The structures of three compounds, namely 7-methoxy-2-[3-(trifluoromethyl)phenyl]-9
H-indeno[1,2-
c]pyridazin-9-one, C
19H
11F
3N
2O
2, (I
d), 6-methoxy-2-[3-(trifluoromethyl)phenyl]-9
H-indeno[1,2-
c]pyridazin-9-one, C
19H
11F
3N
2O
2, (II
d), and 2-methyl-6-(4,4,4-trifluorobutoxy)-9
H-indeno[1,2-
c]pyridazin-9-one, C
16H
13F
3N
2O
2, (II
f), which are potent reversible type-B monoamine oxidase (MAO-B) inhibitors, are presented and discussed. Compounds (I
d) and (II
d) crystallize in a nearly planar conformation. The crystal structures are stabilized by weak C—H
O hydrogen bonds. The packing is dominated by π–π stacking interactions between the heterocyclic central moieties of centrosymmetrically related molecules. In compound (II
f), the trifluoroethyl termination is almost perpendicular to the plane of the ring.
Supporting information
CCDC references: 251302; 251303; 251304
The syntheses of compounds (Id), (IId) and (IIf) will be reported elsewhere. The compounds were crystallized by slow overnight evaporation of acetonitrile solutions.
In all three compounds, the trifluoro groups present very large ellipsoids. In two cases, for (Id) and (IIdB), a disordered model with the trifluoro group distributed over two sites could be defined, whereas no satisfactory models could be defined for (IIdA) and (IIf). The disordered models were constrained to have chemically reasonable dimensions, whereas restraints on the anisotropic displacement parameters were used for all trifluoro groups. The H atoms were introduced geometrically and treated as riding, with C—H distances of 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C). Please check added text..
For all compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1995); cell refinement: CAD-4 EXPRESS. Data reduction: PLATON (Spek, 2003) for (Id), (IId); HELENA (Spek, 1997) for (IIf). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(Id) 7-methoxy-2-[3-(trifluoromethyl)phenyl]-9
H-indeno[1,2-
c]pyridazin-9-one
top
Crystal data top
C19H11F3N2O2 | Z = 2 |
Mr = 356.30 | F(000) = 364 |
Triclinic, P1 | Dx = 1.495 Mg m−3 |
Hall symbol: -P 1 | Melting point: 204 K |
a = 7.768 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 8.750 (2) Å | Cell parameters from 24 reflections |
c = 12.703 (2) Å | θ = 14–47° |
α = 89.01 (1)° | µ = 1.05 mm−1 |
β = 81.59 (2)° | T = 293 K |
γ = 68.05 (1)° | Prism, yellow |
V = 791.6 (3) Å3 | 0.30 × 0.18 × 0.04 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2692 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 75.1°, θmin = 3.5° |
θ/2θ scans | h = −9→9 |
Absorption correction: analytical (Alcock, 1970) | k = −10→0 |
Tmin = 0.743, Tmax = 0.959 | l = −15→15 |
3495 measured reflections | 3 standard reflections every 200 reflections |
3273 independent reflections | intensity decay: 3% |
Refinement top
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 = 1.03 | w = 1/[σ2(Fo2) + (0.0722P)2 + 0.1799P] where P = (Fo2 + 2Fc2)/3 |
3273 reflections | (Δ/σ)max = 0.004 |
263 parameters | Δρmax = 0.20 e Å−3 |
62 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C19H11F3N2O2 | γ = 68.05 (1)° |
Mr = 356.30 | V = 791.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.768 (2) Å | Cu Kα radiation |
b = 8.750 (2) Å | µ = 1.05 mm−1 |
c = 12.703 (2) Å | T = 293 K |
α = 89.01 (1)° | 0.30 × 0.18 × 0.04 mm |
β = 81.59 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2692 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.015 |
Tmin = 0.743, Tmax = 0.959 | 3 standard reflections every 200 reflections |
3495 measured reflections | intensity decay: 3% |
3273 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 62 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.20 e Å−3 |
3273 reflections | Δρmin = −0.22 e Å−3 |
263 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.22710 (19) | 0.46525 (18) | −0.12994 (12) | 0.0668 (4) | |
O2 | 0.9023 (2) | 0.3901 (2) | −0.34062 (13) | 0.0762 (4) | |
N1 | 0.3258 (2) | 0.88744 (19) | 0.05287 (13) | 0.0585 (4) | |
N2 | 0.1629 (2) | 0.9429 (2) | 0.12131 (13) | 0.0583 (4) | |
C1 | 0.5166 (2) | 0.6854 (2) | −0.09655 (14) | 0.0489 (4) | |
C2 | 0.3525 (2) | 0.7651 (2) | −0.01540 (13) | 0.0481 (4) | |
C3 | 0.2209 (2) | 0.6904 (2) | −0.01855 (13) | 0.0474 (4) | |
C4 | 0.3003 (3) | 0.5568 (2) | −0.10466 (14) | 0.0506 (4) | |
C5 | 0.4848 (2) | 0.5612 (2) | −0.15071 (14) | 0.0490 (4) | |
C6 | 0.6139 (3) | 0.4648 (2) | −0.23252 (15) | 0.0563 (4) | |
H6 | 0.5908 | 0.3838 | −0.2678 | 0.068* | |
C7 | 0.7802 (3) | 0.4914 (2) | −0.26118 (15) | 0.0570 (4) | |
C8 | 0.8124 (3) | 0.6147 (2) | −0.20849 (16) | 0.0585 (5) | |
H8 | 0.9234 | 0.6320 | −0.2288 | 0.070* | |
C9 | 0.6809 (3) | 0.7117 (2) | −0.12613 (16) | 0.0566 (4) | |
H9 | 0.7034 | 0.7935 | −0.0914 | 0.068* | |
C10 | 0.0590 (3) | 0.7437 (2) | 0.05089 (14) | 0.0502 (4) | |
H10 | −0.0304 | 0.6965 | 0.0519 | 0.060* | |
C11 | 0.0339 (3) | 0.8758 (2) | 0.12194 (14) | 0.0500 (4) | |
C12 | −0.1365 (3) | 0.9466 (2) | 0.20275 (14) | 0.0529 (4) | |
C13 | −0.3010 (3) | 0.9231 (2) | 0.19324 (16) | 0.0594 (5) | |
H13 | −0.3057 | 0.8635 | 0.1345 | 0.071* | |
C14 | −0.4578 (3) | 0.9873 (3) | 0.26997 (18) | 0.0695 (5) | |
H14 | −0.5664 | 0.9697 | 0.2628 | 0.083* | |
C15 | −0.4544 (3) | 1.0766 (3) | 0.35650 (19) | 0.0754 (6) | |
H15 | −0.5600 | 1.1196 | 0.4081 | 0.091* | |
C16 | −0.2916 (4) | 1.1022 (3) | 0.36619 (17) | 0.0736 (6) | |
C17 | −0.1337 (3) | 1.0377 (2) | 0.29052 (16) | 0.0647 (5) | |
H17 | −0.0252 | 1.0552 | 0.2983 | 0.078* | |
C18 | −0.2855 (6) | 1.2009 (4) | 0.4598 (3) | 0.1084 (10) | |
