Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102000197/de1179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102000197/de1179Isup2.hkl |
CCDC reference: 183005
The title compound was prepared by dissolving 16-(4-cyanobenzylidene)-17-oxo-5-androsten-3β-ol (1 g, 2.49 mmol) in dry toluene (150 ml) by refluxing and then adding cyclohexanone (10 ml). Traces of moisture were removed by azeotropic distillation. The distillation was continued at a slow rate during dropwise addition of a solution of aluminium isopropoxide (1 g) in dry toluene. The reaction mixture was refluxed for 4 h and left overnight. The next day, the solvent was removed by steam distillation. The solid thus obtained was filtered, dried and crystallized from methanol to afford crystals of (I) (yield 0.6 g, 60.3%; m.p 528–531 K).
All H atoms were treated as riding, with C—H = 0.93–0.98 Å, and Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for all others. Are these the correct restraints?
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: DIRDIF98 (Beurskens et al., 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
C27H29NO2 | Dx = 1.216 Mg m−3 |
Mr = 399.51 | Cu Kα radiation, λ = 1.5418 Å |
Orthorhombic, P22121 | Cell parameters from 25 reflections |
a = 7.7638 (10) Å | θ = 20–30° |
b = 8.4584 (10) Å | µ = 0.59 mm−1 |
c = 33.220 (5) Å | T = 293 K |
V = 2181.5 (5) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.25 × 0.10 mm |
F(000) = 856 |
Enraf-Nonius CAD-4 diffractometer | 1957 reflections with I > 2s(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 67.9°, θmin = 2.7° |
ω/2θ scans | h = 0→9 |
Absorption correction: ψ-scan (North et al., 1968) | k = −10→5 |
Tmin = 0.842, Tmax = 0.943 | l = 0→39 |
2365 measured reflections | 2 standard reflections every 120 min |
2363 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.039 | Calculated w = 1/[σ2(Fo2) + (0.0491P)2 + 0.2836P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.105 | (Δ/σ)max = 0.005 |
S = 1.11 | Δρmax = 0.14 e Å−3 |
2363 reflections | Δρmin = −0.12 e Å−3 |
272 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0029 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.9 (5) |
C27H29NO2 | V = 2181.5 (5) Å3 |
Mr = 399.51 | Z = 4 |
Orthorhombic, P22121 | Cu Kα radiation |
a = 7.7638 (10) Å | µ = 0.59 mm−1 |
b = 8.4584 (10) Å | T = 293 K |
c = 33.220 (5) Å | 0.30 × 0.25 × 0.10 mm |
Enraf-Nonius CAD-4 diffractometer | 1957 reflections with I > 2s(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.014 |
Tmin = 0.842, Tmax = 0.943 | 2 standard reflections every 120 min |
2365 measured reflections | intensity decay: none |
2363 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.105 | Δρmax = 0.14 e Å−3 |
S = 1.11 | Δρmin = −0.12 e Å−3 |
2363 reflections | Absolute structure: Flack (1983) |
272 parameters | Absolute structure parameter: 0.9 (5) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.3161 (4) | −1.0084 (4) | −0.24648 (8) | 0.0751 (9) | |
