Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109030339/fa3200sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030339/fa3200Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030339/fa3200IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030339/fa3200IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030339/fa3200IVsup5.hkl |
CCDC references: 749722; 749723; 749724; 749725; 749726
For the preparation of compounds (I)–(IV), sodium tungstate dihydrate, Na2WO4.2H2O (10 mol %), followed by 30% aqueous hydrogen peroxide solution (added dropwise, 0.30 mol) were added to a stirred solution of the appropriately substituted 2-allyl-N-benzylaniline (0.10 mol) in methanol (34 ml), for (I), (III) and (IV), or in a mixture of methanol (34 ml) and nitromethane (3.4 ml) for (II). The resulting mixtures were then stirred at ambient temperature for periods ranging from 30 to 100 h. Each mixture was filtered and the solvent removed under reduced pressure. Toluene (40 ml) for compounds (I), (III) and (IV), or ethyl acetate (40 ml) for (II), was added to the solid residue and the resulting solution was heated to ca 353 K for periods ranging from 6 to 8 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude products were purified by chromatography on silica gel using heptane–ethyl acetate (compositions ranged from 90:1 to 60:1 v/v) as eluant. Crystallization from heptane gave colourless crystals suitable for single-crystal X-ray diffraction. For (I) (m.p. 429–430 K, yield 50%): MS (70 eV) m/z (%) 323 (M+, 35Cl, 17), 306 (3), 294 (1), 280 (1), 164 (3), 138 (100), 125 (6), 111 (4). For (II) (m.p. 433–434 K, yield 65%): MS (70 eV) m/z (%) 289 (M+, 35Cl, 32), 272 (7), 260 (1), 246 (3), 130 (4), 104 (100), 91 (10), 77 (10). For (III) (m.p. 374–376 K, yield 45%): MS (70 eV) m/z (%) 265 (M+, 35), 248 (18), 222 (10), 207 (5), 146 (7), 132 (23), 118 (100), 103 (12), 91 (30), 77 (18), 65 (9), 51 (5). For (IV) (m.p. 385–387 K, yield 63%): MS (70 eV) m/z (%) 271 (M+, 35Cl, 50), 254 (19), 242 (2), 228 (2), 130 (4), 104 (100), 91 (25), 77 (26).
All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H distances of 0.95 Å (aromatic), 0.98 Å (CH3), 0.99 Å (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 k = 1.2 for all other H atoms. For (IV), the absolute configuration of the molecules in the crystal selected for data collection was established as (2S,4R) by means of the Flack (1983) x parameter of 0.07 (6) and the Hooft y parameter (Hooft et al., 2008) of 0.03 (4). Accordingly, the configuration of the reference molecules in the racemic compounds (I)–(III) was set to be S at C2, and on this basis all three compounds have configuration R at C4 for the reference molecules, so that the overall configuration for each of (I)-(III) is (2SR,4RS).
For all compounds, data collection: COLLECT (Hooft, 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) for (I), (II), (III), (IV); SHELXL97 and PLATON for (VII).
C16H12Cl2FNO | F(000) = 664 |
Mr = 324.17 | Dx = 1.593 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3105 reflections |
a = 9.2907 (11) Å | θ = 2.8–27.5° |
b = 10.8720 (9) Å | µ = 0.49 mm−1 |
c = 13.4523 (13) Å | T = 120 K |
β = 95.964 (8)° | Needle, colourless |
V = 1351.4 (2) Å3 | 0.35 × 0.06 × 0.06 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 3105 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1774 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→14 |
Tmin = 0.868, Tmax = 0.971 | l = −17→17 |
19650 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.043P)2 + 1.1028P] where P = (Fo2 + 2Fc2)/3 |
3105 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C16H12Cl2FNO | V = 1351.4 (2) Å3 |
Mr = 324.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2907 (11) Å | µ = 0.49 mm−1 |
b = 10.8720 (9) Å | T = 120 K |
c = 13.4523 (13) Å | 0.35 × 0.06 × 0.06 mm |
β = 95.964 (8)° |
Bruker–Nonius KappaCCD diffractometer | 3105 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1774 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.971 | Rint = 0.103 |
19650 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.38 e Å−3 |
3105 reflections | Δρmin = −0.44 e Å−3 |
190 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.7321 (2) | 0.6590 (2) | 0.26957 (17) | 0.0181 (6) | |
C2 | 0.6684 (3) | 0.5681 (3) | 0.3346 (2) | 0.0184 (7) | |
H2 | 0.5749 | 0.5380 | 0.2994 | 0.022* | |
C3 | 0.7766 (3) | 0.4615 (3) | 0.3429 (2) | 0.0231 (7) | |
H3A | 0.7979 | 0.4343 | 0.4131 | 0.028* | |
H3B | 0.7397 | 0.3907 | 0.3015 | 0.028* | |
C4 | 0.9103 (3) | 0.5176 (3) | 0.3034 (2) | 0.0216 (7) | |
H4 | 0.9995 | 0.4974 | 0.3486 | 0.026* | |
C5 | 0.9267 (3) | 0.4785 (3) | 0.1977 (2) | 0.0249 (7) | |
H5A | 1.0213 | 0.5066 | 0.1783 | 0.030* | |
H5B | 0.9231 | 0.3877 | 0.1927 | 0.030* | |
C5a | 0.8062 (3) | 0.5339 (3) | 0.1294 (2) | 0.0198 (7) | |
C6 | 0.7885 (3) | 0.5070 (3) | 0.0282 (2) | 0.0213 (7) | |
H6 | 0.8512 | 0.4498 | 0.0012 | 0.026* | |
C7 | 0.6809 (3) | 0.5626 (3) | −0.0327 (2) | 0.0229 (7) | |
C8 | 0.5863 (3) | 0.6453 (3) | 0.0032 (2) | 0.0221 (7) | |
H8 | 0.5114 | 0.6823 | −0.0401 | 0.027* | |
C9 | 0.6036 (3) | 0.6724 (3) | 0.1036 (2) | 0.0200 (7) | |
H9 | 0.5396 | 0.7288 | 0.1302 | 0.024* | |
C9a | 0.7130 (3) | 0.6188 (3) | 0.1660 (2) | 0.0188 (7) | |
O14 | 0.8837 (2) | 0.64879 (19) | 0.30251 (14) | 0.0213 (5) | |
C21 | 0.6381 (3) | 0.6264 (3) | 0.4327 (2) | 0.0186 (7) | |
C22 | 0.5012 (3) | 0.6676 (3) | 0.4488 (2) | 0.0186 (7) | |
Cl22 | 0.36167 (8) | 0.66256 (8) | 0.35286 (6) | 0.0282 (2) | |
C23 | 0.4675 (3) | 0.7123 (3) | 0.5395 (2) | 0.0220 (7) | |
H23 | 0.3717 | 0.7384 | 0.5471 | 0.026* | |
C24 | 0.5727 (4) | 0.7190 (3) | 0.6183 (2) | 0.0259 (8) | |
H24 | 0.5502 | 0.7490 | 0.6812 | 0.031* | |
C25 | 0.7115 (3) | 0.6819 (3) | 0.6060 (2) | 0.0227 (7) | |
H25 | 0.7860 | 0.6863 | 0.6598 | 0.027* | |
C26 | 0.7396 (3) | 0.6387 (3) | 0.5146 (2) | 0.0210 (7) | |
F26 | 0.87818 (18) | 0.60327 (18) | 0.50698 (12) | 0.0278 (5) | |
Cl7 | 0.66528 (9) | 0.53017 (8) | −0.15967 (6) | 0.0298 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0158 (13) | 0.0207 (15) | 0.0176 (13) | −0.0005 (11) | 0.0010 (10) | 0.0002 (11) |
C2 | 0.0227 (17) | 0.0174 (17) | 0.0157 (14) | −0.0031 (13) | 0.0044 (12) | −0.0001 (13) |
C3 | 0.0283 (18) | 0.0172 (18) | 0.0246 (17) | 0.0017 (14) | 0.0059 (13) | 0.0018 (14) |
C4 | 0.0208 (17) | 0.0232 (19) | 0.0212 (16) | 0.0045 (14) | 0.0040 (13) | 0.0015 (14) |
C5 | 0.0249 (18) | 0.0252 (19) | 0.0254 (17) | 0.0047 (15) | 0.0069 (14) | 0.0018 (15) |
C5a | 0.0207 (17) | 0.0166 (17) | 0.0226 (16) | −0.0029 (14) | 0.0051 (13) | 0.0040 (13) |
C6 | 0.0227 (17) | 0.0222 (19) | 0.0206 (16) | −0.0041 (14) | 0.0093 (13) | −0.0043 (13) |
C7 | 0.0277 (18) | 0.026 (2) | 0.0157 (15) | −0.0102 (15) | 0.0047 (13) | −0.0032 (13) |
C8 | 0.0197 (16) | 0.0232 (19) | 0.0229 (16) | −0.0027 (14) | 0.0000 (13) | 0.0038 (14) |
C9 | 0.0169 (16) | 0.0200 (18) | 0.0234 (16) | −0.0034 (13) | 0.0040 (13) | 0.0012 (13) |
C9a | 0.0219 (17) | 0.0171 (17) | 0.0184 (15) | −0.0040 (13) | 0.0063 (12) | 0.0006 (13) |
O14 | 0.0200 (11) | 0.0226 (13) | 0.0210 (11) | −0.0009 (10) | 0.0003 (9) | 0.0010 (9) |
C21 | 0.0242 (17) | 0.0150 (17) | 0.0179 (15) | −0.0032 (13) | 0.0079 (12) | 0.0010 (13) |
C22 | 0.0209 (16) | 0.0155 (17) | 0.0192 (15) | −0.0018 (13) | 0.0015 (12) | 0.0006 (13) |
Cl22 | 0.0229 (4) | 0.0350 (5) | 0.0261 (4) | 0.0040 (4) | −0.0002 (3) | −0.0047 (4) |
C23 | 0.0222 (17) | 0.0202 (18) | 0.0243 (17) | 0.0012 (14) | 0.0066 (13) | 0.0035 (14) |
C24 | 0.037 (2) | 0.0221 (19) | 0.0206 (16) | 0.0008 (15) | 0.0103 (15) | −0.0014 (14) |
C25 | 0.0282 (18) | 0.0222 (19) | 0.0173 (16) | −0.0019 (14) | 0.0004 (13) | 0.0013 (13) |
C26 | 0.0183 (17) | 0.0249 (19) | 0.0208 (16) | 0.0023 (14) | 0.0062 (12) | 0.0024 (14) |
F26 | 0.0211 (10) | 0.0411 (12) | 0.0212 (9) | 0.0051 (9) | 0.0018 (7) | −0.0023 (8) |
Cl7 | 0.0313 (5) | 0.0400 (5) | 0.0183 (4) | −0.0078 (4) | 0.0034 (3) | −0.0057 (4) |
N1—O14 | 1.437 (3) | C6—H6 | 0.9500 |
N1—C9a | 1.453 (4) | C7—C8 | 1.379 (4) |
N1—C2 | 1.483 (4) | C7—Cl7 | 1.735 (3) |
C2—C21 | 1.517 (4) | C8—C9 | 1.375 (4) |
C2—C3 | 1.530 (4) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.379 (4) |
C3—C4 | 1.528 (4) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | C21—C26 | 1.380 (4) |
C3—H3B | 0.9900 | C21—C22 | 1.387 (4) |
C4—O14 | 1.447 (4) | C22—C23 | 1.379 (4) |
C4—C5 | 1.507 (4) | C22—Cl22 | 1.733 (3) |