F1A | −0.2136 (9) | 1.0963 (10) | 0.5344 (5) | 0.153 (3) | 0.55 |
F2A | −0.2153 (16) | 1.3005 (11) | 0.4370 (5) | 0.202 (4) | 0.55 |
F3A | −0.4626 (6) | 1.2830 (8) | 0.5139 (4) | 0.1372 (17) | 0.55 |
F1B | −0.0997 (8) | 1.1990 (7) | 0.4616 (5) | 0.1152 (18) | 0.45 |
F2B | −0.3689 (14) | 1.3563 (8) | 0.4583 (8) | 0.184 (3) | 0.45 |
F3B | −0.3021 (18) | 1.1424 (14) | 0.5509 (5) | 0.174 (4) | 0.45 |
C19 | 1.0785 (3) | 0.4037 (3) | −0.37258 (19) | 0.0794 (7) | |
H19A | 1.0593 | 0.5108 | −0.4000 | 0.119* | |
H19B | 1.1515 | 0.3205 | −0.4269 | 0.119* | |
H19C | 1.1441 | 0.3889 | −0.3124 | 0.119* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0660 (8) | 0.0679 (9) | 0.0782 (9) | −0.0382 (7) | −0.0084 (7) | −0.0218 (7) |
O2 | 0.0651 (9) | 0.0824 (10) | 0.0762 (9) | −0.0270 (8) | 0.0046 (7) | −0.0207 (8) |
N1 | 0.0714 (10) | 0.0541 (9) | 0.0604 (9) | −0.0372 (8) | −0.0040 (7) | −0.0098 (7) |
N2 | 0.0709 (10) | 0.0537 (9) | 0.0583 (9) | −0.0346 (8) | −0.0026 (7) | −0.0092 (7) |
C1 | 0.0570 (10) | 0.0442 (9) | 0.0525 (9) | −0.0248 (7) | −0.0137 (7) | 0.0020 (7) |
C2 | 0.0587 (10) | 0.0428 (8) | 0.0501 (9) | −0.0257 (7) | −0.0126 (7) | 0.0014 (7) |
C3 | 0.0555 (9) | 0.0422 (8) | 0.0512 (9) | −0.0234 (7) | −0.0143 (7) | 0.0001 (7) |
C4 | 0.0562 (10) | 0.0483 (9) | 0.0539 (9) | −0.0245 (8) | −0.0143 (8) | −0.0036 (7) |
C5 | 0.0542 (9) | 0.0459 (9) | 0.0523 (9) | −0.0223 (7) | −0.0146 (7) | −0.0001 (7) |
C6 | 0.0606 (11) | 0.0541 (10) | 0.0580 (10) | −0.0242 (8) | −0.0121 (8) | −0.0072 (8) |
C7 | 0.0564 (10) | 0.0563 (10) | 0.0552 (10) | −0.0171 (8) | −0.0096 (8) | −0.0011 (8) |
C8 | 0.0541 (10) | 0.0604 (11) | 0.0668 (11) | −0.0274 (9) | −0.0109 (8) | 0.0053 (9) |
C9 | 0.0618 (11) | 0.0535 (10) | 0.0643 (11) | −0.0314 (9) | −0.0129 (8) | −0.0007 (8) |
C10 | 0.0553 (9) | 0.0471 (9) | 0.0554 (9) | −0.0261 (8) | −0.0114 (7) | −0.0010 (7) |
C11 | 0.0604 (10) | 0.0433 (9) | 0.0507 (9) | −0.0233 (8) | −0.0118 (8) | 0.0015 (7) |
C12 | 0.0660 (11) | 0.0422 (9) | 0.0514 (9) | −0.0215 (8) | −0.0076 (8) | 0.0007 (7) |
C13 | 0.0646 (11) | 0.0540 (10) | 0.0602 (11) | −0.0226 (9) | −0.0094 (9) | −0.0005 (8) |
C14 | 0.0635 (12) | 0.0663 (13) | 0.0745 (13) | −0.0221 (10) | −0.0035 (10) | 0.0002 (10) |
C15 | 0.0780 (14) | 0.0638 (13) | 0.0725 (13) | −0.0209 (11) | 0.0107 (11) | −0.0034 (10) |
C16 | 0.1017 (17) | 0.0552 (12) | 0.0592 (12) | −0.0296 (12) | 0.0043 (11) | −0.0084 (9) |
C17 | 0.0819 (14) | 0.0570 (11) | 0.0602 (11) | −0.0329 (10) | −0.0064 (10) | −0.0057 (9) |
C18 | 0.147 (3) | 0.105 (2) | 0.0790 (18) | −0.065 (2) | 0.0210 (19) | −0.0344 (16) |
F1A | 0.138 (4) | 0.209 (5) | 0.089 (4) | −0.033 (3) | −0.028 (3) | −0.052 (3) |
F2A | 0.320 (9) | 0.208 (7) | 0.144 (4) | −0.219 (7) | 0.102 (6) | −0.106 (5) |
F3A | 0.135 (3) | 0.139 (4) | 0.120 (3) | −0.048 (3) | 0.035 (2) | −0.085 (3) |
F1B | 0.142 (4) | 0.118 (4) | 0.090 (3) | −0.055 (3) | −0.007 (3) | −0.057 (3) |
F2B | 0.193 (7) | 0.091 (3) | 0.220 (8) | 0.004 (4) | −0.031 (6) | −0.091 (4) |
F3B | 0.287 (11) | 0.226 (8) | 0.069 (3) | −0.191 (8) | 0.051 (5) | −0.041 (4) |
C19 | 0.0688 (14) | 0.0930 (17) | 0.0716 (14) | −0.0298 (12) | 0.0043 (11) | −0.0040 (12) |
Geometric parameters (Å, º) top
O1—C4 | 1.212 (2) | C11—C12 | 1.484 (3) |
O2—C7 | 1.351 (2) | C12—C17 | 1.389 (3) |
O2—C19 | 1.418 (3) | C12—C13 | 1.390 (3) |
N1—C2 | 1.325 (2) | C13—C14 | 1.381 (3) |
N1—N2 | 1.351 (2) | C13—H13 | 0.9300 |
N2—C11 | 1.336 (2) | C14—C15 | 1.369 (3) |
C1—C9 | 1.378 (3) | C14—H14 | 0.9300 |
C1—C5 | 1.412 (2) | C15—C16 | 1.387 (3) |
C1—C2 | 1.466 (3) | C15—H15 | 0.9300 |
C2—C3 | 1.409 (2) | C16—C17 | 1.380 (3) |
C3—C10 | 1.352 (3) | C16—C18 | 1.499 (4) |
C3—C4 | 1.501 (2) | C17—H17 | 0.9300 |
C4—C5 | 1.481 (2) | C18—F2A | 1.200 (5) |
C5—C6 | 1.375 (3) | C18—F3B | 1.266 (8) |
C6—C7 | 1.392 (3) | C18—F2B | 1.270 (7) |
C6—H6 | 0.9300 | C18—F1A | 1.338 (7) |
C7—C8 | 1.396 (3) | C18—F3A | 1.372 (5) |
C8—C9 | 1.389 (3) | C18—F1B | 1.440 (6) |
C8—H8 | 0.9300 | C19—H19A | 0.9600 |
C9—H9 | 0.9300 | C19—H19B | 0.9600 |
C10—C11 | 1.416 (2) | C19—H19C | 0.9600 |
C10—H10 | 0.9300 | | |
| | | |
C7—O2—C19 | 119.26 (17) | C12—C13—H13 | 119.6 |
C2—N1—N2 | 117.56 (15) | C15—C14—C13 | 120.5 (2) |
C11—N2—N1 | 121.67 (15) | C15—C14—H14 | 119.7 |
C9—C1—C5 | 119.50 (17) | C13—C14—H14 | 119.7 |
C9—C1—C2 | 132.66 (16) | C14—C15—C16 | 119.1 (2) |
C5—C1—C2 | 107.84 (15) | C14—C15—H15 | 120.4 |
N1—C2—C3 | 123.11 (17) | C16—C15—H15 | 120.4 |
N1—C2—C1 | 127.29 (16) | C17—C16—C15 | 120.9 (2) |
C3—C2—C1 | 109.60 (14) | C17—C16—C18 | 119.1 (2) |
C10—C3—C2 | 119.54 (16) | C15—C16—C18 | 120.0 (2) |
C10—C3—C4 | 132.65 (15) | C16—C17—C12 | 120.1 (2) |
C2—C3—C4 | 107.80 (15) | C16—C17—H17 | 119.9 |
O1—C4—C5 | 128.01 (17) | C12—C17—H17 | 119.9 |
O1—C4—C3 | 126.58 (17) | F2A—C18—F3B | 125.4 (6) |
C5—C4—C3 | 105.40 (13) | F2A—C18—F2B | 52.8 (5) |
C6—C5—C1 | 121.69 (17) | F3B—C18—F2B | 114.2 (6) |
C6—C5—C4 | 128.96 (15) | F2A—C18—F1A | 115.9 (7) |
C1—C5—C4 | 109.35 (15) | F3B—C18—F1A | 29.1 (6) |
C5—C6—C7 | 118.37 (17) | F2B—C18—F1A | 134.3 (5) |
C5—C6—H6 | 120.8 | F2A—C18—F3A | 107.9 (5) |
C7—C6—H6 | 120.8 | F3B—C18—F3A | 69.9 (5) |
O2—C7—C6 | 115.18 (17) | F2B—C18—F3A | 57.5 (5) |
O2—C7—C8 | 124.48 (18) | F1A—C18—F3A | 99.0 (4) |
C6—C7—C8 | 120.33 (18) | F2A—C18—F1B | 47.2 (6) |
C9—C8—C7 | 120.90 (17) | F3B—C18—F1B | 95.8 (6) |
C9—C8—H8 | 119.5 | F2B—C18—F1B | 97.1 (6) |
C7—C8—H8 | 119.5 | F1A—C18—F1B | 73.6 (5) |
C1—C9—C8 | 119.22 (17) | F3A—C18—F1B | 137.0 (3) |
C1—C9—H9 | 120.4 | F2A—C18—C16 | 114.0 (4) |