H1A | −0.4399 | −1.0233 | −0.2456 | 0.090* | |
H1B | −0.2942 | −0.8955 | −0.2475 | 0.090* | |
C2 | −0.2469 (5) | −1.0835 (5) | −0.28461 (9) | 0.0905 (11) | |
H2A | −0.2836 | −1.1931 | −0.2857 | 0.109* | |
H2B | −0.2951 | −1.0295 | −0.3078 | 0.109* | |
C3 | −0.0555 (5) | −1.0768 (4) | −0.28677 (9) | 0.0747 (9) | |
C4 | 0.0336 (4) | −1.0807 (4) | −0.24841 (9) | 0.0655 (8) | |
H4 | 0.1533 | −1.0803 | −0.2488 | 0.079* | |
C5 | −0.0439 (4) | −1.0847 (3) | −0.21254 (8) | 0.0547 (7) | |
C6 | 0.0593 (4) | −1.1122 (4) | −0.17502 (7) | 0.0616 (7) | |
H6A | 0.1810 | −1.1037 | −0.1813 | 0.074* | |
H6B | 0.0378 | −1.2184 | −0.1652 | 0.074* | |
C7 | 0.0142 (3) | −0.9940 (4) | −0.14231 (7) | 0.0578 (7) | |
H7A | 0.0771 | −1.0201 | −0.1180 | 0.069* | |
H7B | 0.0494 | −0.8891 | −0.1508 | 0.069* | |
C8 | −0.1770 (3) | −0.9931 (3) | −0.13326 (7) | 0.0474 (6) | |
H8 | −0.2098 | −1.0976 | −0.1231 | 0.057* | |
C9 | −0.2804 (3) | −0.9595 (3) | −0.17214 (7) | 0.0484 (6) | |
H9 | −0.2448 | −0.8541 | −0.1811 | 0.058* | |
C10 | −0.2381 (4) | −1.0745 (3) | −0.20766 (7) | 0.0529 (6) | |
C11 | −0.4756 (3) | −0.9482 (4) | −0.16359 (8) | 0.0629 (8) | |
H11A | −0.5339 | −0.9148 | −0.1880 | 0.075* | |
H11B | −0.5183 | −1.0525 | −0.1567 | 0.075* | |
C12 | −0.5211 (4) | −0.8337 (4) | −0.12970 (8) | 0.0639 (8) | |
H12A | −0.4940 | −0.7264 | −0.1379 | 0.077* | |
H12B | −0.6436 | −0.8393 | −0.1241 | 0.077* | |
C13 | −0.4206 (3) | −0.8750 (3) | −0.09201 (8) | 0.0512 (6) | |
C14 | −0.2281 (3) | −0.8698 (3) | −0.10241 (7) | 0.0459 (6) | |
H14 | −0.2089 | −0.7673 | −0.1154 | 0.055* | |
C15 | −0.1350 (4) | −0.8609 (4) | −0.06158 (7) | 0.0559 (7) | |
H15A | −0.1166 | −0.9655 | −0.0504 | 0.067* | |
H15B | −0.0249 | −0.8076 | −0.0641 | 0.067* | |
C16 | −0.2580 (3) | −0.7666 (3) | −0.03594 (7) | 0.0509 (6) | |
C17 | −0.4295 (4) | −0.7627 (3) | −0.05658 (8) | 0.0554 (7) | |
C18 | −0.4790 (4) | −1.0340 (4) | −0.07394 (10) | 0.0715 (9) | |
H18A | −0.4769 | −1.1140 | −0.0944 | 0.107* | |
H18B | −0.5940 | −1.0236 | −0.0636 | 0.107* | |
H18C | −0.4026 | −1.0634 | −0.0525 | 0.107* | |
C19 | −0.3070 (4) | −1.2417 (3) | −0.19975 (9) | 0.0699 (9) | |
H19A | −0.2571 | −1.2823 | −0.1754 | 0.105* | |
H19B | −0.2771 | −1.3093 | −0.2219 | 0.105* | |
H19C | −0.4300 | −1.2380 | −0.1970 | 0.105* | |
C20 | −0.2409 (3) | −0.6956 (3) | −0.00009 (8) | 0.0516 (6) | |
H20 | −0.3419 | −0.6517 | 0.0099 | 0.062* | |
C21 | −0.0912 (4) | −0.6756 (3) | 0.02589 (7) | 0.0512 (6) | |
C22 | 0.0775 (4) | −0.7068 (4) | 0.01401 (7) | 0.0601 (7) | |
H22 | 0.0978 | −0.7482 | −0.0115 | 0.072* | |
C23 | 0.2143 (4) | −0.6777 (4) | 0.03905 (7) | 0.0643 (8) | |
H23 | 0.3261 | −0.6975 | 0.0303 | 0.077* | |
C24 | 0.1854 (4) | −0.6187 (3) | 0.07737 (7) | 0.0571 (7) | |
C25 | 0.0199 (4) | −0.5861 (4) | 0.08986 (7) | 0.0615 (8) | |
H25 | 0.0005 | −0.5454 | 0.1155 | 0.074* | |