C4—H4 | 1.0000 | C23—C24 | 1.367 (4) |
C5—C5a | 1.499 (4) | C23—H23 | 0.9500 |
C5—H5A | 0.9900 | C24—C25 | 1.377 (4) |
C5—H5B | 0.9900 | C24—H24 | 0.9500 |
C5a—C6 | 1.386 (4) | C25—C26 | 1.367 (4) |
C5a—C9a | 1.390 (4) | C25—H25 | 0.9500 |
C6—C7 | 1.366 (4) | C26—F26 | 1.358 (3) |
O14—N1—C9a | 106.9 (2) | C5a—C6—H6 | 120.0 |
O14—N1—C2 | 101.8 (2) | C6—C7—C8 | 122.1 (3) |
C9a—N1—C2 | 110.4 (2) | C6—C7—Cl7 | 118.8 (2) |
N1—C2—C21 | 110.8 (2) | C8—C7—Cl7 | 119.1 (2) |
N1—C2—C3 | 104.4 (2) | C9—C8—C7 | 118.1 (3) |
C21—C2—C3 | 115.6 (2) | C9—C8—H8 | 121.0 |
N1—C2—H2 | 108.6 | C7—C8—H8 | 121.0 |
C21—C2—H2 | 108.6 | C8—C9—C9a | 120.7 (3) |
C3—C2—H2 | 108.6 | C8—C9—H9 | 119.6 |
C4—C3—C2 | 102.9 (3) | C9a—C9—H9 | 119.6 |
C4—C3—H3A | 111.2 | C9—C9a—C5a | 120.8 (3) |
C2—C3—H3A | 111.2 | C9—C9a—N1 | 117.7 (3) |
C4—C3—H3B | 111.2 | C5a—C9a—N1 | 121.4 (3) |
C2—C3—H3B | 111.2 | N1—O14—C4 | 103.9 (2) |
H3A—C3—H3B | 109.1 | C26—C21—C22 | 113.9 (3) |
O14—C4—C5 | 107.7 (2) | C26—C21—C2 | 124.2 (3) |
O14—C4—C3 | 104.6 (2) | C22—C21—C2 | 121.8 (3) |
C5—C4—C3 | 112.4 (3) | C23—C22—C21 | 123.3 (3) |
O14—C4—H4 | 110.6 | C23—C22—Cl22 | 116.7 (2) |
C5—C4—H4 | 110.6 | C21—C22—Cl22 | 120.1 (2) |
C3—C4—H4 | 110.6 | C24—C23—C22 | 119.7 (3) |
C5a—C5—C4 | 108.8 (3) | C24—C23—H23 | 120.2 |
C5a—C5—H5A | 109.9 | C22—C23—H23 | 120.2 |
C4—C5—H5A | 109.9 | C23—C24—C25 | 119.6 (3) |
C5a—C5—H5B | 109.9 | C23—C24—H24 | 120.2 |
C4—C5—H5B | 109.9 | C25—C24—H24 | 120.2 |
H5A—C5—H5B | 108.3 | C26—C25—C24 | 118.5 (3) |
C6—C5a—C9a | 118.3 (3) | C26—C25—H25 | 120.7 |
C6—C5a—C5 | 121.5 (3) | C24—C25—H25 | 120.7 |
C9a—C5a—C5 | 120.2 (3) | F26—C26—C25 | 115.9 (3) |
C7—C6—C5a | 120.1 (3) | F26—C26—C21 | 119.1 (3) |
C7—C6—H6 | 120.0 | C25—C26—C21 | 124.9 (3) |
O14—N1—C2—C21 | 87.2 (3) | C2—N1—C9a—C9 | 101.5 (3) |
C9a—N1—C2—C21 | −159.6 (2) | O14—N1—C9a—C5a | 28.1 (4) |
O14—N1—C2—C3 | −37.9 (3) | C2—N1—C9a—C5a | −81.8 (3) |
C9a—N1—C2—C3 | 75.3 (3) | C9a—N1—O14—C4 | −67.6 (3) |
N1—C2—C3—C4 | 14.2 (3) | C2—N1—O14—C4 | 48.3 (2) |
C21—C2—C3—C4 | −107.9 (3) | C5—C4—O14—N1 | 80.7 (3) |
C2—C3—C4—O14 | 14.4 (3) | C3—C4—O14—N1 | −39.1 (3) |
C2—C3—C4—C5 | −102.2 (3) | N1—C2—C21—C26 | −84.4 (4) |
O14—C4—C5—C5a | −47.0 (3) | C3—C2—C21—C26 | 34.1 (4) |
C3—C4—C5—C5a | 67.7 (3) | N1—C2—C21—C22 | 98.6 (3) |
C4—C5—C5a—C6 | −175.8 (3) | C3—C2—C21—C22 | −142.9 (3) |
C4—C5—C5a—C9a | 7.3 (4) | C26—C21—C22—C23 | −2.4 (5) |
C9a—C5a—C6—C7 | −0.5 (5) | C2—C21—C22—C23 | 174.9 (3) |
C5—C5a—C6—C7 | −177.5 (3) | C26—C21—C22—Cl22 | 178.4 (2) |
C5a—C6—C7—C8 | −0.6 (5) | C2—C21—C22—Cl22 | −4.3 (4) |
C5a—C6—C7—Cl7 | 178.1 (2) | C21—C22—C23—C24 | 0.9 (5) |
C6—C7—C8—C9 | 0.7 (5) | Cl22—C22—C23—C24 | −179.9 (3) |
Cl7—C7—C8—C9 | −178.0 (2) | C22—C23—C24—C25 | 0.6 (5) |
C7—C8—C9—C9a | 0.3 (5) | C23—C24—C25—C26 | −0.3 (5) |
C8—C9—C9a—C5a | −1.5 (5) | C24—C25—C26—F26 | −179.8 (3) |
C8—C9—C9a—N1 | 175.2 (3) | C24—C25—C26—C21 | −1.5 (5) |
C6—C5a—C9a—C9 | 1.6 (4) | C22—C21—C26—F26 | −178.9 (3) |
C5—C5a—C9a—C9 | 178.6 (3) | C2—C21—C26—F26 | 3.9 (5) |
C6—C5a—C9a—N1 | −175.0 (3) | C22—C21—C26—C25 | 2.7 (5) |
C5—C5a—C9a—N1 | 2.0 (4) | C2—C21—C26—C25 | −174.5 (3) |
O14—N1—C9a—C9 | −148.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···N1i | 0.99 | 2.72 | 3.617 (3) | 151 |
C4—H4···F26ii | 1.00 | 2.41 | 3.325 (3) | 152 |
C23—H23···Cg1iii | 0.95 | 2.51 | 3.359 (3) | 149 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) x−1/2, −y+3/2, z+1/2. |
C16H13ClFNO | F(000) = 600 |
Mr = 289.72 | Dx = 1.512 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2918 reflections |
a = 9.0768 (13) Å | θ = 2.9–27.5° |
b = 10.9461 (9) Å | µ = 0.31 mm−1 |
c = 12.9971 (18) Å | T = 120 K |
β = 99.768 (9)° | Block, colourless |
V = 1272.6 (3) Å3 | 0.32 × 0.27 × 0.22 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 2918 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2085 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.894, Tmax = 0.936 | l = −16→16 |
18555 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0685P)2 + 1.0363P] where P = (Fo2 + 2Fc2)/3 |
2918 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C16H13ClFNO | V = 1272.6 (3) Å3 |
Mr = 289.72 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0768 (13) Å | µ = 0.31 mm−1 |
b = 10.9461 (9) Å | T = 120 K |
c = 12.9971 (18) Å | 0.32 × 0.27 × 0.22 mm |
β = 99.768 (9)° |
Bruker–Nonius KappaCCD diffractometer | 2918 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2085 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 0.936 | Rint = 0.055 |
18555 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2918 reflections | Δρmin = −0.37 e Å−3 |
181 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.7145 (2) | 0.65076 (17) | 0.24705 (14) | 0.0199 (4) | |
C2 | 0.6488 (3) | 0.5567 (2) | 0.30773 (17) | 0.0204 (5) | |
H2 | 0.5530 | 0.5275 | 0.2653 | 0.024* | |
C3 | 0.7627 (3) | 0.4517 (2) | 0.31834 (19) | 0.0264 (5) | |
H3A | 0.7834 | 0.4204 | 0.3908 | 0.032* | |
H3B | 0.7265 | 0.3836 | 0.2705 | 0.032* | |
C4 | 0.9008 (3) | 0.5109 (2) | 0.28836 (19) | 0.0268 (5) | |
H4 | 0.9925 | 0.4894 | 0.3394 | 0.032* | |
C5 | 0.9196 (3) | 0.4789 (2) | 0.17850 (19) | 0.0298 (6) | |
H5A | 1.0169 | 0.5098 | 0.1648 | 0.036* | |
H5B | 0.9180 | 0.3891 | 0.1696 | 0.036* | |
C5a | 0.7949 (3) | 0.5354 (2) | 0.10301 (18) | 0.0239 (5) | |
C6 | 0.7746 (3) | 0.5114 (2) | −0.00327 (19) | 0.0302 (6) | |
H6 | 0.8391 | 0.4551 | −0.0293 | 0.036* | |
C7 | 0.6625 (3) | 0.5677 (2) | −0.07180 (19) | 0.0325 (6) | |
H7 | 0.6518 | 0.5512 | −0.1445 | 0.039* | |
C8 | 0.5663 (3) | 0.6474 (2) | −0.03567 (18) | 0.0286 (5) | |
H8 | 0.4885 | 0.6855 | −0.0829 | 0.034* | |
C9 | 0.5837 (3) | 0.6719 (2) | 0.07019 (18) | 0.0246 (5) | |
H9 | 0.5171 | 0.7264 | 0.0960 | 0.030* | |
C9a | 0.6982 (3) | 0.6171 (2) | 0.13842 (17) | 0.0206 (5) | |
O14 | 0.87073 (17) | 0.64086 (15) | 0.28991 (12) | 0.0240 (4) | |
C21 | 0.6157 (2) | 0.6097 (2) | 0.40802 (17) | 0.0205 (5) | |
C22 | 0.4739 (3) | 0.6527 (2) | 0.41653 (17) | 0.0212 (5) | |
Cl22 | 0.33178 (7) | 0.64951 (6) | 0.30903 (4) | 0.02951 (19) | |
C23 | 0.4377 (3) | 0.6999 (2) | 0.50739 (18) | 0.0243 (5) | |
H23 | 0.3395 | 0.7289 | 0.5090 | 0.029* | |
C24 | 0.5458 (3) | 0.7046 (2) | 0.59600 (18) | 0.0268 (5) | |
H24 | 0.5221 | 0.7362 | 0.6593 | 0.032* | |
C25 | 0.6876 (3) | 0.6635 (2) | 0.59201 (18) | 0.0271 (5) | |
H25 | 0.7628 | 0.6654 | 0.6525 | 0.033* | |
C26 | 0.7186 (3) | 0.6197 (2) | 0.49940 (18) | 0.0247 (5) | |
F26 | 0.86059 (15) | 0.58170 (14) | 0.49996 (11) | 0.0321 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0203 (10) | 0.0217 (10) | 0.0177 (9) | 0.0003 (7) | 0.0031 (7) | 0.0005 (7) |
C2 | 0.0250 (11) | 0.0183 (11) | 0.0190 (11) | −0.0004 (9) | 0.0068 (9) | 0.0001 (8) |
C3 | 0.0334 (13) | 0.0228 (12) | 0.0253 (12) | 0.0066 (10) | 0.0120 (10) | 0.0030 (9) |
C4 | 0.0276 (12) | 0.0271 (13) | 0.0267 (12) | 0.0075 (10) | 0.0072 (10) | 0.0062 (10) |
C5 | 0.0336 (13) | 0.0289 (13) | 0.0302 (13) | 0.0071 (11) | 0.0151 (11) | 0.0049 (10) |
C5a | 0.0283 (12) | 0.0220 (12) | 0.0234 (12) | −0.0027 (9) | 0.0100 (10) | 0.0014 (9) |
C6 | 0.0402 (14) | 0.0273 (13) | 0.0261 (13) | −0.0066 (11) | 0.0143 (11) | −0.0053 (10) |
C7 | 0.0420 (15) | 0.0350 (14) | 0.0215 (12) | −0.0192 (12) | 0.0087 (10) | −0.0073 (10) |
C8 | 0.0283 (13) | 0.0344 (14) | 0.0219 (12) | −0.0097 (10) | 0.0009 (9) | 0.0052 (10) |
C9 | 0.0229 (12) | 0.0257 (12) | 0.0258 (12) | −0.0052 (9) | 0.0053 (9) | 0.0001 (10) |
C9a | 0.0234 (11) | 0.0200 (11) | 0.0196 (11) | −0.0047 (9) | 0.0070 (9) | −0.0010 (9) |
O14 | 0.0208 (8) | 0.0256 (9) | 0.0246 (8) | −0.0007 (6) | 0.0014 (6) | 0.0016 (7) |
C21 | 0.0258 (12) | 0.0160 (10) | 0.0207 (11) | 0.0000 (9) | 0.0064 (9) | 0.0021 (8) |
C22 | 0.0254 (11) | 0.0178 (11) | 0.0210 (11) | −0.0008 (9) | 0.0056 (9) | 0.0031 (9) |
Cl22 | 0.0262 (3) | 0.0368 (4) | 0.0246 (3) | 0.0054 (2) | 0.0017 (2) | 0.0012 (2) |
C23 | 0.0287 (12) | 0.0191 (11) | 0.0278 (12) | 0.0005 (9) | 0.0124 (10) | 0.0025 (9) |
C24 | 0.0385 (14) | 0.0227 (12) | 0.0212 (12) | −0.0022 (10) | 0.0104 (10) | −0.0025 (9) |
C25 | 0.0352 (14) | 0.0247 (12) | 0.0209 (11) | −0.0024 (10) | 0.0036 (10) | −0.0011 (9) |
C26 | 0.0257 (12) | 0.0244 (12) | 0.0245 (12) | −0.0004 (9) | 0.0058 (9) | 0.0013 (9) |
F26 | 0.0243 (7) | 0.0454 (9) | 0.0263 (7) | 0.0068 (6) | 0.0034 (6) | −0.0019 (6) |
N1—O14 | 1.437 (2) | C6—H6 | 0.9500 |
N1—C9a | 1.442 (3) | C7—C8 | 1.373 (4) |
N1—C2 | 1.482 (3) | C7—H7 | 0.9500 |
C2—C21 | 1.503 (3) | C8—C9 | 1.384 (3) |