C8—C9—H9 | 120.4 | F3B—C18—C16 | 117.3 (4) |
C3—C10—C11 | 115.92 (16) | F2B—C18—C16 | 116.5 (5) |
C3—C10—H10 | 122.0 | F1A—C18—C16 | 108.2 (4) |
C11—C10—H10 | 122.0 | F3A—C18—C16 | 110.8 (3) |
N2—C11—C10 | 122.19 (17) | F1B—C18—C16 | 111.7 (3) |
N2—C11—C12 | 115.95 (16) | O2—C19—H19A | 109.5 |
C10—C11—C12 | 121.85 (16) | O2—C19—H19B | 109.5 |
C17—C12—C13 | 118.55 (19) | H19A—C19—H19B | 109.5 |
C17—C12—C11 | 120.08 (18) | O2—C19—H19C | 109.5 |
C13—C12—C11 | 121.36 (16) | H19A—C19—H19C | 109.5 |
C14—C13—C12 | 120.77 (19) | H19B—C19—H19C | 109.5 |
C14—C13—H13 | 119.6 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O1i | 0.93 | 2.54 | 3.408 (2) | 156 |
Symmetry code: (i) −x, −y+1, −z. |
(IId) 6-methoxy-2-[3-(trifluoromethyl)phenyl]-9
H-indeno[1,2-
c]pyridazin-9-one
top
Crystal data top
C19H11F3N2O2 | Z = 4 |
Mr = 356.30 | F(000) = 728 |
Triclinic, P1 | Dx = 1.507 Mg m−3 |
Hall symbol: -P 1 | Melting point: 214 K |
a = 10.306 (1) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 10.798 (1) Å | Cell parameters from 24 reflections |
c = 14.986 (1) Å | θ = 18–42° |
α = 73.453 (6)° | µ = 1.06 mm−1 |
β = 79.592 (7)° | T = 293 K |
γ = 89.422 (7)° | Plate, yellow |
V = 1570.8 (2) Å3 | 0.38 × 0.15 × 0.04 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 4032 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 71.9°, θmin = 3.1° |
θ/2θ scans | h = −12→12 |
Absorption correction: analytical (Alcock, 1970) | k = −13→0 |
Tmin = 0.689, Tmax = 0.959 | l = −18→17 |
6538 measured reflections | 3 standard reflections every 200 reflections |
6193 independent reflections | intensity decay: 2% |
Refinement top
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) = 0.147 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.065P)2 + 0.4238P] where P = (Fo2 + 2Fc2)/3 |
6193 reflections | (Δ/σ)max = 0.001 |
498 parameters | Δρmax = 0.22 e Å−3 |
86 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C19H11F3N2O2 | γ = 89.422 (7)° |
Mr = 356.30 | V = 1570.8 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.306 (1) Å | Cu Kα radiation |
b = 10.798 (1) Å | µ = 1.06 mm−1 |
c = 14.986 (1) Å | T = 293 K |
α = 73.453 (6)° | 0.38 × 0.15 × 0.04 mm |
β = 79.592 (7)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 4032 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.015 |
Tmin = 0.689, Tmax = 0.959 | 3 standard reflections every 200 reflections |
6538 measured reflections | intensity decay: 2% |
6193 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 86 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.22 e Å−3 |
6193 reflections | Δρmin = −0.27 e Å−3 |
498 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
F3 | 0.4996 (3) | 0.8514 (4) | 0.62198 (18) | 0.1688 (13) | |
F2 | 0.3435 (3) | 0.7210 (4) | 0.64617 (16) | 0.1663 (12) | |
F1 | 0.3348 (3) | 0.9054 (3) | 0.55514 (16) | 0.1635 (12) | |
O2 | 0.07242 (16) | 1.03571 (18) | −0.14894 (12) | 0.0638 (5) | |
O1 | 0.60999 (16) | 0.75863 (19) | −0.04513 (12) | 0.0641 (5) | |
N1 | 0.28645 (18) | 0.9006 (2) | 0.16846 (13) | 0.0522 (5) | |
N2 | 0.34104 (18) | 0.8603 (2) | 0.24698 (13) | 0.0523 (5) | |
C10 | 0.5288 (2) | 0.7804 (2) | 0.16210 (15) | 0.0438 (5) | |
H10 | 0.6104 | 0.7428 | 0.1608 | 0.053* | |
C1 | 0.3090 (2) | 0.9097 (2) | −0.00235 (14) | 0.0416 (5) | |
C3 | 0.4725 (2) | 0.8183 (2) | 0.08426 (15) | 0.0414 (5) | |
C17 | 0.4428 (2) | 0.8052 (3) | 0.41151 (17) | 0.0608 (7) | |
H17 | 0.3762 | 0.8639 | 0.4027 | 0.073* | |
C6 | 0.3974 (2) | 0.8935 (2) | −0.15903 (16) | 0.0489 (5) | |
H6 | 0.4634 | 0.8690 | −0.2010 | 0.059* | |
C5 | 0.4087 (2) | 0.8720 (2) | −0.06567 (15) | 0.0427 (5) | |
C11 | 0.4559 (2) | 0.8014 (2) | 0.24530 (15) | 0.0441 (5) | |
C9 | 0.1982 (2) | 0.9650 (2) | −0.03114 (16) | 0.0480 (5) | |
H9 | 0.1320 | 0.9887 | 0.0111 | 0.058* | |
C2 | 0.3502 (2) | 0.8770 (2) | 0.09068 (15) | 0.0420 (5) | |
C12 | 0.5010 (2) | 0.7588 (2) | 0.33759 (15) | 0.0491 (5) | |
C16 | 0.4821 (3) | 0.7658 (3) | 0.49834 (18) | 0.0672 (7) | |
C8 | 0.1866 (2) | 0.9852 (2) | −0.12604 (16) | 0.0482 (5) | |
C7 | 0.2867 (2) | 0.9518 (2) | −0.18989 (16) | 0.0518 (6) | |
H7 | 0.2793 | 0.9687 | −0.2531 | 0.062* | |
C19 | 0.0618 (3) | 1.0791 (3) | −0.24721 (19) | 0.0691 (8) | |
H19A | 0.1296 | 1.1446 | −0.2808 | 0.104* | |
H19B | −0.0232 | 1.1142 | −0.2529 | 0.104* | |
H19C | 0.0720 | 1.0075 | −0.2735 | 0.104* | |
C4 | 0.5131 (2) | 0.8102 (2) | −0.01548 (15) | 0.0452 (5) | |
C13 | 0.5996 (3) | 0.6711 (3) | 0.35268 (19) | 0.0670 (7) | |
H13 | 0.6400 | 0.6387 | 0.3038 | 0.080* | |
C15 | 0.5800 (3) | 0.6785 (3) | 0.5129 (2) | 0.0766 (9) | |
H15 | 0.6064 | 0.6517 | 0.5714 | 0.092* | |
C14 | 0.6384 (3) | 0.6314 (3) | 0.4397 (2) | 0.0825 (9) | |
H14 | 0.7046 | 0.5724 | 0.4489 | 0.099* | |
C18 | 0.4174 (4) | 0.8148 (5) | 0.5778 (2) | 0.1114 (14) | |
O4 | 0.57687 (17) | 0.51958 (18) | −0.23769 (12) | 0.0628 (5) | |
O3 | 1.15461 (17) | 0.3164 (2) | −0.16338 (13) | 0.0693 (5) | |
N3 | 0.81428 (18) | 0.3828 (2) | 0.07603 (13) | 0.0506 (5) | |
N4 | 0.87510 (18) | 0.34240 (19) | 0.15163 (13) | 0.0505 (5) | |
C32 | 1.0490 (2) | 0.2531 (2) | 0.23202 (16) | 0.0484 (5) | |
C21 | 0.8307 (2) | 0.4088 (2) | −0.09628 (15) | 0.0439 (5) | |
C37 | 0.9883 (2) | 0.2855 (2) | 0.31253 (16) | 0.0522 (6) | |
H37 | 0.9156 | 0.3372 | 0.3099 | 0.063* | |
C25 | 0.9298 (2) | 0.3841 (2) | −0.16543 (16) | 0.0480 (5) | |
C28 | 0.6901 (2) | 0.4758 (2) | −0.20869 (16) | 0.0495 (5) | |
C27 | 0.7873 (2) | 0.4485 (2) | −0.27753 (16) | 0.0553 (6) | |
H27 | 0.7707 | 0.4607 | −0.3384 | 0.066* | |
C23 | 1.0079 (2) | 0.3305 (2) | −0.02026 (16) | 0.0451 (5) | |
