused R43(20) rings, anti-parallel pairs of which are weakly linked by two rather long C—H···π(arene) hydrogen bonds. It is noteworthy that (X) is the only example amongst (I)–(XII) where the Z' value is other than 1 and the only example where the structure contains a C—H···N hydrogen bond.
As with the closely related (V), there are no hydrogen bonds of any kind in the structure of (XI), although the molecules of (XI) are weakly linked into centrosymmetric dimers by a single aromatic π–π stacking interaction involving the fluoro-substituted ring. Compounds (V) and (XI) both crystallize in space group P21/c with Z' = 1, and with somewhat similar unit-cell dimensions. Comparison of the two sets of atomic coordinates shows that these also are somewhat similar, but with sufficient differences in detail that (V) and (XI) could, at best, be described as only approximately isostructural. In particular, the π–π stacking interaction present in the structure of (XI) is absent from the structure of (V).
Compound (XII) is the only example in the series (I)–(XV) which crystallizes as a single enantiomorph. The molecules of (XII) are linked by two C—H···O hydrogen bonds, both having the fused-ring O atom as the acceptor, to form a sheet containing a single type of R43(20) ring.
Although (XIII) and (XIV) both crystallize with Z' = 1 in space group Pbca, the unit-cell dimensions for these two compounds are very different, as are their modes of supramolecular assembly. Paired C—H···π(thienyl) hydrogen bonds link molecules of (XIII) into centrosymmetric dimers, while a combination of C—H···O and C—H···π(thienyl) hydrogen bonds links the molecules of (XIV) into a chain of rings. A more complex chain of rings is formed in (XV) built from four independent hydrogen bonds, two of C—H···O type and one each of C—H···π(thienyl) and C—H···π(arene) types.
Accordingly, despite the rather small differences in molecular composition and molecular constitution amongst the members of the series (I)–(XV), no two of the compounds display the same pattern of supramolecular assembly.