C2—C3 | 1.537 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.384 (3) |
C3—C4 | 1.520 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | C21—C26 | 1.385 (3) |
C3—H3B | 0.9900 | C21—C22 | 1.392 (3) |
C4—O14 | 1.450 (3) | C22—C23 | 1.379 (3) |
C4—C5 | 1.507 (3) | C22—Cl22 | 1.734 (2) |
C4—H4 | 1.0000 | C23—C24 | 1.381 (3) |
C5—C5a | 1.500 (3) | C23—H23 | 0.9500 |
C5—H5A | 0.9900 | C24—C25 | 1.373 (4) |
C5—H5B | 0.9900 | C24—H24 | 0.9500 |
C5a—C9a | 1.385 (3) | C25—C26 | 1.369 (3) |
C5a—C6 | 1.388 (3) | C25—H25 | 0.9500 |
C6—C7 | 1.379 (4) | C26—F26 | 1.353 (3) |
O14—N1—C9a | 106.94 (16) | C5a—C6—H6 | 119.4 |
O14—N1—C2 | 101.60 (15) | C8—C7—C6 | 120.4 (2) |
C9a—N1—C2 | 111.05 (17) | C8—C7—H7 | 119.8 |
N1—C2—C21 | 110.57 (17) | C6—C7—H7 | 119.8 |
N1—C2—C3 | 104.00 (18) | C7—C8—C9 | 119.4 (2) |
C21—C2—C3 | 116.19 (19) | C7—C8—H8 | 120.3 |
N1—C2—H2 | 108.6 | C9—C8—H8 | 120.3 |
C21—C2—H2 | 108.6 | C9a—C9—C8 | 120.0 (2) |
C3—C2—H2 | 108.6 | C9a—C9—H9 | 120.0 |
C4—C3—C2 | 103.28 (18) | C8—C9—H9 | 120.0 |
C4—C3—H3A | 111.1 | C9—C9a—C5a | 121.1 (2) |
C2—C3—H3A | 111.1 | C9—C9a—N1 | 117.2 (2) |
C4—C3—H3B | 111.1 | C5a—C9a—N1 | 121.6 (2) |
C2—C3—H3B | 111.1 | N1—O14—C4 | 104.16 (16) |
H3A—C3—H3B | 109.1 | C26—C21—C22 | 113.8 (2) |
O14—C4—C5 | 107.01 (19) | C26—C21—C2 | 124.7 (2) |
O14—C4—C3 | 104.43 (18) | C22—C21—C2 | 121.5 (2) |
C5—C4—C3 | 112.0 (2) | C23—C22—C21 | 123.5 (2) |
O14—C4—H4 | 111.0 | C23—C22—Cl22 | 116.41 (18) |
C5—C4—H4 | 111.0 | C21—C22—Cl22 | 120.05 (17) |
C3—C4—H4 | 111.0 | C22—C23—C24 | 119.3 (2) |
C5a—C5—C4 | 109.3 (2) | C22—C23—H23 | 120.3 |
C5a—C5—H5A | 109.8 | C24—C23—H23 | 120.3 |
C4—C5—H5A | 109.8 | C25—C24—C23 | 119.6 (2) |
C5a—C5—H5B | 109.8 | C25—C24—H24 | 120.2 |
C4—C5—H5B | 109.8 | C23—C24—H24 | 120.2 |
H5A—C5—H5B | 108.3 | C26—C25—C24 | 118.8 (2) |
C9a—C5a—C6 | 118.0 (2) | C26—C25—H25 | 120.6 |
C9a—C5a—C5 | 120.0 (2) | C24—C25—H25 | 120.6 |
C6—C5a—C5 | 122.1 (2) | F26—C26—C25 | 116.2 (2) |
C7—C6—C5a | 121.1 (2) | F26—C26—C21 | 118.9 (2) |
C7—C6—H6 | 119.4 | C25—C26—C21 | 124.9 (2) |
O14—N1—C2—C21 | 87.0 (2) | O14—N1—C9a—C5a | 29.0 (3) |
C9a—N1—C2—C21 | −159.60 (18) | C2—N1—C9a—C5a | −81.0 (3) |
O14—N1—C2—C3 | −38.4 (2) | C9a—N1—O14—C4 | −67.99 (19) |
C9a—N1—C2—C3 | 75.0 (2) | C2—N1—O14—C4 | 48.49 (19) |
N1—C2—C3—C4 | 15.0 (2) | C5—C4—O14—N1 | 80.1 (2) |
C21—C2—C3—C4 | −106.7 (2) | C3—C4—O14—N1 | −38.8 (2) |
C2—C3—C4—O14 | 13.6 (2) | N1—C2—C21—C26 | −84.6 (3) |
C2—C3—C4—C5 | −101.8 (2) | C3—C2—C21—C26 | 33.6 (3) |
O14—C4—C5—C5a | −47.0 (3) | N1—C2—C21—C22 | 96.1 (2) |
C3—C4—C5—C5a | 66.9 (3) | C3—C2—C21—C22 | −145.7 (2) |
C4—C5—C5a—C9a | 8.5 (3) | C26—C21—C22—C23 | −0.6 (3) |
C4—C5—C5a—C6 | −173.4 (2) | C2—C21—C22—C23 | 178.8 (2) |
C9a—C5a—C6—C7 | 0.6 (4) | C26—C21—C22—Cl22 | 178.94 (17) |
C5—C5a—C6—C7 | −177.6 (2) | C2—C21—C22—Cl22 | −1.7 (3) |
C5a—C6—C7—C8 | −1.3 (4) | C21—C22—C23—C24 | −0.6 (3) |
C6—C7—C8—C9 | 0.7 (4) | Cl22—C22—C23—C24 | 179.78 (18) |
C7—C8—C9—C9a | 0.6 (3) | C22—C23—C24—C25 | 0.6 (3) |
C8—C9—C9a—C5a | −1.3 (3) | C23—C24—C25—C26 | 0.6 (4) |
C8—C9—C9a—N1 | 177.2 (2) | C24—C25—C26—F26 | 179.3 (2) |
C6—C5a—C9a—C9 | 0.7 (3) | C24—C25—C26—C21 | −2.1 (4) |
C5—C5a—C9a—C9 | 179.0 (2) | C22—C21—C26—F26 | −179.4 (2) |
C6—C5a—C9a—N1 | −177.7 (2) | C2—C21—C26—F26 | 1.2 (3) |
C5—C5a—C9a—N1 | 0.6 (3) | C22—C21—C26—C25 | 2.0 (3) |
O14—N1—C9a—C9 | −149.42 (19) | C2—C21—C26—C25 | −177.3 (2) |
C2—N1—C9a—C9 | 100.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···N1i | 0.99 | 2.62 | 3.417 (3) | 137 |
C4—H4···F26ii | 1.00 | 2.41 | 3.356 (3) | 158 |
C23—H23···Cg1iii | 0.95 | 2.49 | 3.324 (3) | 147 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) x−1/2, −y+3/2, z+1/2. |
C18H19NO | F(000) = 568 |
Mr = 265.34 | Dx = 1.295 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3133 reflections |
a = 9.7687 (9) Å | θ = 3.0–27.5° |
b = 10.3022 (17) Å | µ = 0.08 mm−1 |
c = 14.239 (2) Å | T = 120 K |
β = 108.222 (10)° | Block, colourless |
V = 1361.1 (3) Å3 | 0.33 × 0.27 × 0.12 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 3133 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.096 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ & ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.962, Tmax = 0.991 | l = −18→18 |
20555 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0346P)2 + 1.1025P] where P = (Fo2 + 2Fc2)/3 |
3133 reflections | (Δ/σ)max = 0.001 |
183 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C18H19NO | V = 1361.1 (3) Å3 |
Mr = 265.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7687 (9) Å | µ = 0.08 mm−1 |
b = 10.3022 (17) Å | T = 120 K |
c = 14.239 (2) Å | 0.33 × 0.27 × 0.12 mm |
β = 108.222 (10)° |
Bruker–Nonius KappaCCD diffractometer | 3133 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1788 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.991 | Rint = 0.096 |
20555 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.27 e Å−3 |
3133 reflections | Δρmin = −0.26 e Å−3 |
183 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5776 (2) | 0.74452 (19) | 0.11344 (14) | 0.0240 (5) | |
C2 | 0.4350 (2) | 0.8051 (2) | 0.06260 (17) | 0.0234 (5) | |
H2 | 0.4391 | 0.8989 | 0.0814 | 0.028* | |
C3 | 0.4205 (2) | 0.7951 (3) | −0.04817 (17) | 0.0271 (6) | |
H3A | 0.3288 | 0.7525 | −0.0856 | 0.033* | |
H3B | 0.4245 | 0.8821 | −0.0768 | 0.033* | |
C4 | 0.5488 (3) | 0.7131 (2) | −0.04985 (18) | 0.0270 (6) | |
H4 | 0.5204 | 0.6497 | −0.1058 | 0.032* | |
C5 | 0.6774 (3) | 0.7917 (3) | −0.05328 (18) | 0.0279 (6) | |
H5A | 0.7522 | 0.7331 | −0.0629 | 0.033* | |
H5B | 0.6483 | 0.8527 | −0.1097 | 0.033* | |
C5a | 0.7380 (2) | 0.8664 (2) | 0.04163 (17) | 0.0229 (5) | |
C6 | 0.8399 (2) | 0.9631 (2) | 0.05250 (18) | 0.0247 (5) | |
H6 | 0.8738 | 0.9828 | −0.0015 | 0.030* | |
C7 | 0.8940 (2) | 1.0321 (2) | 0.13958 (18) | 0.0244 (5) | |
C8 | 0.8469 (2) | 0.9994 (2) | 0.21876 (18) | 0.0266 (6) | |
H8 | 0.8841 | 1.0443 | 0.2798 | 0.032* | |
C9 | 0.7467 (2) | 0.9025 (2) | 0.20966 (17) | 0.0253 (6) | |
H9 | 0.7158 | 0.8801 | 0.2645 | 0.030* | |
C9a | 0.6909 (2) | 0.8376 (2) | 0.12113 (17) | 0.0219 (5) | |
O14 | 0.58803 (17) | 0.64596 (16) | 0.04384 (12) | 0.0272 (4) | |
C21 | 0.3162 (2) | 0.7410 (2) | 0.09166 (17) | 0.0234 (5) | |
C22 | 0.2453 (3) | 0.8088 (2) | 0.14585 (17) | 0.0266 (6) | |
H22 | 0.2732 | 0.8957 | 0.1651 | 0.032* | |
C23 | 0.1343 (2) | 0.7532 (3) | 0.17280 (18) | 0.0292 (6) | |
H23 | 0.0865 | 0.8024 | 0.2096 | 0.035* | |
C24 | 0.0923 (3) | 0.6271 (3) | 0.14689 (19) | 0.0292 (6) | |
C25 | 0.1652 (3) | 0.5583 (3) | 0.0938 (2) | 0.0329 (6) | |
H25 | 0.1391 | 0.4707 | 0.0762 | 0.040* | |
C26 | 0.2748 (3) | 0.6139 (2) | 0.0658 (2) | 0.0303 (6) | |
H26 | 0.3221 | 0.5649 | 0.0285 | 0.036* | |
C27 | −0.0301 (3) | 0.5662 (3) | 0.1741 (2) | 0.0386 (7) | |
H27A | −0.0443 | 0.6129 | 0.2304 | 0.058* | |
H27B | −0.0073 | 0.4752 | 0.1922 | 0.058* | |
H27C | −0.1184 | 0.5710 | 0.1176 | 0.058* | |
C71 | 0.9999 (3) | 1.1401 (3) | 0.1486 (2) | 0.0340 (6) | |
H71A | 1.0981 | 1.1060 | 0.1752 | 0.051* | |
H71B | 0.9843 | 1.2069 | 0.1931 | 0.051* | |
H71C | 0.9867 | 1.1781 | 0.0832 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0247 (10) | 0.0219 (11) | 0.0243 (11) | 0.0022 (8) | 0.0060 (8) | −0.0016 (9) |
C2 | 0.0237 (12) | 0.0206 (13) | 0.0239 (13) | 0.0038 (10) | 0.0048 (10) | 0.0020 (10) |
C3 | 0.0234 (12) | 0.0313 (14) | 0.0245 (13) | 0.0007 (11) | 0.0045 (10) | 0.0012 (12) |
C4 | 0.0296 (13) | 0.0271 (14) | 0.0228 (13) | 0.0025 (11) | 0.0061 (10) | −0.0023 (11) |
C5 | 0.0279 (13) | 0.0301 (15) | 0.0260 (13) | 0.0026 (11) | 0.0091 (11) | −0.0055 (12) |
C5a | 0.0192 (11) | 0.0245 (13) | 0.0240 (13) | 0.0043 (10) | 0.0051 (10) | −0.0016 (11) |
C6 | 0.0199 (11) | 0.0294 (14) | 0.0248 (13) | 0.0066 (10) | 0.0070 (10) | 0.0001 (11) |
C7 | 0.0177 (11) | 0.0247 (13) | 0.0287 (14) | 0.0042 (10) | 0.0043 (10) | −0.0020 (11) |
C8 | 0.0227 (12) | 0.0294 (14) | 0.0246 (13) | 0.0037 (11) | 0.0029 (10) | −0.0044 (11) |
C9 | 0.0260 (13) | 0.0292 (15) | 0.0200 (13) | 0.0056 (11) | 0.0062 (10) | 0.0006 (11) |
C9a | 0.0187 (11) | 0.0207 (13) | 0.0252 (13) | 0.0033 (9) | 0.0054 (10) | 0.0014 (10) |
O14 | 0.0308 (9) | 0.0192 (9) | 0.0300 (10) | 0.0032 (7) | 0.0074 (8) | −0.0024 (8) |
C21 | 0.0230 (12) | 0.0223 (13) | 0.0231 (12) | 0.0018 (10) | 0.0047 (10) | 0.0032 (10) |
C22 | 0.0280 (13) | 0.0240 (14) | 0.0252 (13) | 0.0038 (10) | 0.0048 (11) | 0.0023 (11) |