C31 | 0.9966 (2) | 0.2976 (2) | 0.14269 (15) | 0.0446 (5) | |
C22 | 0.8798 (2) | 0.3742 (2) | −0.00594 (15) | 0.0437 (5) | |
C29 | 0.7117 (2) | 0.4566 (2) | −0.11611 (16) | 0.0477 (5) | |
H29 | 0.6480 | 0.4754 | −0.0699 | 0.057* | |
C36 | 1.0349 (2) | 0.2419 (3) | 0.39629 (18) | 0.0578 (6) | |
C26 | 0.9069 (2) | 0.4040 (2) | −0.25697 (17) | 0.0552 (6) | |
H26 | 0.9716 | 0.3874 | −0.3036 | 0.066* | |
C30 | 1.0700 (2) | 0.2918 (2) | 0.05461 (16) | 0.0484 (5) | |
H30 | 1.1556 | 0.2631 | 0.0486 | 0.058* | |
C34 | 1.2030 (3) | 0.1318 (3) | 0.3225 (2) | 0.0822 (9) | |
H34 | 1.2755 | 0.0799 | 0.3257 | 0.099* | |
C35 | 1.1425 (3) | 0.1651 (3) | 0.4015 (2) | 0.0740 (8) | |
H35 | 1.1738 | 0.1359 | 0.4580 | 0.089* | |
C33 | 1.1568 (3) | 0.1750 (3) | 0.23851 (19) | 0.0651 (7) | |
H33 | 1.1983 | 0.1514 | 0.1857 | 0.078* | |
C24 | 1.0481 (2) | 0.3394 (2) | −0.12393 (16) | 0.0506 (6) | |
C38 | 0.9709 (3) | 0.2778 (4) | 0.4822 (2) | 0.0807 (9) | |
F4 | 0.8816 (5) | 0.3663 (4) | 0.4664 (3) | 0.1143 (15) | 0.77 |
F5 | 0.9093 (5) | 0.1790 (5) | 0.5501 (4) | 0.1380 (19) | 0.77 |
F6 | 1.0565 (5) | 0.3239 (6) | 0.5215 (4) | 0.1395 (18) | 0.77 |
F4A | 0.8462 (11) | 0.2952 (18) | 0.4881 (11) | 0.119 (5) | 0.23 |
F5A | 0.9840 (16) | 0.1934 (17) | 0.5578 (9) | 0.122 (5) | 0.23 |
F6A | 1.0237 (17) | 0.3857 (12) | 0.4870 (11) | 0.119 (4) | 0.23 |
C39 | 0.4728 (3) | 0.5492 (3) | −0.1696 (2) | 0.0698 (8) | |
H39A | 0.4466 | 0.4729 | −0.1176 | 0.105* | |
H39B | 0.3986 | 0.5787 | −0.1992 | 0.105* | |
H39C | 0.5040 | 0.6157 | −0.1467 | 0.105* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F3 | 0.135 (2) | 0.315 (4) | 0.1217 (18) | 0.044 (2) | −0.0479 (16) | −0.152 (2) |
F2 | 0.1192 (18) | 0.285 (4) | 0.0652 (13) | 0.030 (2) | 0.0150 (13) | −0.0247 (18) |
F1 | 0.193 (2) | 0.252 (3) | 0.0859 (15) | 0.130 (2) | −0.0550 (16) | −0.0985 (18) |
O2 | 0.0535 (10) | 0.0838 (13) | 0.0528 (10) | 0.0151 (9) | −0.0196 (8) | −0.0119 (9) |
O1 | 0.0547 (10) | 0.0911 (14) | 0.0527 (10) | 0.0274 (9) | −0.0110 (8) | −0.0305 (9) |
N1 | 0.0448 (10) | 0.0715 (14) | 0.0448 (10) | 0.0123 (9) | −0.0106 (8) | −0.0225 (10) |
N2 | 0.0480 (11) | 0.0721 (14) | 0.0414 (10) | 0.0111 (10) | −0.0115 (8) | −0.0219 (9) |
C10 | 0.0393 (11) | 0.0502 (13) | 0.0455 (12) | 0.0036 (9) | −0.0112 (9) | −0.0173 (10) |
C1 | 0.0417 (11) | 0.0423 (12) | 0.0409 (11) | −0.0006 (9) | −0.0077 (9) | −0.0120 (9) |
C3 | 0.0392 (11) | 0.0450 (12) | 0.0418 (11) | 0.0017 (9) | −0.0068 (9) | −0.0160 (9) |
C17 | 0.0555 (14) | 0.0855 (19) | 0.0458 (13) | 0.0139 (13) | −0.0147 (11) | −0.0227 (13) |
C6 | 0.0513 (13) | 0.0558 (14) | 0.0420 (12) | 0.0053 (11) | −0.0079 (10) | −0.0187 (10) |
C5 | 0.0428 (11) | 0.0444 (12) | 0.0422 (11) | 0.0021 (9) | −0.0080 (9) | −0.0144 (9) |
C11 | 0.0412 (11) | 0.0511 (13) | 0.0431 (12) | 0.0015 (10) | −0.0113 (9) | −0.0161 (10) |
C9 | 0.0409 (11) | 0.0568 (14) | 0.0468 (12) | 0.0060 (10) | −0.0078 (10) | −0.0162 (11) |
C2 | 0.0390 (11) | 0.0467 (13) | 0.0413 (11) | 0.0014 (9) | −0.0073 (9) | −0.0146 (10) |
C12 | 0.0441 (12) | 0.0616 (15) | 0.0426 (12) | −0.0007 (11) | −0.0108 (10) | −0.0151 (11) |
C16 | 0.0614 (16) | 0.098 (2) | 0.0447 (13) | 0.0063 (15) | −0.0141 (12) | −0.0219 (14) |
C8 | 0.0436 (12) | 0.0515 (14) | 0.0486 (12) | 0.0001 (10) | −0.0141 (10) | −0.0095 (10) |
C7 | 0.0596 (14) | 0.0574 (15) | 0.0395 (11) | 0.0011 (11) | −0.0146 (10) | −0.0121 (11) |
C19 | 0.0705 (17) | 0.079 (2) | 0.0596 (16) | 0.0120 (15) | −0.0310 (14) | −0.0104 (14) |
C4 | 0.0442 (12) | 0.0510 (13) | 0.0424 (12) | 0.0040 (10) | −0.0075 (9) | −0.0172 (10) |
C13 | 0.0681 (16) | 0.087 (2) | 0.0533 (15) | 0.0217 (15) | −0.0229 (13) | −0.0255 (14) |
C15 | 0.0757 (19) | 0.109 (3) | 0.0485 (15) | 0.0114 (18) | −0.0277 (14) | −0.0175 (16) |
C14 | 0.082 (2) | 0.106 (3) | 0.0660 (18) | 0.0341 (19) | −0.0322 (16) | −0.0247 (17) |
C18 | 0.095 (2) | 0.206 (4) | 0.0513 (17) | 0.051 (3) | −0.0309 (17) | −0.058 (2) |
O4 | 0.0610 (10) | 0.0777 (12) | 0.0536 (10) | 0.0189 (9) | −0.0232 (8) | −0.0178 (9) |
O3 | 0.0518 (10) | 0.1024 (15) | 0.0600 (11) | 0.0171 (10) | −0.0065 (8) | −0.0363 (10) |
N3 | 0.0454 (10) | 0.0631 (13) | 0.0455 (10) | 0.0072 (9) | −0.0106 (8) | −0.0179 (9) |
N4 | 0.0478 (11) | 0.0615 (13) | 0.0436 (10) | 0.0064 (9) | −0.0101 (8) | −0.0167 (9) |
C32 | 0.0439 (12) | 0.0523 (14) | 0.0484 (13) | −0.0018 (10) | −0.0104 (10) | −0.0123 (11) |
C21 | 0.0447 (12) | 0.0450 (12) | 0.0434 (11) | 0.0003 (10) | −0.0088 (9) | −0.0147 (10) |
C37 | 0.0489 (13) | 0.0590 (15) | 0.0496 (13) | 0.0036 (11) | −0.0115 (10) | −0.0157 (11) |
C25 | 0.0477 (12) | 0.0506 (13) | 0.0473 (12) | 0.0013 (10) | −0.0081 (10) | −0.0171 (10) |
C28 | 0.0521 (13) | 0.0489 (13) | 0.0485 (13) | 0.0023 (11) | −0.0150 (10) | −0.0120 (10) |
C27 | 0.0635 (15) | 0.0635 (16) | 0.0429 (12) | 0.0034 (12) | −0.0158 (11) | −0.0179 (11) |
C23 | 0.0418 (11) | 0.0474 (13) | 0.0492 (12) | 0.0019 (10) | −0.0081 (10) | −0.0189 (10) |
C31 | 0.0422 (11) | 0.0470 (13) | 0.0469 (12) | −0.0008 (10) | −0.0094 (9) | −0.0162 (10) |
C22 | 0.0407 (11) | 0.0465 (13) | 0.0460 (12) | −0.0007 (9) | −0.0092 (9) | −0.0159 (10) |
C29 | 0.0482 (12) | 0.0512 (14) | 0.0453 (12) | 0.0042 (10) | −0.0093 (10) | −0.0158 (10) |
C36 | 0.0597 (15) | 0.0647 (16) | 0.0507 (14) | 0.0007 (13) | −0.0161 (12) | −0.0155 (12) |
C26 | 0.0584 (14) | 0.0627 (16) | 0.0467 (13) | 0.0040 (12) | −0.0069 (11) | −0.0209 (12) |
C30 | 0.0405 (11) | 0.0566 (14) | 0.0520 (13) | 0.0046 (10) | −0.0112 (10) | −0.0201 (11) |
C34 | 0.0763 (19) | 0.101 (2) | 0.0697 (19) | 0.0389 (18) | −0.0281 (16) | −0.0168 (17) |
C35 | 0.0785 (19) | 0.089 (2) | 0.0532 (16) | 0.0156 (17) | −0.0266 (14) | −0.0094 (15) |
C33 | 0.0615 (15) | 0.0772 (19) | 0.0572 (15) | 0.0203 (14) | −0.0126 (12) | −0.0197 (14) |
C24 | 0.0459 (12) | 0.0588 (15) | 0.0512 (13) | 0.0026 (11) | −0.0075 (10) | −0.0232 (11) |
C38 | 0.086 (2) | 0.111 (3) | 0.0530 (16) | 0.0137 (19) | −0.0221 (15) | −0.0302 (17) |
F4 | 0.144 (3) | 0.141 (3) | 0.073 (2) | 0.071 (3) | −0.029 (2) | −0.052 (2) |
F5 | 0.156 (4) | 0.143 (3) | 0.078 (3) | −0.002 (3) | 0.038 (3) | −0.011 (2) |
F6 | 0.125 (3) | 0.226 (5) | 0.115 (4) | 0.018 (3) | −0.049 (2) | −0.110 (4) |
F4A | 0.083 (5) | 0.215 (13) | 0.065 (7) | 0.018 (7) | −0.007 (5) | −0.055 (9) |
F5A | 0.160 (11) | 0.146 (9) | 0.037 (4) | 0.035 (9) | −0.008 (7) | 0.002 (5) |
F6A | 0.160 (10) | 0.120 (7) | 0.093 (8) | −0.011 (7) | −0.013 (7) | −0.064 (6) |
C39 | 0.0658 (17) | 0.084 (2) | 0.0667 (17) | 0.0295 (15) | −0.0231 (14) | −0.0277 (15) |
Geometric parameters (Å, º) top
F3—C18 | 1.293 (4) | O3—C24 | 1.208 (3) |
F2—C18 | 1.341 (5) | N3—C22 | 1.318 (3) |
F1—C18 | 1.302 (4) | N3—N4 | 1.355 (2) |
O2—C8 | 1.352 (3) | N4—C31 | 1.336 (3) |
O2—C19 | 1.437 (3) | C32—C33 | 1.389 (3) |
O1—C4 | 1.214 (3) | C32—C37 | 1.390 (3) |
N1—C2 | 1.320 (3) | C32—C31 | 1.485 (3) |
N1—N2 | 1.354 (2) | C21—C29 | 1.375 (3) |
N2—C11 | 1.337 (3) | C21—C25 | 1.399 (3) |
C10—C3 | 1.354 (3) | C21—C22 | 1.478 (3) |
C10—C11 | 1.411 (3) | C37—C36 | 1.380 (3) |
C10—H10 | 0.9300 | C37—H37 | 0.9300 |
C1—C9 | 1.366 (3) | C25—C26 | 1.390 (3) |
C1—C5 | 1.407 (3) | C25—C24 | 1.483 (3) |
C1—C2 | 1.476 (3) | C28—C27 | 1.395 (3) |
C3—C2 | 1.406 (3) | C28—C29 | 1.402 (3) |
C3—C4 | 1.505 (3) | C27—C26 | 1.374 (3) |
C17—C12 | 1.382 (3) | C27—H27 | 0.9300 |
C17—C16 | 1.382 (3) | C23—C30 | 1.353 (3) |
C17—H17 | 0.9300 | C23—C22 | 1.398 (3) |
C6—C5 | 1.378 (3) | C23—C24 | 1.509 (3) |
C6—C7 | 1.386 (3) | C31—C30 | 1.415 (3) |
C6—H6 | 0.9300 | C29—H29 | 0.9300 |
C5—C4 | 1.470 (3) | C36—C35 | 1.378 (4) |
C11—C12 | 1.485 (3) | C36—C38 | 1.489 (4) |
C9—C8 | 1.403 (3) | C26—H26 | 0.9300 |
C9—H9 | 0.9300 | C30—H30 | 0.9300 |
C12—C13 | 1.387 (3) | C34—C35 | 1.375 (4) |
C16—C15 | 1.378 (4) | C34—C33 | 1.381 (4) |
C16—C18 | 1.485 (4) | C34—H34 | 0.9300 |
C8—C7 | 1.394 (3) | C35—H35 | 0.9300 |
C7—H7 | 0.9300 | C33—H33 | 0.9300 |
C19—H19A | 0.9600 | C38—F5A | 1.263 (11) |
C19—H19B | 0.9600 | C38—F4A | 1.288 (11) |
C19—H19C | 0.9600 | C38—F6A | 1.316 (11) |
C13—C14 | 1.383 (4) | C38—F6 | 1.318 (5) |
C13—H13 | 0.9300 | C38—F5 | 1.318 (5) |
C15—C14 | 1.378 (4) | C38—F4 | 1.322 (5) |
C15—H15 | 0.9300 | C39—H39A | 0.9600 |
C14—H14 | 0.9300 | C39—H39B | 0.9600 |
O4—C28 | 1.353 (3) | C39—H39C | 0.9600 |
O4—C39 | 1.441 (3) | | |
| | | |
C8—O2—C19 | 118.57 (19) | C25—C21—C22 | 107.74 (19) |
C2—N1—N2 | 117.16 (18) | C36—C37—C32 | 120.7 (2) |
C11—N2—N1 | 121.36 (18) | C36—C37—H37 | 119.6 |
C3—C10—C11 | 115.83 (19) | C32—C37—H37 | 119.6 |
C3—C10—H10 | 122.1 | C26—C25—C21 | 119.5 (2) |
C11—C10—H10 | 122.1 | C26—C25—C24 | 130.7 (2) |
C9—C1—C5 | 121.1 (2) | C21—C25—C24 | 109.81 (19) |
C9—C1—C2 | 131.3 (2) | O4—C28—C27 | 115.6 (2) |
C5—C1—C2 | 107.64 (18) | O4—C28—C29 | 123.8 (2) |
C10—C3—C2 | 119.13 (19) | C27—C28—C29 | 120.6 (2) |
C10—C3—C4 | 133.05 (19) | C26—C27—C28 | 121.1 (2) |
C2—C3—C4 | 107.82 (18) | C26—C27—H27 | 119.4 |
C12—C17—C16 | 120.9 (2) | C28—C27—H27 | 119.4 |
C12—C17—H17 | 119.5 | C30—C23—C22 | 118.8 (2) |
C16—C17—H17 | 119.5 | C30—C23—C24 | 133.2 (2) |
C5—C6—C7 | 119.5 (2) | C22—C23—C24 | 107.99 (19) |
C5—C6—H6 | 120.3 | N4—C31—C30 | 122.5 (2) |
C7—C6—H6 | 120.3 | N4—C31—C32 | 115.20 (19) |
C6—C5—C1 | 120.2 (2) | C30—C31—C32 | 122.3 (2) |
C6—C5—C4 | 130.0 (2) | N3—C22—C23 | 124.6 (2) |
C1—C5—C4 | 109.79 (18) | N3—C22—C21 | 125.92 (19) |
N2—C11—C10 | 122.57 (19) | C23—C22—C21 | 109.51 (19) |
N2—C11—C12 | 115.20 (19) | C21—C29—C28 | 117.4 (2) |
C10—C11—C12 | 122.23 (19) | C21—C29—H29 | 121.3 |
C1—C9—C8 | 118.4 (2) | C28—C29—H29 | 121.3 |
C1—C9—H9 | 120.8 | C35—C36—C37 | 120.4 (2) |
C8—C9—H9 | 120.8 | C35—C36—C38 | 118.8 (2) |
N1—C2—C3 | 123.86 (19) | C37—C36—C38 | 120.7 (2) |
N1—C2—C1 | 126.83 (19) | C27—C26—C25 | 119.0 (2) |
C3—C2—C1 | 109.29 (18) | C27—C26—H26 | 120.5 |
C17—C12—C13 | 118.4 (2) | C25—C26—H26 | 120.5 |
C17—C12—C11 | 119.9 (2) | C23—C30—C31 | 115.9 (2) |
C13—C12—C11 | 121.7 (2) | C23—C30—H30 | 122.0 |
C15—C16—C17 | 120.4 (3) | C31—C30—H30 | 122.0 |
C15—C16—C18 | 119.1 (3) | C35—C34—C33 | 120.5 (3) |
C17—C16—C18 | 120.5 (3) | C35—C34—H34 | 119.8 |
O2—C8—C7 | 123.7 (2) | C33—C34—H34 | 119.8 |
O2—C8—C9 | 115.4 (2) | C34—C35—C36 | 119.4 (2) |
C7—C8—C9 | 120.9 (2) | C34—C35—H35 | 120.3 |
C6—C7—C8 | 119.9 (2) | C36—C35—H35 | 120.3 |
C6—C7—H7 | 120.0 | C34—C33—C32 | 120.8 (3) |
C8—C7—H7 | 120.0 | C34—C33—H33 | 119.6 |
O2—C19—H19A | 109.5 | C32—C33—H33 | 119.6 |
O2—C19—H19B | 109.5 | O3—C24—C25 | 128.4 (2) |
H19A—C19—H19B | 109.5 | O3—C24—C23 | 126.8 (2) |
O2—C19—H19C | 109.5 | C25—C24—C23 | 104.81 (18) |
H19A—C19—H19C | 109.5 | F5A—C38—F4A | 106.3 (10) |
H19B—C19—H19C | 109.5 | F5A—C38—F6A | 105.3 (10) |
O1—C4—C5 | 128.6 (2) | F4A—C38—F6A | 105.9 (11) |
O1—C4—C3 | 125.9 (2) | F5A—C38—F6 | 71.5 (9) |
C5—C4—C3 | 105.41 (17) | F4A—C38—F6 | 129.2 (9) |
C14—C13—C12 | 120.6 (3) | F6A—C38—F6 | 36.7 (6) |
C14—C13—H13 | 119.7 | F5A—C38—F5 | 37.1 (8) |
C12—C13—H13 | 119.7 | F4A—C38—F5 | 72.9 (8) |
C14—C15—C16 | 119.1 (2) | F6A—C38—F5 | 130.3 (7) |
C14—C15—H15 | 120.5 | F6—C38—F5 | 104.9 (4) |
C16—C15—H15 | 120.5 | F5A—C38—F4 | 130.2 (8) |
C15—C14—C13 | 120.6 (3) | F4A—C38—F4 | 35.9 (8) |