C23 | 0.0268 (13) | 0.0324 (15) | 0.0288 (14) | 0.0067 (11) | 0.0092 (11) | 0.0050 (12) |
C24 | 0.0247 (13) | 0.0323 (15) | 0.0283 (14) | 0.0018 (11) | 0.0047 (11) | 0.0083 (12) |
C25 | 0.0307 (14) | 0.0233 (14) | 0.0427 (16) | −0.0021 (11) | 0.0084 (12) | 0.0006 (12) |
C26 | 0.0291 (13) | 0.0249 (14) | 0.0377 (15) | 0.0010 (11) | 0.0116 (12) | −0.0027 (12) |
C27 | 0.0280 (14) | 0.0434 (18) | 0.0451 (17) | −0.0021 (13) | 0.0125 (12) | 0.0091 (14) |
C71 | 0.0299 (14) | 0.0349 (16) | 0.0375 (16) | −0.0035 (12) | 0.0109 (12) | −0.0076 (13) |
N1—C9a | 1.442 (3) | C8—C9 | 1.376 (3) |
N1—O14 | 1.444 (2) | C8—H8 | 0.9500 |
N1—C2 | 1.492 (3) | C9—C9a | 1.380 (3) |
C2—C21 | 1.502 (3) | C9—H9 | 0.9500 |
C2—C3 | 1.542 (3) | C21—C22 | 1.378 (3) |
C2—H2 | 1.0000 | C21—C26 | 1.386 (3) |
C3—C4 | 1.518 (3) | C22—C23 | 1.382 (3) |
C3—H3A | 0.9900 | C22—H22 | 0.9500 |
C3—H3B | 0.9900 | C23—C24 | 1.377 (4) |
C4—O14 | 1.444 (3) | C23—H23 | 0.9500 |
C4—C5 | 1.508 (3) | C24—C25 | 1.386 (4) |
C4—H4 | 1.0000 | C24—C27 | 1.504 (3) |
C5—C5a | 1.506 (3) | C25—C26 | 1.378 (3) |
C5—H5A | 0.9900 | C25—H25 | 0.9500 |
C5—H5B | 0.9900 | C26—H26 | 0.9500 |
C5a—C9a | 1.381 (3) | C27—H27A | 0.9800 |
C5a—C6 | 1.382 (3) | C27—H27B | 0.9800 |
C6—C7 | 1.383 (3) | C27—H27C | 0.9800 |
C6—H6 | 0.9500 | C71—H71A | 0.9800 |
C7—C8 | 1.386 (3) | C71—H71B | 0.9800 |
C7—C71 | 1.497 (3) | C71—H71C | 0.9800 |
C9a—N1—O14 | 107.61 (16) | C7—C8—H8 | 119.8 |
C9a—N1—C2 | 109.68 (18) | C8—C9—C9a | 120.3 (2) |
O14—N1—C2 | 102.51 (16) | C8—C9—H9 | 119.9 |
N1—C2—C21 | 111.55 (19) | C9a—C9—H9 | 119.9 |
N1—C2—C3 | 103.98 (18) | C9—C9a—C5a | 120.5 (2) |
C21—C2—C3 | 114.9 (2) | C9—C9a—N1 | 117.8 (2) |
N1—C2—H2 | 108.7 | C5a—C9a—N1 | 121.7 (2) |
C21—C2—H2 | 108.7 | C4—O14—N1 | 103.99 (16) |
C3—C2—H2 | 108.7 | C22—C21—C26 | 118.2 (2) |
C4—C3—C2 | 103.95 (19) | C22—C21—C2 | 119.9 (2) |
C4—C3—H3A | 111.0 | C26—C21—C2 | 121.9 (2) |
C2—C3—H3A | 111.0 | C21—C22—C23 | 121.3 (2) |
C4—C3—H3B | 111.0 | C21—C22—H22 | 119.3 |
C2—C3—H3B | 111.0 | C23—C22—H22 | 119.3 |
H3A—C3—H3B | 109.0 | C24—C23—C22 | 120.7 (2) |
O14—C4—C5 | 107.7 (2) | C24—C23—H23 | 119.6 |
O14—C4—C3 | 103.53 (18) | C22—C23—H23 | 119.6 |
C5—C4—C3 | 113.7 (2) | C23—C24—C25 | 117.9 (2) |
O14—C4—H4 | 110.5 | C23—C24—C27 | 121.2 (2) |
C5—C4—H4 | 110.5 | C25—C24—C27 | 120.9 (2) |
C3—C4—H4 | 110.5 | C26—C25—C24 | 121.6 (2) |
C5a—C5—C4 | 110.1 (2) | C26—C25—H25 | 119.2 |
C5a—C5—H5A | 109.6 | C24—C25—H25 | 119.2 |
C4—C5—H5A | 109.6 | C25—C26—C21 | 120.3 (2) |
C5a—C5—H5B | 109.6 | C25—C26—H26 | 119.9 |
C4—C5—H5B | 109.6 | C21—C26—H26 | 119.9 |
H5A—C5—H5B | 108.2 | C24—C27—H27A | 109.5 |
C9a—C5a—C6 | 118.4 (2) | C24—C27—H27B | 109.5 |
C9a—C5a—C5 | 119.2 (2) | H27A—C27—H27B | 109.5 |
C6—C5a—C5 | 122.4 (2) | C24—C27—H27C | 109.5 |
C5a—C6—C7 | 122.1 (2) | H27A—C27—H27C | 109.5 |
C5a—C6—H6 | 119.0 | H27B—C27—H27C | 109.5 |
C7—C6—H6 | 119.0 | C7—C71—H71A | 109.5 |
C6—C7—C8 | 118.3 (2) | C7—C71—H71B | 109.5 |
C6—C7—C71 | 121.2 (2) | H71A—C71—H71B | 109.5 |
C8—C7—C71 | 120.5 (2) | C7—C71—H71C | 109.5 |
C9—C8—C7 | 120.5 (2) | H71A—C71—H71C | 109.5 |
C9—C8—H8 | 119.8 | H71B—C71—H71C | 109.5 |
C9a—N1—C2—C21 | −154.23 (19) | C5—C5a—C9a—N1 | −4.6 (3) |
O14—N1—C2—C21 | 91.7 (2) | O14—N1—C9a—C9 | −150.51 (19) |
C9a—N1—C2—C3 | 81.4 (2) | C2—N1—C9a—C9 | 98.7 (2) |
O14—N1—C2—C3 | −32.7 (2) | O14—N1—C9a—C5a | 32.6 (3) |
N1—C2—C3—C4 | 7.3 (2) | C2—N1—C9a—C5a | −78.2 (3) |
C21—C2—C3—C4 | −114.9 (2) | C5—C4—O14—N1 | 78.1 (2) |
C2—C3—C4—O14 | 20.8 (2) | C3—C4—O14—N1 | −42.6 (2) |
C2—C3—C4—C5 | −95.8 (2) | C9a—N1—O14—C4 | −68.0 (2) |
O14—C4—C5—C5a | −47.5 (3) | C2—N1—O14—C4 | 47.6 (2) |
C3—C4—C5—C5a | 66.6 (3) | N1—C2—C21—C22 | 113.0 (2) |
C4—C5—C5a—C9a | 11.6 (3) | C3—C2—C21—C22 | −129.0 (2) |
C4—C5—C5a—C6 | −168.6 (2) | N1—C2—C21—C26 | −66.9 (3) |
C9a—C5a—C6—C7 | −0.8 (3) | C3—C2—C21—C26 | 51.1 (3) |
C5—C5a—C6—C7 | 179.4 (2) | C26—C21—C22—C23 | −0.9 (4) |
C5a—C6—C7—C8 | 2.0 (3) | C2—C21—C22—C23 | 179.2 (2) |
C5a—C6—C7—C71 | −177.5 (2) | C21—C22—C23—C24 | 0.6 (4) |
C6—C7—C8—C9 | −1.3 (3) | C22—C23—C24—C25 | 0.4 (4) |
C71—C7—C8—C9 | 178.3 (2) | C22—C23—C24—C27 | −178.8 (2) |
C7—C8—C9—C9a | −0.6 (4) | C23—C24—C25—C26 | −1.1 (4) |
C8—C9—C9a—C5a | 1.9 (4) | C27—C24—C25—C26 | 178.1 (2) |
C8—C9—C9a—N1 | −175.0 (2) | C24—C25—C26—C21 | 0.9 (4) |
C6—C5a—C9a—C9 | −1.2 (3) | C22—C21—C26—C25 | 0.1 (4) |
C5—C5a—C9a—C9 | 178.6 (2) | C2—C21—C26—C25 | −180.0 (2) |
C6—C5a—C9a—N1 | 175.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···N1i | 0.95 | 2.52 | 3.395 (3) | 153 |
C3—H3B···Cg1ii | 0.99 | 2.77 | 3.465 (3) | 127 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z. |
C16H14ClNO | F(000) = 284 |
Mr = 271.73 | Dx = 1.419 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2889 reflections |
a = 8.8558 (19) Å | θ = 3.5–27.5° |
b = 7.3585 (13) Å | µ = 0.29 mm−1 |
c = 9.9622 (18) Å | T = 120 K |
β = 101.622 (17)° | Plate, colourless |
V = 635.9 (2) Å3 | 0.25 × 0.15 × 0.07 mm |
Z = 2 |
Bruker–Nonius KappaCCD diffractometer | 2889 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2400 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.919, Tmax = 0.980 | l = −12→12 |
10226 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.0138P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2889 reflections | Δρmax = 0.23 e Å−3 |
172 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1323 Bijvoet pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (6) |
C16H14ClNO | V = 635.9 (2) Å3 |
Mr = 271.73 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.8558 (19) Å | µ = 0.29 mm−1 |
b = 7.3585 (13) Å | T = 120 K |
c = 9.9622 (18) Å | 0.25 × 0.15 × 0.07 mm |
β = 101.622 (17)° |
Bruker–Nonius KappaCCD diffractometer | 2889 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2400 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.980 | Rint = 0.048 |
10226 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 0.23 e Å−3 |
S = 1.08 | Δρmin = −0.22 e Å−3 |
2889 reflections | Absolute structure: Flack (1983), 1323 Bijvoet pairs |
172 parameters | Absolute structure parameter: 0.07 (6) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3548 (2) | 0.4825 (2) | 0.18686 (17) | 0.0189 (4) | |
C2 | 0.4652 (2) | 0.4263 (3) | 0.3111 (2) | 0.0167 (4) | |
H2 | 0.4106 | 0.4142 | 0.3893 | 0.020* | |
C3 | 0.5224 (3) | 0.2389 (3) | 0.2750 (2) | 0.0193 (5) | |
H3A | 0.6364 | 0.2325 | 0.2970 | 0.023* | |
H3B | 0.4800 | 0.1410 | 0.3248 | 0.023* | |
C4 | 0.4615 (2) | 0.2243 (3) | 0.1217 (2) | 0.0198 (5) | |
H4 | 0.5423 | 0.1742 | 0.0748 | 0.024* | |
C5 | 0.3142 (3) | 0.1174 (3) | 0.0832 (2) | 0.0233 (5) | |
H5A | 0.2902 | 0.0968 | −0.0171 | 0.028* | |
H5B | 0.3270 | −0.0025 | 0.1291 | 0.028* | |
C5a | 0.1839 (2) | 0.2184 (3) | 0.1251 (2) | 0.0186 (5) | |
C6 | 0.0384 (3) | 0.1435 (3) | 0.1122 (2) | 0.0220 (5) | |
H6 | 0.0188 | 0.0249 | 0.0750 | 0.026* | |
C7 | −0.0781 (2) | 0.2391 (3) | 0.1528 (2) | 0.0224 (5) | |
H7 | −0.1782 | 0.1873 | 0.1412 | 0.027* | |
C8 | −0.0511 (2) | 0.4091 (3) | 0.2101 (2) | 0.0220 (5) | |
H8 | −0.1307 | 0.4723 | 0.2417 | 0.026* | |
C9 | 0.0924 (3) | 0.4869 (3) | 0.2211 (2) | 0.0211 (5) | |
H9 | 0.1114 | 0.6054 | 0.2585 | 0.025* | |
C9a | 0.2083 (2) | 0.3927 (3) | 0.17793 (18) | 0.0176 (4) | |
O14 | 0.42541 (16) | 0.4106 (2) | 0.08003 (13) | 0.0212 (4) | |
C21 | 0.5933 (2) | 0.5633 (3) | 0.3468 (2) | 0.0163 (4) | |
C22 | 0.7029 (2) | 0.5473 (3) | 0.4668 (2) | 0.0181 (5) | |
C23 | 0.8225 (3) | 0.6676 (3) | 0.5033 (2) | 0.0228 (5) | |
H23 | 0.8945 | 0.6540 | 0.5873 | 0.027* | |
C24 | 0.8362 (3) | 0.8084 (3) | 0.4157 (2) | 0.0276 (5) | |
H24 | 0.9180 | 0.8933 | 0.4392 | 0.033* | |
C25 | 0.7315 (3) | 0.8262 (3) | 0.2941 (2) | 0.0251 (5) | |
H25 | 0.7429 | 0.9211 | 0.2322 | 0.030* | |
C26 | 0.6099 (2) | 0.7062 (3) | 0.2620 (2) | 0.0197 (5) | |
H26 | 0.5360 | 0.7226 | 0.1794 | 0.024* | |
Cl22 | 0.69066 (6) | 0.36764 (7) | 0.57757 (5) | 0.02486 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0174 (10) | 0.0213 (9) | 0.0182 (9) | 0.0005 (8) | 0.0041 (7) | −0.0013 (7) |
C2 | 0.0161 (11) | 0.0163 (10) | 0.0173 (9) | −0.0003 (8) | 0.0024 (8) | 0.0011 (8) |
C3 | 0.0181 (11) | 0.0151 (10) | 0.0244 (11) | −0.0007 (9) | 0.0036 (9) | 0.0006 (8) |
C4 | 0.0188 (12) | 0.0205 (11) | 0.0204 (11) | 0.0009 (9) | 0.0046 (9) | −0.0032 (9) |
C5 | 0.0208 (12) | 0.0262 (12) | 0.0230 (11) | −0.0018 (9) | 0.0044 (9) | −0.0067 (9) |
C5a | 0.0190 (12) | 0.0208 (12) | 0.0150 (10) | −0.0014 (9) | 0.0013 (9) | −0.0008 (8) |
C6 | 0.0230 (13) | 0.0230 (12) | 0.0183 (11) | −0.0045 (9) | 0.0003 (9) | −0.0012 (9) |
C7 | 0.0139 (12) | 0.0313 (13) | 0.0216 (11) | −0.0007 (10) | 0.0030 (9) | 0.0057 (10) |
C8 | 0.0163 (11) | 0.0287 (13) | 0.0203 (10) | 0.0052 (9) | 0.0023 (9) | 0.0032 (9) |
C9 | 0.0208 (12) | 0.0215 (11) | 0.0187 (10) | 0.0049 (10) | −0.0013 (9) | −0.0003 (9) |
C9a | 0.0160 (10) | 0.0202 (12) | 0.0154 (9) | −0.0003 (9) | 0.0001 (7) | 0.0005 (9) |
O14 | 0.0199 (8) | 0.0279 (9) | 0.0166 (7) | −0.0017 (6) | 0.0053 (6) | 0.0012 (6) |
C21 | 0.0167 (11) | 0.0153 (10) | 0.0186 (10) | 0.0016 (9) | 0.0076 (9) | −0.0023 (8) |
C22 | 0.0207 (12) | 0.0194 (11) | 0.0154 (10) | 0.0011 (9) | 0.0067 (9) | −0.0015 (8) |
C23 | 0.0197 (12) | 0.0233 (12) | 0.0245 (11) | −0.0007 (10) | 0.0021 (9) | −0.0067 (9) |
C24 | 0.0228 (13) | 0.0219 (12) | 0.0381 (13) | −0.0064 (9) | 0.0064 (11) | −0.0102 (10) |
C25 | 0.0262 (13) | 0.0173 (13) | 0.0339 (12) | 0.0000 (9) | 0.0113 (10) | 0.0015 (9) |
C26 | 0.0193 (12) | 0.0169 (10) | 0.0232 (11) | 0.0020 (9) | 0.0051 (9) | 0.0009 (9) |
Cl22 | 0.0284 (3) | 0.0247 (3) | 0.0202 (2) | 0.0007 (2) | 0.0016 (2) | 0.0033 (2) |
N1—O14 | 1.439 (2) | C6—H6 | 0.9500 |
N1—C9a | 1.443 (3) | C7—C8 | 1.375 (3) |
N1—C2 | 1.474 (3) | C7—H7 | 0.9500 |
C2—C21 | 1.506 (3) | C8—C9 | 1.378 (3) |
C2—C3 | 1.537 (3) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.378 (3) |
C3—C4 | 1.518 (3) | C9—H9 | 0.9500 |
C3—H3A | 0.9900 | C21—C26 | 1.375 (3) |
C3—H3B | 0.9900 | C21—C22 | 1.385 (3) |
C4—O14 | 1.449 (3) | C22—C23 | 1.372 (3) |
C4—C5 | 1.505 (3) | C22—Cl22 | 1.739 (2) |
C4—H4 | 1.0000 | C23—C24 | 1.375 (3) |
C5—C5a | 1.501 (3) | C23—H23 | 0.9500 |
C5—H5A | 0.9900 | C24—C25 | 1.376 (3) |
C5—H5B | 0.9900 | C24—H24 | 0.9500 |
C5a—C6 | 1.384 (3) | C25—C26 | 1.379 (3) |
C5a—C9a | 1.386 (3) | C25—H25 | 0.9500 |
C6—C7 | 1.376 (3) | C26—H26 | 0.9500 |
O14—N1—C9a | 107.77 (15) | C5a—C6—H6 | 119.7 |
O14—N1—C2 | 101.79 (14) | C8—C7—C6 | 120.6 (2) |
C9a—N1—C2 | 111.08 (16) | C8—C7—H7 | 119.7 |
N1—C2—C21 | 110.59 (17) | C6—C7—H7 | 119.7 |
N1—C2—C3 | 104.42 (16) | C7—C8—C9 | 119.5 (2) |
C21—C2—C3 | 112.85 (17) | C7—C8—H8 | 120.3 |
N1—C2—H2 | 109.6 | C9—C8—H8 | 120.3 |
C21—C2—H2 | 109.6 | C9a—C9—C8 | 119.9 (2) |
C3—C2—H2 | 109.6 | C9a—C9—H9 | 120.0 |
C4—C3—C2 | 103.42 (17) | C8—C9—H9 | 120.0 |
C4—C3—H3A | 111.1 | C9—C9a—C5a | 121.03 (19) |
C2—C3—H3A | 111.1 | C9—C9a—N1 | 117.85 (19) |
C4—C3—H3B | 111.1 | C5a—C9a—N1 | 121.11 (18) |
C2—C3—H3B | 111.1 | N1—O14—C4 | 103.87 (14) |
H3A—C3—H3B | 109.0 | C26—C21—C22 | 116.92 (19) |
O14—C4—C5 | 106.96 (17) | C26—C21—C2 | 122.36 (19) |
O14—C4—C3 | 103.56 (16) | C22—C21—C2 | 120.70 (18) |
C5—C4—C3 | 114.01 (18) | C23—C22—C21 | 122.9 (2) |
O14—C4—H4 | 110.7 | C23—C22—Cl22 | 117.79 (16) |
C5—C4—H4 | 110.7 | C21—C22—Cl22 | 119.34 (16) |
C3—C4—H4 | 110.7 | C22—C23—C24 | 118.7 (2) |
C5a—C5—C4 | 110.22 (18) | C22—C23—H23 | 120.6 |
C5a—C5—H5A | 109.6 | C24—C23—H23 | 120.6 |
C4—C5—H5A | 109.6 | C23—C24—C25 | 120.0 (2) |
C5a—C5—H5B | 109.6 | C23—C24—H24 | 120.0 |
C4—C5—H5B | 109.6 | C25—C24—H24 | 120.0 |
H5A—C5—H5B | 108.1 | C24—C25—C26 | 119.9 (2) |
C6—C5a—C9a | 118.3 (2) | C24—C25—H25 | 120.0 |
C6—C5a—C5 | 122.06 (19) | C26—C25—H25 | 120.0 |
C9a—C5a—C5 | 119.60 (19) | C21—C26—C25 | 121.5 (2) |
C7—C6—C5a | 120.6 (2) | C21—C26—H26 | 119.3 |
C7—C6—H6 | 119.7 | C25—C26—H26 | 119.3 |
O14—N1—C2—C21 | 85.61 (18) | O14—N1—C9a—C9 | −150.88 (16) |
C9a—N1—C2—C21 | −159.89 (16) | C2—N1—C9a—C9 | 98.4 (2) |
O14—N1—C2—C3 | −36.05 (19) | O14—N1—C9a—C5a | 27.9 (2) |
C9a—N1—C2—C3 | 78.4 (2) | C2—N1—C9a—C5a | −82.8 (2) |
N1—C2—C3—C4 | 11.1 (2) | C9a—N1—O14—C4 | −68.07 (18) |
C21—C2—C3—C4 | −109.06 (19) | C2—N1—O14—C4 | 48.85 (17) |
C2—C3—C4—O14 | 17.8 (2) | C5—C4—O14—N1 | 79.27 (17) |
C2—C3—C4—C5 | −98.1 (2) | C3—C4—O14—N1 | −41.47 (19) |
O14—C4—C5—C5a | −45.7 (2) | N1—C2—C21—C26 | −7.6 (3) |
C3—C4—C5—C5a | 68.2 (2) | C3—C2—C21—C26 | 109.0 (2) |
C4—C5—C5a—C6 | −174.42 (19) | N1—C2—C21—C22 | 174.08 (17) |
C4—C5—C5a—C9a | 5.9 (3) | C3—C2—C21—C22 | −69.4 (2) |
C9a—C5a—C6—C7 | −0.9 (3) | C26—C21—C22—C23 | 1.0 (3) |
C5—C5a—C6—C7 | 179.38 (19) | C2—C21—C22—C23 | 179.41 (19) |
C5a—C6—C7—C8 | −1.6 (3) | C26—C21—C22—Cl22 | −179.01 (15) |
C6—C7—C8—C9 | 2.8 (3) | C2—C21—C22—Cl22 | −0.6 (3) |
C7—C8—C9—C9a | −1.5 (3) | C21—C22—C23—C24 | −1.3 (3) |
C8—C9—C9a—C5a | −1.0 (3) | Cl22—C22—C23—C24 | 178.62 (17) |
C8—C9—C9a—N1 | 177.72 (18) | C22—C23—C24—C25 | −0.2 (3) |
C6—C5a—C9a—C9 | 2.2 (3) | C23—C24—C25—C26 | 2.1 (3) |
C5—C5a—C9a—C9 | −178.05 (19) | C22—C21—C26—C25 | 1.0 (3) |
C6—C5a—C9a—N1 | −176.48 (18) | C2—C21—C26—C25 | −177.46 (19) |
C5—C5a—C9a—N1 | 3.2 (3) | C24—C25—C26—C21 | −2.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···Cl22i | 0.99 | 2.81 | 3.781 (3) | 169 |
C4—H4···O14ii | 1.00 | 2.53 | 3.344 (3) | 138 |
C6—H6···Cg1iii | 0.95 | 2.83 | 3.657 (2) | 146 |
C8—H8···Cg2iv | 0.95 | 2.65 | 3.571 (2) | 163 |
C23—H23···Cg1v | 0.95 | 2.68 | 3.415 (2) | 134 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y−1/2, −z; (iii) −x, y−1/2, −z; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1. |
C17H16ClNO | Z = 4 |
Mr = 285.76 | F(000) = 600 |
Triclinic, P1 | Dx = 1.396 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7150 (9) Å | Cell parameters from 6196 reflections |
b = 10.406 (2) Å | θ = 2.9–27.5° |
c = 15.312 (4) Å | µ = 0.28 mm−1 |
α = 99.547 (19)° | T = 120 K |
β = 90.621 (14)° | Block, colourless |
γ = 96.514 (13)° | 0.15 × 0.10 × 0.08 mm |
V = 1359.9 (5) Å3 |
Bruker-Nonius KappaCCD diffractometer | 6196 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 4084 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003) | k = −13→13 |
Tmin = 0.949, Tmax = 0.978 | l = −19→19 |
34637 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.113 | H-atom parameters constrained |
wR(F2) = 0.308 | w = 1/[σ2(Fo2) + (0.0668P)2 + 15.6862P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
6196 reflections | Δρmax = 1.67 e Å−3 |
365 parameters | Δρmin = −0.55 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.012 (2) |
C17H16ClNO | γ = 96.514 (13)° |
Mr = 285.76 | V = 1359.9 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.7150 (9) Å | Mo Kα radiation |
b = 10.406 (2) Å | µ = 0.28 mm−1 |
c = 15.312 (4) Å | T = 120 K |
α = 99.547 (19)° | 0.15 × 0.10 × 0.08 mm |
β = 90.621 (14)° |
Bruker-Nonius KappaCCD diffractometer | 6196 independent reflections |
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003) | 4084 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.978 | Rint = 0.093 |
34637 measured reflections |
R[F2 > 2σ(F2)] = 0.113 | 0 restraints |
wR(F2) = 0.308 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0668P)2 + 15.6862P] where P = (Fo2 + 2Fc2)/3 |
6196 reflections | Δρmax = 1.67 e Å−3 |
365 parameters | Δρmin = −0.55 e Å−3 |
x | y | z | Uiso*/Ueq | ||
N11 | 0.8122 (6) | 0.5215 (5) | 0.6500 (3) | 0.0148 (10) | |
C12 | 0.9373 (7) | 0.4383 (6) | 0.6243 (4) | 0.0178 (13) | |
H12 | 0.9373 | 0.4143 | 0.5583 | 0.021* | |
C13 | 1.0866 (7) | 0.5282 (6) | 0.6571 (4) | 0.0171 (12) | |
H13A | 1.1551 | 0.4831 | 0.6908 | 0.020* | |
H13B | 1.1436 | 0.5576 | 0.6070 | 0.020* | |
C14 | 1.0268 (8) | 0.6435 (7) | 0.7168 (4) | 0.0215 (14) | |
H14 | 1.0897 | 0.6677 | 0.7734 | 0.026* | |
C15 | 1.0204 (8) | 0.7618 (6) | 0.6724 (4) | 0.0219 (14) | |
H15A | 0.9942 | 0.8368 | 0.7162 | 0.026* | |
H15B | 1.1226 | 0.7867 | 0.6486 | 0.026* | |
C15A | 0.9001 (7) | 0.7302 (6) | 0.5983 (4) | 0.0166 (12) | |
C16 | 0.8798 (8) | 0.8132 (7) | 0.5378 (4) | 0.0223 (14) | |
H16 | 0.9436 | 0.8946 | 0.5435 | 0.027* | |
C17 | 0.7706 (8) | 0.7814 (6) | 0.4700 (4) | 0.0196 (13) | |
C18 | 0.6785 (8) | 0.6631 (6) | 0.4616 (4) | 0.0207 (13) | |
H18 | 0.6035 | 0.6393 | 0.4144 | 0.025* | |
C19 | 0.6938 (7) | 0.5799 (6) | 0.5203 (4) | 0.0197 (13) | |
H19 | 0.6295 | 0.4986 | 0.5138 | 0.024* | |
C19A | 0.8028 (7) | 0.6130 (6) | 0.5893 (4) | 0.0158 (12) | |
O114 | 0.8712 (5) | 0.5942 (5) | 0.7337 (3) | 0.0205 (10) | |
C121 | 0.9021 (7) | 0.3167 (6) | 0.6641 (4) | 0.0196 (13) | |
C122 | 0.7992 (8) | 0.2126 (7) | 0.6218 (4) | 0.0209 (13) | |
Cl12 | 0.7100 (2) | 0.22299 (17) | 0.52121 (11) | 0.0259 (4) | |
C123 | 0.7594 (9) | 0.1006 (7) | 0.6563 (5) | 0.0292 (16) | |
H123 | 0.6886 | 0.0314 | 0.6254 | 0.035* | |
C124 | 0.8249 (9) | 0.0906 (7) | 0.7378 (5) | 0.0324 (17) | |
H124 | 0.7997 | 0.0134 | 0.7628 | 0.039* | |
C125 | 0.9255 (9) | 0.1915 (8) | 0.7823 (5) | 0.0320 (17) | |