C15—C14—H14 | 119.7 | F6A—C38—F4 | 73.5 (8) |
C13—C14—H14 | 119.7 | F6—C38—F4 | 106.0 (4) |
F3—C18—F1 | 109.5 (4) | F5—C38—F4 | 105.5 (4) |
F3—C18—F2 | 102.9 (3) | F5A—C38—C36 | 112.2 (9) |
F1—C18—F2 | 103.8 (3) | F4A—C38—C36 | 114.6 (8) |
F3—C18—C16 | 113.7 (3) | F6A—C38—C36 | 111.9 (8) |
F1—C18—C16 | 114.7 (3) | F6—C38—C36 | 112.5 (3) |
F2—C18—C16 | 111.1 (4) | F5—C38—C36 | 113.2 (4) |
C28—O4—C39 | 118.07 (18) | F4—C38—C36 | 114.0 (3) |
C22—N3—N4 | 116.97 (18) | O4—C39—H39A | 109.5 |
C31—N4—N3 | 121.19 (18) | O4—C39—H39B | 109.5 |
C33—C32—C37 | 118.2 (2) | H39A—C39—H39B | 109.5 |
C33—C32—C31 | 121.2 (2) | O4—C39—H39C | 109.5 |
C37—C32—C31 | 120.5 (2) | H39A—C39—H39C | 109.5 |
C29—C21—C25 | 122.3 (2) | H39B—C39—H39C | 109.5 |
C29—C21—C22 | 129.9 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O3i | 0.93 | 2.50 | 3.418 (3) | 168 |
C33—H33···O1i | 0.93 | 2.58 | 3.320 (3) | 137 |
C30—H30···O1i | 0.93 | 2.42 | 3.322 (3) | 164 |
Symmetry code: (i) −x+2, −y+1, −z. |
(IIf) 2-methyl-6-(4,4,4-trifluorobutoxy)-9
H-indeno[1,2-
c]pyridazin-9-one
top
Crystal data top
C16H13F3N2O2 | F(000) = 664 |
Mr = 322.28 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/c | Melting point: 116 K |
Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54178 Å |
a = 4.918 (2) Å | Cell parameters from 25 reflections |
b = 11.978 (6) Å | θ = 30–38° |
c = 24.659 (5) Å | µ = 1.08 mm−1 |
β = 96.65 (2)° | T = 293 K |
V = 1442.8 (10) Å3 | Needle, yellow |
Z = 4 | 0.40 × 0.10 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1160 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 71.9°, θmin = 3.6° |
θ/2θ scans | h = −6→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→10 |
Tmin = 0.672, Tmax = 0.900 | l = −30→30 |
4511 measured reflections | 3 standard reflections every 200 reflections |
2816 independent reflections | intensity decay: 6% |
Refinement top
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.249 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.1307P)2] where P = (Fo2 + 2Fc2)/3 |
2816 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.25 e Å−3 |
24 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C16H13F3N2O2 | V = 1442.8 (10) Å3 |
Mr = 322.28 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 4.918 (2) Å | µ = 1.08 mm−1 |
b = 11.978 (6) Å | T = 293 K |
c = 24.659 (5) Å | 0.40 × 0.10 × 0.10 mm |
β = 96.65 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1160 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.057 |
Tmin = 0.672, Tmax = 0.900 | 3 standard reflections every 200 reflections |
4511 measured reflections | intensity decay: 6% |
2816 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.068 | 24 restraints |
wR(F2) = 0.249 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.25 e Å−3 |
2816 reflections | Δρmin = −0.26 e Å−3 |
209 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | −0.0043 (9) | 0.2002 (4) | −0.00081 (14) | 0.1391 (16) | |
F3 | 0.3718 (9) | 0.2522 (3) | 0.03748 (15) | 0.1220 (14) | |
F2 | 0.3277 (10) | 0.0920 (4) | 0.00307 (16) | 0.1381 (15) | |
O2 | 0.3519 (6) | 0.2059 (2) | 0.19211 (12) | 0.0587 (9) | |
O1 | 1.2839 (7) | 0.4498 (3) | 0.36004 (14) | 0.0777 (11) | |
N1 | 1.1566 (9) | 0.0585 (3) | 0.34306 (16) | 0.0662 (12) | |
N2 | 1.3635 (9) | 0.0236 (4) | 0.38086 (17) | 0.0722 (13) | |
C1 | 0.9177 (9) | 0.2222 (4) | 0.29706 (16) | 0.0480 (11) | |
C15 | 0.1329 (11) | 0.1206 (4) | 0.08398 (19) | 0.0705 (15) | |
H15A | 0.2982 | 0.0929 | 0.1049 | 0.085* | |
H15B | 0.0102 | 0.0577 | 0.0764 | 0.085* | |
C8 | 0.5450 (9) | 0.2537 (4) | 0.22866 (16) | 0.0492 (11) | |
C14 | −0.0014 (10) | 0.2035 (5) | 0.11881 (19) | 0.0652 (14) | |
H14A | −0.1214 | 0.2509 | 0.0948 | 0.078* | |
H14B | −0.1155 | 0.1623 | 0.1414 | 0.078* | |
C9 | 0.7168 (9) | 0.1787 (4) | 0.26015 (17) | 0.0535 (12) | |
H9 | 0.6947 | 0.1019 | 0.2560 | 0.064* | |
C13 | 0.1866 (10) | 0.2774 (4) | 0.15546 (19) | 0.0588 (13) | |
H13A | 0.3008 | 0.3214 | 0.1340 | 0.071* | |
H13B | 0.0813 | 0.3279 | 0.1757 | 0.071* | |
C12 | 1.7425 (11) | 0.0496 (5) | 0.4499 (2) | 0.0875 (18) | |
H12A | 1.7336 | −0.0304 | 0.4483 | 0.131* | |
H12B | 1.7155 | 0.0742 | 0.4860 | 0.131* | |
H12C | 1.9186 | 0.0740 | 0.4414 | 0.131* | |
C3 | 1.2875 (9) | 0.2475 (4) | 0.36425 (17) | 0.0530 (12) | |
C7 | 0.5770 (9) | 0.3682 (4) | 0.23509 (18) | 0.0570 (12) | |
H7 | 0.4613 | 0.4167 | 0.2139 | 0.068* | |
C5 | 0.9522 (9) | 0.3378 (4) | 0.30377 (16) | 0.0505 (11) | |
C10 | 1.4916 (10) | 0.2128 (5) | 0.40277 (18) | 0.0610 (13) | |
H10 | 1.6034 | 0.2634 | 0.4235 | 0.073* | |
C2 | 1.1265 (9) | 0.1662 (4) | 0.33574 (17) | 0.0513 (11) | |
C4 | 1.1873 (10) | 0.3600 (4) | 0.34528 (19) | 0.0558 (12) | |
C11 | 1.5240 (10) | 0.0979 (5) | 0.40945 (19) | 0.0655 (14) | |
C6 | 0.7817 (10) | 0.4107 (4) | 0.27308 (18) | 0.0583 (13) | |
H6 | 0.8030 | 0.4874 | 0.2777 | 0.070* | |
C16 | 0.2047 (13) | 0.1643 (5) | 0.0319 (2) | 0.0797 (16) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.111 (3) | 0.229 (4) | 0.070 (2) | 0.024 (3) | −0.020 (2) | 0.047 (3) |
F3 | 0.135 (3) | 0.132 (3) | 0.104 (3) | −0.046 (3) | 0.038 (3) | −0.005 (2) |
F2 | 0.188 (4) | 0.139 (3) | 0.094 (3) | 0.031 (3) | 0.048 (3) | −0.021 (2) |
O2 | 0.0596 (19) | 0.0589 (19) | 0.0540 (17) | −0.0017 (17) | −0.0088 (16) | −0.0012 (15) |
O1 | 0.085 (3) | 0.066 (2) | 0.078 (3) | −0.010 (2) | −0.006 (2) | −0.0154 (19) |
N1 | 0.073 (3) | 0.062 (3) | 0.059 (2) | 0.007 (2) | −0.013 (2) | −0.005 (2) |
N2 | 0.078 (3) | 0.074 (3) | 0.060 (3) | 0.018 (3) | −0.013 (2) | −0.002 (2) |
C1 | 0.050 (3) | 0.055 (3) | 0.038 (2) | 0.001 (2) | −0.001 (2) | −0.005 (2) |
C15 | 0.087 (4) | 0.061 (3) | 0.061 (3) | 0.005 (3) | −0.003 (3) | −0.005 (3) |
C8 | 0.049 (3) | 0.057 (3) | 0.040 (2) | −0.003 (2) | 0.000 (2) | −0.001 (2) |
C14 | 0.059 (3) | 0.082 (3) | 0.052 (3) | 0.002 (3) | −0.009 (3) | 0.005 (3) |
C9 | 0.055 (3) | 0.051 (3) | 0.054 (3) | 0.000 (2) | 0.005 (2) | −0.003 (2) |
C13 | 0.059 (3) | 0.064 (3) | 0.051 (2) | 0.008 (2) | −0.006 (2) | −0.005 (2) |
C12 | 0.081 (4) | 0.114 (5) | 0.062 (3) | 0.022 (4) | −0.018 (3) | 0.004 (3) |
C3 | 0.045 (3) | 0.067 (3) | 0.047 (2) | 0.002 (2) | 0.005 (2) | −0.013 (2) |
C7 | 0.058 (3) | 0.060 (3) | 0.051 (3) | 0.008 (2) | 0.001 (2) | 0.006 (2) |
C5 | 0.056 (3) | 0.049 (3) | 0.046 (2) | 0.001 (2) | 0.000 (2) | −0.005 (2) |
C10 | 0.052 (3) | 0.081 (4) | 0.048 (3) | 0.002 (3) | −0.002 (2) | −0.014 (3) |
C2 | 0.053 (3) | 0.056 (3) | 0.045 (2) | 0.005 (2) | 0.005 (2) | −0.006 (2) |
C4 | 0.058 (3) | 0.053 (3) | 0.057 (3) | −0.008 (3) | 0.010 (2) | −0.009 (2) |
C11 | 0.061 (3) | 0.082 (4) | 0.051 (3) | 0.011 (3) | −0.006 (3) | −0.007 (3) |
C6 | 0.069 (3) | 0.049 (3) | 0.057 (3) | 0.000 (3) | 0.007 (3) | −0.004 (2) |
C16 | 0.080 (4) | 0.094 (4) | 0.063 (3) | 0.004 (3) | 0.002 (3) | −0.001 (3) |
Geometric parameters (Å, º) top
F1—C16 | 1.304 (6) | C14—H14A | 0.9700 |
F3—C16 | 1.333 (6) | C14—H14B | 0.9700 |
F2—C16 | 1.312 (6) | C9—H9 | 0.9300 |
O2—C8 | 1.358 (5) | C13—H13A | 0.9700 |
O2—C13 | 1.429 (5) | C13—H13B | 0.9700 |
O1—C4 | 1.214 (5) | C12—C11 | 1.495 (6) |
N1—C2 | 1.309 (6) | C12—H12A | 0.9600 |
N1—N2 | 1.364 (5) | C12—H12B | 0.9600 |
N2—C11 | 1.335 (6) | C12—H12C | 0.9600 |
C1—C9 | 1.367 (6) | C3—C10 | 1.364 (6) |
C1—C5 | 1.403 (6) | C3—C2 | 1.392 (6) |
C1—C2 | 1.479 (6) | C3—C4 | 1.492 (6) |
C15—C16 | 1.467 (7) | C7—C6 | 1.390 (6) |
C15—C14 | 1.514 (7) | C7—H7 | 0.9300 |
C15—H15A | 0.9700 | C5—C6 | 1.375 (6) |
C15—H15B | 0.9700 | C5—C4 | 1.477 (6) |
C8—C7 | 1.388 (6) | C10—C11 | 1.394 (7) |
C8—C9 | 1.404 (6) | C10—H10 | 0.9300 |
C14—C13 | 1.504 (6) | C6—H6 | 0.9300 |
| | | |
C8—O2—C13 | 118.1 (3) | C11—C12—H12C | 109.5 |
C2—N1—N2 | 117.4 (4) | H12A—C12—H12C | 109.5 |
C11—N2—N1 | 120.4 (4) | H12B—C12—H12C | 109.5 |
C9—C1—C5 | 121.6 (4) | C10—C3—C2 | 118.0 (4) |
C9—C1—C2 | 130.6 (4) | C10—C3—C4 | 133.0 (4) |
C5—C1—C2 | 107.8 (4) | C2—C3—C4 | 109.0 (4) |
C16—C15—C14 | 115.3 (5) | C8—C7—C6 | 120.2 (4) |
C16—C15—H15A | 108.4 | C8—C7—H7 | 119.9 |
C14—C15—H15A | 108.4 | C6—C7—H7 | 119.9 |
C16—C15—H15B | 108.4 | C6—C5—C1 | 120.3 (4) |
C14—C15—H15B | 108.4 | C6—C5—C4 | 130.2 (4) |
H15A—C15—H15B | 107.5 | C1—C5—C4 | 109.5 (4) |
O2—C8—C7 | 123.6 (4) | C3—C10—C11 | 116.6 (5) |
O2—C8—C9 | 115.3 (4) | C3—C10—H10 | 121.7 |
C7—C8—C9 | 121.1 (4) | C11—C10—H10 | 121.7 |
C13—C14—C15 | 116.7 (4) | N1—C2—C3 | 124.8 (4) |
C13—C14—H14A | 108.1 | N1—C2—C1 | 126.5 (4) |
C15—C14—H14A | 108.1 | C3—C2—C1 | 108.7 (4) |
C13—C14—H14B | 108.1 | O1—C4—C5 | 127.9 (4) |
C15—C14—H14B | 108.1 | O1—C4—C3 | 127.1 (4) |
H14A—C14—H14B | 107.3 | C5—C4—C3 | 105.0 (4) |
C1—C9—C8 | 117.8 (4) | N2—C11—C10 | 122.9 (4) |
C1—C9—H9 | 121.1 | N2—C11—C12 | 115.5 (5) |
C8—C9—H9 | 121.1 | C10—C11—C12 | 121.6 (5) |
O2—C13—C14 | 107.0 (4) | C5—C6—C7 | 119.1 (4) |
O2—C13—H13A | 110.3 | C5—C6—H6 | 120.4 |
C14—C13—H13A | 110.3 | C7—C6—H6 | 120.4 |
O2—C13—H13B | 110.3 | F1—C16—F2 | 105.2 (5) |
C14—C13—H13B | 110.3 | F1—C16—F3 | 103.7 (5) |
H13A—C13—H13B | 108.6 | F2—C16—F3 | 105.0 (5) |
C11—C12—H12A | 109.5 | F1—C16—C15 | 114.0 (5) |
C11—C12—H12B | 109.5 | F2—C16—C15 | 114.3 (5) |
H12A—C12—H12B | 109.5 | F3—C16—C15 | 113.5 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15B···O1i | 0.97 | 2.60 | 3.309 (6) | 130 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
| (Id) | (IId) | (IIf) |
Crystal data |
Chemical formula | C19H11F3N2O2 | C19H11F3N2O2 | C16H13F3N2O2 |
Mr | 356.30 | 356.30 | 322.28 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 7.768 (2), 8.750 (2), 12.703 (2) | 10.306 (1), 10.798 (1), 14.986 (1) | 4.918 (2), 11.978 (6), 24.659 (5) |
α, β, γ (°) | 89.01 (1), 81.59 (2), 68.05 (1) | 73.453 (6), 79.592 (7), 89.422 (7) | 90, 96.65 (2), 90 |
V (Å3) | 791.6 (3) | 1570.8 (2) | 1442.8 (10) |
Z | 2 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 1.05 | 1.06 | 1.08 |
Crystal size (mm) | 0.30 × 0.18 × 0.04 | 0.38 × 0.15 × 0.04 | 0.40 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Analytical (Alcock, 1970) | Analytical (Alcock, 1970) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.743, 0.959 | 0.689, 0.959 | 0.672, 0.900 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3495, 3273, 2692 | 6538, 6193, 4032 | 4511, 2816, 1160 |
Rint | 0.015 | 0.015 | 0.057 |
(sin θ/λ)max (Å−1) | 0.627 | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.139, 1.03 | 0.048, 0.147, 1.04 | 0.068, 0.249, 0.98 |
No. of reflections | 3273 | 6193 | 2816 |
No. of parameters | 263 | 498 | 209 |
No. of restraints | 62 | 86 | 24 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.22 | 0.22, −0.27 | 0.25, −0.26 |
Hydrogen-bond geometry (Å, º) for (Id) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O1i | 0.93 | 2.54 | 3.408 (2) | 156 |
Symmetry code: (i) −x, −y+1, −z. |
Geometry of short Cg···Cg ring interactions for (Id) (Å,°) topCgi | Cgj | Cgi···Cgj | α |
CgA | CgCi | 3.722 (1) | 0.27 (13) |
CgA | CgDii | 3.885 (1) | 18.56 (11) |
CgB | CgBi | 3.427 (1) | 0.00 (15) |
CgB | CgDii | 3.811 (1) | 18.75 (12) |
CgC | CgCii | 3.841 (1) | 0.00 (15) |