H125 | 0.9690 | 0.1850 | 0.8383 | 0.038* | |
C126 | 0.9634 (8) | 0.3030 (7) | 0.7452 (5) | 0.0246 (15) | |
H126 | 1.0337 | 0.3722 | 0.7764 | 0.030* | |
C171 | 0.7550 (10) | 0.8732 (7) | 0.4047 (5) | 0.0310 (17) | |
H17A | 0.8177 | 0.8486 | 0.3532 | 0.046* | |
H17B | 0.7907 | 0.9634 | 0.4330 | 0.046* | |
H17C | 0.6464 | 0.8675 | 0.3855 | 0.046* | |
N21 | 0.3111 (6) | 0.4643 (5) | 0.8385 (3) | 0.0161 (11) | |
C22 | 0.4461 (7) | 0.5619 (6) | 0.8685 (4) | 0.0168 (12) | |
H22 | 0.4404 | 0.5943 | 0.9335 | 0.020* | |
C23 | 0.5851 (7) | 0.4832 (6) | 0.8512 (4) | 0.0192 (13) | |
H23A | 0.6687 | 0.5323 | 0.8227 | 0.023* | |
H23B | 0.6263 | 0.4620 | 0.9070 | 0.023* | |
C24 | 0.5180 (8) | 0.3609 (7) | 0.7902 (4) | 0.0216 (14) | |
H24 | 0.5864 | 0.3407 | 0.7389 | 0.026* | |
C25 | 0.4852 (9) | 0.2428 (7) | 0.8363 (5) | 0.0262 (15) | |
H25A | 0.4512 | 0.1636 | 0.7921 | 0.031* | |
H25B | 0.5802 | 0.2276 | 0.8671 | 0.031* | |
C25A | 0.3611 (7) | 0.2682 (6) | 0.9018 (4) | 0.0191 (13) | |
C26 | 0.3235 (8) | 0.1881 (7) | 0.9642 (4) | 0.0235 (14) | |
H26 | 0.3778 | 0.1142 | 0.9650 | 0.028* | |
C27 | 0.2096 (8) | 0.2118 (6) | 1.0255 (4) | 0.0206 (14) | |
C28 | 0.1315 (8) | 0.3188 (7) | 1.0211 (4) | 0.0252 (15) | |
H28 | 0.0514 | 0.3363 | 1.0614 | 0.030* | |
C29 | 0.1651 (8) | 0.4007 (7) | 0.9609 (5) | 0.0243 (15) | |
H29 | 0.1102 | 0.4744 | 0.9604 | 0.029* | |
C29A | 0.2795 (7) | 0.3753 (6) | 0.9008 (4) | 0.0163 (12) | |
O214 | 0.3700 (5) | 0.3906 (4) | 0.7602 (3) | 0.0201 (10) | |
C221 | 0.4435 (7) | 0.6739 (6) | 0.8192 (4) | 0.0180 (13) | |
C222 | 0.3678 (8) | 0.7813 (6) | 0.8513 (4) | 0.0205 (13) | |
Cl22 | 0.2754 (2) | 0.78872 (17) | 0.95132 (11) | 0.0289 (4) | |
C223 | 0.3570 (8) | 0.8832 (6) | 0.8051 (5) | 0.0230 (14) | |
H223 | 0.3037 | 0.9552 | 0.8288 | 0.028* | |
C224 | 0.4248 (8) | 0.8785 (7) | 0.7242 (5) | 0.0247 (15) | |
H224 | 0.4194 | 0.9484 | 0.6919 | 0.030* | |
C225 | 0.4997 (8) | 0.7743 (7) | 0.6901 (4) | 0.0225 (14) | |
H225 | 0.5463 | 0.7718 | 0.6341 | 0.027* | |
C226 | 0.5082 (8) | 0.6725 (7) | 0.7365 (4) | 0.0207 (13) | |
H226 | 0.5594 | 0.5998 | 0.7114 | 0.025* | |
C271 | 0.1754 (10) | 0.1262 (8) | 1.0932 (5) | 0.0329 (17) | |
H27A | 0.0731 | 0.0763 | 1.0804 | 0.049* | |
H27B | 0.1770 | 0.1806 | 1.1521 | 0.049* | |
H27C | 0.2536 | 0.0653 | 1.0919 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.014 (3) | 0.016 (3) | 0.014 (2) | 0.003 (2) | −0.0007 (19) | 0.003 (2) |
C12 | 0.016 (3) | 0.022 (3) | 0.015 (3) | 0.003 (2) | 0.001 (2) | 0.002 (2) |
C13 | 0.014 (3) | 0.020 (3) | 0.018 (3) | 0.004 (2) | 0.000 (2) | 0.005 (2) |
C14 | 0.020 (3) | 0.028 (4) | 0.018 (3) | 0.002 (3) | 0.000 (2) | 0.009 (3) |
C15 | 0.028 (4) | 0.018 (3) | 0.018 (3) | 0.001 (3) | 0.004 (3) | −0.001 (2) |
C15A | 0.020 (3) | 0.017 (3) | 0.013 (3) | 0.002 (2) | 0.000 (2) | 0.002 (2) |
C16 | 0.024 (3) | 0.020 (3) | 0.024 (3) | 0.002 (3) | 0.005 (3) | 0.005 (3) |
C17 | 0.033 (4) | 0.015 (3) | 0.013 (3) | 0.009 (3) | 0.003 (3) | 0.003 (2) |
C18 | 0.024 (3) | 0.021 (3) | 0.016 (3) | 0.005 (3) | −0.002 (2) | −0.002 (2) |
C19 | 0.021 (3) | 0.018 (3) | 0.022 (3) | 0.008 (2) | 0.001 (2) | 0.003 (3) |
C19A | 0.016 (3) | 0.017 (3) | 0.016 (3) | 0.008 (2) | 0.004 (2) | 0.004 (2) |
O114 | 0.020 (2) | 0.027 (2) | 0.014 (2) | 0.0009 (19) | 0.0006 (17) | 0.0017 (18) |
C121 | 0.017 (3) | 0.021 (3) | 0.023 (3) | 0.004 (2) | 0.006 (2) | 0.010 (3) |
C122 | 0.024 (3) | 0.023 (3) | 0.018 (3) | 0.008 (3) | −0.001 (3) | 0.005 (3) |
Cl12 | 0.0315 (9) | 0.0232 (8) | 0.0222 (8) | 0.0029 (7) | −0.0040 (6) | 0.0023 (6) |
C123 | 0.031 (4) | 0.020 (3) | 0.037 (4) | 0.001 (3) | 0.007 (3) | 0.006 (3) |
C124 | 0.042 (5) | 0.025 (4) | 0.036 (4) | 0.009 (3) | 0.009 (3) | 0.019 (3) |
C125 | 0.036 (4) | 0.036 (4) | 0.030 (4) | 0.010 (3) | 0.004 (3) | 0.019 (3) |
C126 | 0.025 (4) | 0.026 (4) | 0.025 (4) | 0.003 (3) | 0.005 (3) | 0.010 (3) |
C171 | 0.049 (5) | 0.023 (4) | 0.023 (4) | 0.010 (3) | 0.000 (3) | 0.006 (3) |
N21 | 0.022 (3) | 0.015 (3) | 0.011 (2) | 0.001 (2) | 0.000 (2) | 0.0039 (19) |
C22 | 0.018 (3) | 0.017 (3) | 0.014 (3) | −0.002 (2) | 0.000 (2) | 0.001 (2) |
C23 | 0.020 (3) | 0.019 (3) | 0.020 (3) | 0.001 (2) | −0.001 (2) | 0.009 (3) |
C24 | 0.025 (3) | 0.024 (3) | 0.018 (3) | 0.009 (3) | 0.007 (3) | 0.005 (3) |
C25 | 0.033 (4) | 0.024 (4) | 0.023 (3) | 0.009 (3) | 0.010 (3) | 0.004 (3) |
C25A | 0.021 (3) | 0.019 (3) | 0.016 (3) | −0.004 (2) | 0.003 (2) | 0.003 (2) |
C26 | 0.032 (4) | 0.018 (3) | 0.021 (3) | 0.000 (3) | −0.003 (3) | 0.005 (3) |
C27 | 0.033 (4) | 0.012 (3) | 0.016 (3) | −0.004 (3) | −0.001 (3) | 0.005 (2) |
C28 | 0.026 (4) | 0.029 (4) | 0.020 (3) | 0.001 (3) | 0.010 (3) | 0.005 (3) |
C29 | 0.020 (3) | 0.023 (3) | 0.032 (4) | 0.003 (3) | 0.007 (3) | 0.009 (3) |
C29A | 0.016 (3) | 0.019 (3) | 0.013 (3) | −0.003 (2) | 0.000 (2) | 0.003 (2) |
O214 | 0.027 (2) | 0.024 (2) | 0.009 (2) | 0.0017 (19) | 0.0015 (17) | 0.0009 (17) |
C221 | 0.017 (3) | 0.022 (3) | 0.015 (3) | 0.000 (2) | −0.001 (2) | 0.003 (2) |
C222 | 0.022 (3) | 0.022 (3) | 0.015 (3) | −0.001 (3) | 0.001 (2) | −0.002 (2) |
Cl22 | 0.0338 (10) | 0.0286 (9) | 0.0234 (9) | 0.0032 (7) | 0.0112 (7) | 0.0009 (7) |
C223 | 0.023 (3) | 0.018 (3) | 0.028 (4) | 0.004 (3) | 0.001 (3) | 0.002 (3) |
C224 | 0.028 (4) | 0.019 (3) | 0.029 (4) | 0.000 (3) | 0.003 (3) | 0.011 (3) |
C225 | 0.027 (4) | 0.024 (3) | 0.018 (3) | 0.002 (3) | 0.002 (3) | 0.009 (3) |
C226 | 0.024 (3) | 0.021 (3) | 0.017 (3) | −0.002 (3) | 0.001 (2) | 0.005 (3) |
C271 | 0.047 (5) | 0.028 (4) | 0.023 (4) | −0.006 (3) | 0.006 (3) | 0.009 (3) |
N11—O114 | 1.434 (6) | N21—C29A | 1.443 (8) |
N11—C19A | 1.444 (8) | N21—O214 | 1.445 (6) |
N11—C12 | 1.485 (8) | N21—C22 | 1.480 (8) |
C12—C121 | 1.496 (9) | C22—C221 | 1.493 (9) |
C12—C13 | 1.541 (9) | C22—C23 | 1.539 (9) |
C12—H12 | 1.0000 | C22—H22 | 1.0000 |
C13—C14 | 1.529 (9) | C23—C24 | 1.503 (9) |
C13—H13A | 0.9900 | C23—H23A | 0.9900 |
C13—H13B | 0.9900 | C23—H23B | 0.9900 |
C14—O114 | 1.436 (8) | C24—O214 | 1.447 (8) |
C14—C15 | 1.507 (9) | C24—C25 | 1.517 (9) |
C14—H14 | 1.0000 | C24—H24 | 1.0000 |
C15—C15A | 1.506 (9) | C25—C25A | 1.499 (9) |
C15—H15A | 0.9900 | C25—H25A | 0.9900 |
C15—H15B | 0.9900 | C25—H25B | 0.9900 |
C15A—C16 | 1.390 (9) | C25A—C26 | 1.388 (9) |
C15A—C19A | 1.390 (9) | C25A—C29A | 1.390 (9) |
C16—C17 | 1.374 (9) | C26—C27 | 1.387 (10) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C18 | 1.377 (9) | C27—C28 | 1.380 (10) |
C17—C171 | 1.508 (9) | C27—C271 | 1.487 (9) |
C18—C19 | 1.363 (9) | C28—C29 | 1.368 (10) |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C19—C19A | 1.386 (9) | C29—C29A | 1.381 (9) |
C19—H19 | 0.9500 | C29—H29 | 0.9500 |
C121—C126 | 1.381 (9) | C221—C222 | 1.385 (9) |
C121—C122 | 1.390 (9) | C221—C226 | 1.390 (9) |
C122—C123 | 1.370 (10) | C222—C223 | 1.379 (10) |
C122—Cl12 | 1.743 (7) | C222—Cl22 | 1.733 (7) |
C123—C124 | 1.391 (11) | C223—C224 | 1.375 (10) |
C123—H123 | 0.9500 | C223—H223 | 0.9500 |
C124—C125 | 1.370 (11) | C224—C225 | 1.362 (10) |
C124—H124 | 0.9500 | C224—H224 | 0.9500 |
C125—C126 | 1.384 (10) | C225—C226 | 1.378 (9) |
C125—H125 | 0.9500 | C225—H225 | 0.9500 |
C126—H126 | 0.9500 | C226—H226 | 0.9500 |
C171—H17A | 0.9800 | C271—H27A | 0.9800 |
C171—H17B | 0.9800 | C271—H27B | 0.9800 |
C171—H17C | 0.9800 | C271—H27C | 0.9800 |
O114—N11—C19A | 108.0 (5) | C29A—N21—O214 | 107.2 (5) |
O114—N11—C12 | 101.4 (4) | C29A—N21—C22 | 111.2 (5) |
C19A—N11—C12 | 110.1 (5) | O214—N21—C22 | 101.0 (4) |
N11—C12—C121 | 106.9 (5) | N21—C22—C221 | 108.6 (5) |
N11—C12—C13 | 104.1 (5) | N21—C22—C23 | 103.9 (5) |
C121—C12—C13 | 117.2 (5) | C221—C22—C23 | 115.4 (5) |
N11—C12—H12 | 109.5 | N21—C22—H22 | 109.6 |
C121—C12—H12 | 109.5 | C221—C22—H22 | 109.6 |
C13—C12—H12 | 109.5 | C23—C22—H22 | 109.6 |
C14—C13—C12 | 103.0 (5) | C24—C23—C22 | 103.3 (5) |
C14—C13—H13A | 111.2 | C24—C23—H23A | 111.1 |
C12—C13—H13A | 111.2 | C22—C23—H23A | 111.1 |
C14—C13—H13B | 111.2 | C24—C23—H23B | 111.1 |
C12—C13—H13B | 111.2 | C22—C23—H23B | 111.1 |
H13A—C13—H13B | 109.1 | H23A—C23—H23B | 109.1 |
O114—C14—C15 | 107.9 (5) | O214—C24—C23 | 104.9 (5) |
O114—C14—C13 | 103.8 (5) | O214—C24—C25 | 106.6 (5) |
C15—C14—C13 | 113.3 (5) | C23—C24—C25 | 113.5 (6) |
O114—C14—H14 | 110.5 | O214—C24—H24 | 110.6 |
C15—C14—H14 | 110.5 | C23—C24—H24 | 110.6 |
C13—C14—H14 | 110.5 | C25—C24—H24 | 110.6 |
C15A—C15—C14 | 109.4 (5) | C25A—C25—C24 | 108.9 (6) |
C15A—C15—H15A | 109.8 | C25A—C25—H25A | 109.9 |
C14—C15—H15A | 109.8 | C24—C25—H25A | 109.9 |
C15A—C15—H15B | 109.8 | C25A—C25—H25B | 109.9 |
C14—C15—H15B | 109.8 | C24—C25—H25B | 109.9 |
H15A—C15—H15B | 108.2 | H25A—C25—H25B | 108.3 |
C16—C15A—C19A | 117.5 (6) | C26—C25A—C29A | 118.0 (6) |
C16—C15A—C15 | 123.3 (6) | C26—C25A—C25 | 122.3 (6) |
C19A—C15A—C15 | 119.2 (5) | C29A—C25A—C25 | 119.6 (6) |
C17—C16—C15A | 122.2 (6) | C27—C26—C25A | 122.6 (6) |
C17—C16—H16 | 118.9 | C27—C26—H26 | 118.7 |
C15A—C16—H16 | 118.9 | C25A—C26—H26 | 118.7 |
C16—C17—C18 | 118.8 (6) | C28—C27—C26 | 116.9 (6) |
C16—C17—C171 | 120.4 (6) | C28—C27—C271 | 121.9 (6) |
C18—C17—C171 | 120.8 (6) | C26—C27—C271 | 121.2 (6) |
C19—C18—C17 | 120.6 (6) | C29—C28—C27 | 122.5 (6) |
C19—C18—H18 | 119.7 | C29—C28—H28 | 118.8 |
C17—C18—H18 | 119.7 | C27—C28—H28 | 118.8 |
C18—C19—C19A | 120.4 (6) | C28—C29—C29A | 119.5 (6) |
C18—C19—H19 | 119.8 | C28—C29—H29 | 120.3 |
C19A—C19—H19 | 119.8 | C29A—C29—H29 | 120.3 |
C19—C19A—C15A | 120.4 (6) | C29—C29A—C25A | 120.5 (6) |
C19—C19A—N11 | 117.8 (6) | C29—C29A—N21 | 117.6 (6) |
C15A—C19A—N11 | 121.8 (5) | C25A—C29A—N21 | 121.9 (5) |
N11—O114—C14 | 104.5 (4) | N21—O214—C24 | 103.6 (4) |
C126—C121—C122 | 116.4 (6) | C222—C221—C226 | 116.5 (6) |
C126—C121—C12 | 122.8 (6) | C222—C221—C22 | 121.4 (6) |
C122—C121—C12 | 120.7 (6) | C226—C221—C22 | 122.0 (6) |
C123—C122—C121 | 123.2 (6) | C223—C222—C221 | 122.7 (6) |
C123—C122—Cl12 | 116.8 (6) | C223—C222—Cl22 | 117.2 (5) |
C121—C122—Cl12 | 119.9 (5) | C221—C222—Cl22 | 120.1 (5) |
C122—C123—C124 | 118.4 (7) | C224—C223—C222 | 118.8 (6) |
C122—C123—H123 | 120.8 | C224—C223—H223 | 120.6 |
C124—C123—H123 | 120.8 | C222—C223—H223 | 120.6 |
C125—C124—C123 | 120.3 (7) | C225—C224—C223 | 120.4 (6) |
C125—C124—H124 | 119.8 | C225—C224—H224 | 119.8 |
C123—C124—H124 | 119.8 | C223—C224—H224 | 119.8 |
C124—C125—C126 | 119.6 (7) | C224—C225—C226 | 120.2 (6) |
C124—C125—H125 | 120.2 | C224—C225—H225 | 119.9 |
C126—C125—H125 | 120.2 | C226—C225—H225 | 119.9 |
C121—C126—C125 | 122.0 (7) | C225—C226—C221 | 121.4 (6) |
C121—C126—H126 | 119.0 | C225—C226—H226 | 119.3 |
C125—C126—H126 | 119.0 | C221—C226—H226 | 119.3 |
C17—C171—H17A | 109.5 | C27—C271—H27A | 109.5 |
C17—C171—H17B | 109.5 | C27—C271—H27B | 109.5 |
H17A—C171—H17B | 109.5 | H27A—C271—H27B | 109.5 |
C17—C171—H17C | 109.5 | C27—C271—H27C | 109.5 |
H17A—C171—H17C | 109.5 | H27A—C271—H27C | 109.5 |
H17B—C171—H17C | 109.5 | H27B—C271—H27C | 109.5 |
O114—N11—C12—C121 | 87.6 (5) | C29A—N21—C22—C221 | −162.3 (5) |
C19A—N11—C12—C121 | −158.2 (5) | O214—N21—C22—C221 | 84.2 (5) |
O114—N11—C12—C13 | −37.0 (5) | C29A—N21—C22—C23 | 74.4 (6) |
C19A—N11—C12—C13 | 77.2 (6) | O214—N21—C22—C23 | −39.1 (5) |
N11—C12—C13—C14 | 12.4 (6) | N21—C22—C23—C24 | 15.5 (6) |
C121—C12—C13—C14 | −105.3 (6) | C221—C22—C23—C24 | −103.2 (6) |
C12—C13—C14—O114 | 16.5 (6) | C22—C23—C24—O214 | 13.9 (6) |
C12—C13—C14—C15 | −100.2 (6) | C22—C23—C24—C25 | −102.0 (6) |
O114—C14—C15—C15A | −47.5 (7) | O214—C24—C25—C25A | −49.8 (7) |
C13—C14—C15—C15A | 66.8 (7) | C23—C24—C25—C25A | 65.1 (7) |
C14—C15—C15A—C16 | −171.7 (6) | C24—C25—C25A—C26 | −169.3 (6) |
C14—C15—C15A—C19A | 8.7 (8) | C24—C25—C25A—C29A | 10.9 (9) |
C19A—C15A—C16—C17 | −1.4 (10) | C29A—C25A—C26—C27 | −0.7 (10) |
C15—C15A—C16—C17 | 179.1 (6) | C25—C25A—C26—C27 | 179.5 (6) |
C15A—C16—C17—C18 | −0.2 (10) | C25A—C26—C27—C28 | 1.1 (10) |
C15A—C16—C17—C171 | −178.7 (6) | C25A—C26—C27—C271 | −178.1 (7) |
C16—C17—C18—C19 | 0.9 (10) | C26—C27—C28—C29 | −1.3 (10) |
C171—C17—C18—C19 | 179.4 (6) | C271—C27—C28—C29 | 177.9 (7) |
C17—C18—C19—C19A | −0.1 (10) | C27—C28—C29—C29A | 1.1 (11) |
C18—C19—C19A—C15A | −1.5 (9) | C28—C29—C29A—C25A | −0.6 (10) |
C18—C19—C19A—N11 | 179.2 (6) | C28—C29—C29A—N21 | −180.0 (6) |
C16—C15A—C19A—C19 | 2.2 (9) | C26—C25A—C29A—C29 | 0.4 (9) |
C15—C15A—C19A—C19 | −178.2 (6) | C25—C25A—C29A—C29 | −179.7 (6) |
C16—C15A—C19A—N11 | −178.6 (5) | C26—C25A—C29A—N21 | 179.7 (6) |
C15—C15A—C19A—N11 | 1.0 (9) | C25—C25A—C29A—N21 | −0.4 (9) |
O114—N11—C19A—C19 | −153.1 (5) | O214—N21—C29A—C29 | −152.2 (5) |
C12—N11—C19A—C19 | 97.0 (6) | C22—N21—C29A—C29 | 98.3 (7) |
O114—N11—C19A—C15A | 27.6 (7) | O214—N21—C29A—C25A | 28.4 (7) |
C12—N11—C19A—C15A | −82.2 (7) | C22—N21—C29A—C25A | −81.1 (7) |
C19A—N11—O114—C14 | −66.2 (5) | C29A—N21—O214—C24 | −67.4 (6) |
C12—N11—O114—C14 | 49.4 (5) | C22—N21—O214—C24 | 49.1 (5) |
C15—C14—O114—N11 | 79.2 (6) | C23—C24—O214—N21 | −39.4 (6) |
C13—C14—O114—N11 | −41.3 (6) | C25—C24—O214—N21 | 81.2 (6) |
N11—C12—C121—C126 | −94.3 (7) | N21—C22—C221—C222 | 90.0 (7) |
C13—C12—C121—C126 | 21.9 (9) | C23—C22—C221—C222 | −153.8 (6) |
N11—C12—C121—C122 | 83.1 (7) | N21—C22—C221—C226 | −86.0 (7) |
C13—C12—C121—C122 | −160.7 (6) | C23—C22—C221—C226 | 30.1 (9) |
C126—C121—C122—C123 | −0.6 (10) | C226—C221—C222—C223 | −0.5 (10) |
C12—C121—C122—C123 | −178.1 (6) | C22—C221—C222—C223 | −176.8 (6) |
C126—C121—C122—Cl12 | 177.6 (5) | C226—C221—C222—Cl22 | 177.0 (5) |
C12—C121—C122—Cl12 | 0.1 (9) | C22—C221—C222—Cl22 | 0.7 (9) |
C121—C122—C123—C124 | 0.1 (11) | C221—C222—C223—C224 | −0.5 (10) |
Cl12—C122—C123—C124 | −178.1 (6) | Cl22—C222—C223—C224 | −178.0 (5) |
C122—C123—C124—C125 | 0.7 (11) | C222—C223—C224—C225 | 0.7 (10) |
C123—C124—C125—C126 | −0.9 (12) | C223—C224—C225—C226 | 0.0 (11) |
C122—C121—C126—C125 | 0.4 (10) | C224—C225—C226—C221 | −1.0 (10) |
C12—C121—C126—C125 | 177.8 (7) | C222—C221—C226—C225 | 1.2 (10) |
C124—C125—C126—C121 | 0.3 (11) | C22—C221—C226—C225 | 177.5 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23A···O114 | 0.99 | 2.34 | 3.305 (8) | 165 |
C226—H226···N11 | 0.95 | 2.57 | 3.402 (9) | 146 |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C16H12Cl2FNO | C16H13ClFNO | C18H19NO | C16H14ClNO |
Mr | 324.17 | 289.72 | 265.34 | 271.73 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 9.2907 (11), 10.8720 (9), 13.4523 (13) | 9.0768 (13), 10.9461 (9), 12.9971 (18) | 9.7687 (9), 10.3022 (17), 14.239 (2) | 8.8558 (19), 7.3585 (13), 9.9622 (18) |
α, β, γ (°) | 90, 95.964 (8), 90 | 90, 99.768 (9), 90 | 90, 108.222 (10), 90 | 90, 101.622 (17), 90 |
V (Å3) | 1351.4 (2) | 1272.6 (3) | 1361.1 (3) | 635.9 (2) |
Z | 4 | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.49 | 0.31 | 0.08 | 0.29 |
Crystal size (mm) | 0.35 × 0.06 × 0.06 | 0.32 × 0.27 × 0.22 | 0.33 × 0.27 × 0.12 | 0.25 × 0.15 × 0.07 |
Data collection | ||||
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD 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 | 0.868, 0.971 | 0.894, 0.936 | 0.962, 0.991 | 0.919, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19650, 3105, 1774 | 18555, 2918, 2085 | 20555, 3133, 1788 | 10226, 2889, 2400 |
Rint | 0.103 | 0.055 | 0.096 | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.649 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.121, 1.07 | 0.047, 0.137, 1.04 | 0.063, 0.135, 1.08 | 0.038, 0.078, 1.08 |
No. of reflections | 3105 | 2918 | 3133 | 2889 |
No. of parameters | 190 | 181 | 183 | 172 |
No. of restraints | 0 | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.043P)2 + 1.1028P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0685P)2 + 1.0363P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0346P)2 + 1.1025P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.0138P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.38, −0.44 | 0.29, −0.37 | 0.27, −0.26 | 0.23, −0.22 |
Absolute structure | ? | ? | ? | Flack (1983), 1323 Bijvoet pairs |
Absolute structure parameter | ? | ? | ? | 0.07 (6) |
(VII) | |
Crystal data | |
Chemical formula | C17H16ClNO |
Mr | 285.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 8.7150 (9), 10.406 (2), 15.312 (4) |
α, β, γ (°) | 99.547 (19), 90.621 (14), 96.514 (13) |
V (Å3) | 1359.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.15 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker-Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan SADABS 2.10 (Sheldrick, 2003) |
Tmin, Tmax | 0.949, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34637, 6196, 4084 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.113, 0.308, 1.15 |
No. of reflections | 6196 |
No. of parameters | 365 |
No. of restraints | 0 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0668P)2 + 15.6862P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.67, −0.55 |
Absolute structure | ? |
Absolute structure parameter | ? |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXL97 and PLATON.