Cgi and Cgj denote the centres of gravity for rings i and j in (Id). α is the dihedral angle between the planes of rings i and j. Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) −x, 2 − y, −z. |
Hydrogen-bond geometry (Å, º) for (IId) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O3i | 0.93 | 2.50 | 3.418 (3) | 168 |
C33—H33···O1i | 0.93 | 2.58 | 3.320 (3) | 137 |
C30—H30···O1i | 0.93 | 2.42 | 3.322 (3) | 164 |
Symmetry code: (i) −x+2, −y+1, −z. |
Geometry of short Cg···Cg ring interactions for (IId) (Å,°) topCgi | Cgj | Cgi···Cgj | α |
CgA1 | CgC2ii | 3.686 (1) | 5.17 (11) |
CgA2 | CgD2iii | 3.874 (1) | 15.66 (15) |
CgB1 | CgB1i | 3.464 (1) | 0.00 (14) |
CgC1 | CgA1i | 3.753 (1) | 1.86 (12) |
CgC1 | CgA2ii | 3.587 (1) | 6.77 (11) |
CgC2 | CgB2iii | 3.525 (1) | 1.82 (11) |
Cgi and Cgj denote the centres of gravity for rings i and j in (IId). α denotes the dihedral angle between the planes of rings i and j. Symmetry codes: (i) 1 − x,2 − y,-z; (ii) 1 − x,1 − y,-z; (iii) 2 − x,1 − y,-z. |
Hydrogen-bond geometry (Å, º) for (IIf) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15B···O1i | 0.97 | 2.60 | 3.309 (6) | 130 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
5H-Indeno[1,2-c]pyridazin-5-ones, (Ia)-(Ie), have been described by Testa (Kneubühler et al., 1993, 1995) to be reversible and selective MAO-B inhibitors. As part of a project aiming to improve the biological activity of compounds of this family, we recently described a general MAO-B pharmacophore. This led to the rational design of compounds (If) and (IIf), bearing a hydrophobic (4,4,4)-trifluorobutoxy side chain on positions 7 and 6, respectively, of the indeno[1,2-c]pyridazin-5-one ring (Ooms et al., 2003). The values of IC50 given for compounds (Ia)-(Id) are taken from Kneubühler et al. (1995). \sch
We planned for synthesis of (If), possessing the side chain on position 7, using the strategy successfully used by Testa (Kneubühler et al., 1995) to produce two related compounds, (Ic) and (Id). Surprisingly, we found that the resulting product possesses the isomeric structure (IIf), with the side chain on position 6.
In order to validate the results obtained by Testa, we repeated the synthesis of (Id). We found that the major isomer (47% yield, yellow, m.p. 487 K, 1H NMR spectrum identical to that published) was in fact (IId) and not (Id), as proved unambiguously by the X-ray crystal data. The minor product (3.5% yield, orange, m.p. 477 K), on the other hand, presented the structure (Id), again proved by X-ray crystallography.
Compound (Id) (Fig. 1), the minor isomer, crystallized in the triclinic P1 space group. This compound possesses the methoxy group on position C7 of the 5H-indeno[1,2-c]pyridazine ring [O2—C7—C8—C9 torsion angle −178.7 (2)°]. The dihedral angle between the phenyl ring D and the adjacent pyridazine ring C is approximately 19° (Fig. 1). Atom C10 acts as a donor for a weak intermolecular C—H···O hydrogen-bond with carboxyl atom O1 (Table 1). The crystal packing is dominated by π–π stacking interactions between the centrosymmetrically related molecules (Fig. 2, Table 2). The stacking geometry is such that rings A, B, C of one molecule are superimposed on rings C, B and A, respectively, of a symmetry-related molecule at (1 − x, 1 − y, −z). On the other hand, π–π stacking interactions arise between one molecule and its symmetry-related molecule at (-x, 2 − y, −z) (Table 2).
Compound (IId) (Fig. 3), the major isomer, also crystallized in the triclinic P1 space group. In this compound, the asymmetric unit contains two independent molecules, one, (IIdA), with the methoxy group located on position 6 (atom C8) of the 5H-indeno[1,2-c]pyridazine ring and defined by a C19—O2—C8—C9 torsion angle of 169.8 (2)°, and the other, (IIdB), with the methoxy group also located at the same position 6 (atom C28) but with a value for the same torsion angle of 0.5 (3)°. This leads to an arrangement in which atom C10 in molecule (IIdA) acts as donor for a weak intermolecular C—H···O hydrogen bond with carboxyl atom O3 in (IIdB) (Table 3). Atoms C30 and C33 in molecule (IIdB) are also donors for weak intermolecular C—H···O hydrogen bonds with carboxyl atom O1 of a neighbouring (IIdA) molecule (Table 3). The crystal packing is dominated by π–π stacking interactions between the heterocyclic central moiety of (IIdA) and its centrosymmetrically related structure at (1 − x, 2 − y, −z), and between the heterocyclic central moiety of (IIdB) and its centrosymmetrically related structure at (2 − x, 1 − y, −z) (Fig. 4, Table 4). Other π–π stacking interactions arise between (IIdA) and a symmetry-related (IIdB) molecule situated at (1 − x, 1 − y, −z), and also between (IIdB) and a symmetry-related (IIdA) molecule at (1 − x, 1 − y, −z) (Fig. 4, Table 4).
Derivative (IIf), bearing a hydrophobic 4,4,4-triflorobutoxy side-chain at position 6 (atom C8), crystallized in the monoclinic P21/c space group (Fig. 5). The molecular structure of (IIf) shows a nearly planar conformation of the 5H-indeno[1,2-c]pyridazin-5-one ring, except for the trifluoroethyl termination of the side-chain, which is almost perpendicular to the plane of the ring [O2—C13—C14—C15 torsion angle −60.6 (5)° and C13—C14—C15 bond angle 116.6 (4)°]. Atom C14 acts as donor for a weak intermolecular C—H···O hydrogen bond with carboxyl atom O1 of a neighbouring molecule (Table 5). The crystalline cohesion is maintained by π–π stacking interactions between one molecule and the translated structures at (x − 1, y, z) and (1 + x, y, z), leading to a parallel arrangement along the a axis (Fig. 6).