Compound | Five-membered ring | Six-membered ring | ||||
Q2 | ϕ2 | Q | θ | ϕ | ||
(I) | 0.436 (3) | 198.2 (4) | 0.623 (3) | 52.9 (3) | 346.3 (3) | |
(II) | 0.438 (3) | 199.3 (3) | 0.621 (2) | 52.0 (2) | 346.2 (3) | |
(III) | 0.433 (2) | 189.2 (3) | 0.606 (2) | 49.1 (2) | 347.6 (3) | |
(IV) | 0.441 (2) | 193.8 (3) | 0.625 (2) | 53.9 (2) | 346.8 (2) | |
(V)a | 0.447 (3) | 197.4 (4) | 0.618 (3) | 51.0 (3) | 341.9 (4) | |
(VI)a | 0.436 (6) | 195.7 (8) | 0.620 (5) | 51.3 (3) | 344.5 (7) |
Note: (a) data taken from Gómez et al. (2008); puckering parameters for five-membered rings are defined for the atom sequence O14—N1—C2—C3—C4, and those for six-membered rings are defined for the atom sequence O14—N1—C9a—C5a—C5—C4. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | C3—H3B···N1i | 0.99 | 2.72 | 3.617 (3) | 151 | |
C4—H4···F26ii | 1.00 | 2.41 | 3.325 (3) | 152 | ||
C23—H23···Cg1a,iii | 0.95 | 2.51 | 3.359 (3) | 149 | ||
(II) | C3—H3B···N1i | 0.99 | 2.62 | 3.417 (3) | 137 | |
C4—H4···F26ii | 1.00 | 2.41 | 3.356 (3) | 158 | ||
C23—H23···Cg1a,iii | 0.95 | 2.49 | 3.324 (3) | 147 | ||
(III) | C8—H8···N1iv | 0.95 | 2.52 | 3.395 (3) | 153 | |
C3—H3B···Cg1a,v | 0.99 | 2.77 | 3.465 (3) | 127 | ||
(IV) | C3—H3B···Cl22vi | 0.99 | 2.81 | 3.781 (3) | 169 | |
C4—H4···O14vii | 1.00 | 2.53 | 3.344 (3) | 138 | ||
C6—H6···Cg1a,viii | 0.95 | 2.83 | 3.657 (2) | 146 | ||
C8—H8···Cg2b,ix | 0.95 | 2.65 | 3.571 (2) | 163 | ||
C23—H23···Cg1a,x | 0.95 | 2.68 | 3.415 (2) | 134 |
Notes: (a) Cg1 represents the centroid of the C5a/C6–C9/C9a ring; (b) Cg2 represents the centroid of the C21–C26 ring. Symmetry codes: (i) -x+3/2, y-1/2, -z+1/2; (ii) -x+2, -y+1, -z+1; (iii) x-1/2, -y+3/2, z+1/2; (iv) -x+3/2, y+1/2, -z+1/2; (v) -x+1, -y+2, -z; (vi) -x+1, y-0.5, -z+1; (vii) -x+1, y-1/2, -z; (viii) -x, y-1/2, -z; (ix) x-1, y, z; (x) -x+1, y+1/2, -z+1. |
We report here the structures of four new substituted 2-aryl-1,4-epoxytetrahydro-1-benzazepines, namely (2SR,4RS)-7-chloro-2-exo-(2-chloro-6-fluorophenyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine, (I), (2SR,4RS)-2-exo-(2-chloro-6-fluorophenyl)-2,3,4,5- tetrahydro-1H-1,4-epoxy-1-benzazepine, (II), (2SR,4RS)-7-methyl-2-exo-(4-methylphenyl)-2,3,4,5- tetrahydro-1H-1,4-epoxy-1-benzazepine, (III), and (2S,4R)-2-exo-(2-chlorophenyl)-2,3,4,5-tetrahydro-1H- 1,4-epoxy-1-benzazepine, (IV) (Fig. 1). The work reported here is a continuation of our structural study (Acosta et al., 2008; Blanco et al., 2008; Gómez et al., 2008) of 2-substituted 1,4-epoxytetrahydro-1-benzazepines, which included two close analogues of the present compounds, namely compounds (V) and (VI) (see scheme): compounds (I)–(IV) were all synthesized using our previously reported synthetic approach (Gómez Ayala et al., 2006), with the eventual aim of identifying structurally novel antiparasitic compounds which are active against Trypanosoma cruzi and Leishmania chagasi parasites (Palma et al., 2009).
Compounds (I)–(III) all crystallize as racemates, while the crystals of (IV) contain only a single enantiomer, (2S,4R), in the crystal selected for data collection. Given the racemic nature of (I)–(III) and the absence of any reagent in the synthetic procedure likely to be able to provide enantiomeric selectivity, it seems probable that compound (IV) is, in fact, produced as a mixture of (2S,4R) and (2R,4S) enantiomers, but that it happens to crystallize as a conglomerate rather than as a racemate. In this connection, it is interesting to note that, while (V) crystallizes as a racemate in space group Pna21, (VI) crystallizes as a single enantiomer in space group P212121 (Gómez et al., 2008).
Compounds (I) and (II), which differ only in the presence of the 7-chloro substituent in (I), are isomorphous, with similar unit-cell dimensions and similar atomic coordinates for the corresponding atoms. However, they are not strictly isostructural (Acosta et al., 2009), as the direction-specific intermolecular interactions in the two crystal structures are subtly different, as discussed below. Although pairs of analogous compounds carrying, respectively, a methyl or a chloro substituent at equivalent sites are not infrequently isomorphous, no such relationship is evident for (III) and (V), which crystallize, respectively, in space groups P21/n and Pna21 and which exhibit entirely different modes of supramolecular aggregation.
The ring-puckering parameters (Cremer & Pople, 1975) for (I)–(IV) are collected in Table 1, along with those for (V) and (VI) (Gómez et al., 2008) for comparison. All six compounds exhibit very similar shapes for the fused heterocyclic ring system. The five-membered ring component in (I), (II), (V) and (VI) adopts a nearly perfect half-chair conformation, for which the idealized value of the puckering angle ϕ is (36k +18)°, where k represents an integer; the conformations in (III) and (IV) are intermediate between half-chair and envelope forms, for which the idealized value of ϕ is 36k°. The six-membered ring components all adopt conformations closer to the half-chair form, for which the ideal values of the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, than to the envelope conformation, where the ideal values of the puckering angles are θ = 54.7° and ϕ = 60k°.
The supramolecular aggregation in (I)–(IV) is dominated by C—H···O, C—H···N and C—H···π(arene) hydrogen bonds, augmented by aromatic π–π stacking interactions in (II) only. There are short intermolecular C—H···F contacts in (I) and (II) and an intermolecular C—H···Cl contact in (IV). None of these contacts is likely to be of structural significance, firstly because the C—H bonds involved are of low acidity, and secondly because it has been well established that F and Cl atoms when bound to C atoms are extremely poor acceptors of hydrogen bonds, even from donors such as O or N (Aakeröy et al., 1999; Brammer et al., 2001; Howard et al., 1996; Thallapally & Nangia, 2001). Similarly, in the intermolecular C—H···N contacts in (I) and (II), involving a C—H bond of low acidity, the H···N distances are probably too long for these contacts to be of structural significance.
On this basis, the molecules of (I) are linked by just a single C—H···π(arene) hydrogen bond (Table 2) to form a simple chain running parallel to the [101] direction (Fig. 2), with no direction-specific interactions between adjacent chains. Entirely analogous chains are formed in (II), but these chains are now linked into sheets by a π–π stacking interaction. The fused aryl rings in the molecules at (x, y, z) and (1 - x, 1 - y, -z) are strictly parallel with an interplanar spacing of 3.426 (2) Å; the ring-centroid separation is 3.810 (2) Å, with a ring-centroid offset of 1.667 (2) Å. The effect of this interaction is to link the chains parallel to [101] into a sheet lying parallel to (101) (Fig. 3).
The crystal structure of (III) also contains sheets but these are built solely from two hydrogen bonds, one each of C—H···N and C—H···π(arene) types (Table 2). The C—H···π(arene) interaction links a pair of molecules into a cyclic centrosymmetric dimer centred at (1/2, 1, 0), and this dimer can be regarded as the building block for the sheet formation. The C—H···N hydrogen bond links the reference dimer centred at (1/2, 1, 0) directly to four other such dimers, those centred at (0, 1/2, -1/2), (0, 3/2, -1/2), (1, 1/2, 1/2) and (1, 3/2, 1/2), and propagation of these two interactions then generates a hydrogen-bonded sheet lying parallel to (101) (Fig. 4).
Four hydrogen bonds, one of C—H···O type and three of C—H···π(arene) type, combine to link the molecules of (IV) into a single three-dimensional framework. The formation of the framework is most readily analysed in terms of two independent two-dimensional substructures. The three hydrogen bonds involving atoms C4, C6 and C8 as the donors combine to generate a sheet lying parallel to (001) (Fig. 5), while the two hydrogen bonds having C4 and C23 as the donors combine to form a sheet parallel to (100) (Fig. 6). The combination of the (100) and (001) sheets is sufficient to generate a three-dimensional structure.
It is of interest briefly to compare the aggregation in (I)–(IV) with that in the related compounds (V) and (VI) (Gómez et al., 2008) (see scheme). In (V), the molecules are linked by a combination of C—H···O and C—H···N hydrogen bonds to form a chain of edge-fused R33(12) (Bernstein et al., 1995) rings, while in (VI), a combination of two C—H···O hydrogen bonds and one C—H···π(arene) hydrogen bonds generates a three-dimensional framework structure. In the course of the present work, we have also investigated (VII), which crystallizes in space group P1 with Z' = 2, but we have been unable to refine this below R = 0.10. However, it is clear that the two independent molecules within the asymmetric unit are linked by one C—H···O hydrogen bond and one C—H···N hydrogen bond to form an R22(8) motif, but that there are no further direction-specific interactions between the molecules. Thus despite the very close constitutional, configurational and conformational similarity between the molecules of compounds (I)–(VII), no two of these compounds exhibits the same pattern of supramolecular aggregation.