C26 | −0.1163 (4) | −0.6138 (3) | 0.06447 (7) | 0.0578 (7) | |
H26 | −0.2275 | −0.5910 | 0.0731 | 0.069* | |
C27 | 0.3309 (5) | −0.5952 (4) | 0.10370 (9) | 0.0690 (9) | |
N28 | 0.4465 (5) | −0.5835 (4) | 0.12435 (9) | 0.0941 (10) | |
O29 | −0.5539 (3) | −0.6869 (3) | −0.04586 (6) | 0.0787 (7) | |
O30 | 0.0211 (4) | −1.0746 (3) | −0.31863 (6) | 0.1015 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.078 (2) | 0.095 (2) | 0.0520 (15) | −0.001 (2) | −0.0221 (15) | 0.0012 (17) |
C2 | 0.111 (3) | 0.111 (3) | 0.0495 (16) | −0.007 (3) | −0.0205 (19) | −0.0058 (19) |
C3 | 0.110 (3) | 0.0641 (19) | 0.0499 (16) | −0.010 (2) | 0.0021 (18) | 0.0044 (14) |
C4 | 0.071 (2) | 0.0675 (19) | 0.0583 (15) | −0.0093 (16) | 0.0043 (15) | −0.0007 (14) |
C5 | 0.0620 (17) | 0.0522 (15) | 0.0498 (14) | −0.0090 (14) | −0.0042 (13) | 0.0004 (12) |
C6 | 0.0508 (15) | 0.082 (2) | 0.0518 (14) | 0.0060 (16) | −0.0053 (13) | −0.0054 (14) |
C7 | 0.0470 (14) | 0.0753 (19) | 0.0513 (14) | 0.0012 (15) | −0.0115 (12) | −0.0061 (14) |
C8 | 0.0423 (13) | 0.0533 (14) | 0.0467 (12) | 0.0005 (13) | −0.0085 (11) | 0.0001 (11) |
C9 | 0.0507 (14) | 0.0470 (14) | 0.0473 (13) | −0.0018 (12) | −0.0135 (12) | 0.0017 (11) |
C10 | 0.0560 (16) | 0.0562 (15) | 0.0465 (13) | −0.0047 (14) | −0.0087 (12) | 0.0004 (12) |
C11 | 0.0503 (16) | 0.074 (2) | 0.0646 (16) | 0.0051 (15) | −0.0183 (13) | −0.0079 (15) |
C12 | 0.0472 (16) | 0.0733 (19) | 0.0712 (17) | 0.0083 (15) | −0.0157 (14) | −0.0062 (15) |
C13 | 0.0442 (14) | 0.0533 (14) | 0.0562 (14) | 0.0002 (13) | −0.0053 (12) | 0.0001 (12) |
C14 | 0.0448 (13) | 0.0468 (13) | 0.0461 (12) | −0.0023 (12) | −0.0087 (11) | 0.0000 (11) |
C15 | 0.0530 (16) | 0.0684 (17) | 0.0463 (13) | 0.0023 (15) | −0.0095 (12) | −0.0051 (13) |
C16 | 0.0543 (16) | 0.0524 (15) | 0.0461 (13) | −0.0031 (13) | 0.0003 (12) | 0.0020 (11) |
C17 | 0.0525 (16) | 0.0565 (16) | 0.0570 (15) | 0.0021 (15) | 0.0019 (13) | 0.0025 (13) |
C18 | 0.0688 (19) | 0.0639 (19) | 0.082 (2) | −0.0130 (17) | 0.0058 (17) | 0.0011 (15) |
C19 | 0.076 (2) | 0.0598 (18) | 0.0742 (18) | −0.0167 (16) | 0.0048 (17) | −0.0158 (15) |
C20 | 0.0556 (14) | 0.0492 (13) | 0.0499 (12) | −0.0012 (14) | 0.0059 (14) | 0.0029 (12) |
C21 | 0.0659 (17) | 0.0437 (14) | 0.0441 (12) | −0.0027 (13) | 0.0009 (13) | 0.0008 (11) |
C22 | 0.0632 (17) | 0.0735 (18) | 0.0437 (13) | 0.0024 (16) | −0.0002 (12) | −0.0125 (13) |
C23 | 0.0655 (18) | 0.079 (2) | 0.0486 (14) | 0.0064 (17) | −0.0046 (14) | −0.0097 (14) |
C24 | 0.0779 (19) | 0.0485 (14) | 0.0449 (13) | 0.0030 (15) | −0.0122 (13) | −0.0011 (12) |
C25 | 0.088 (2) | 0.0573 (17) | 0.0392 (13) | 0.0064 (17) | −0.0016 (14) | −0.0043 (12) |
C26 | 0.0699 (19) | 0.0580 (16) | 0.0456 (14) | 0.0055 (16) | 0.0048 (14) | −0.0001 (13) |
C27 | 0.093 (2) | 0.0580 (17) | 0.0560 (16) | 0.0136 (18) | −0.0224 (17) | −0.0078 (14) |
N28 | 0.115 (3) | 0.083 (2) | 0.0838 (18) | 0.021 (2) | −0.044 (2) | −0.0177 (17) |
O29 | 0.0659 (13) | 0.0997 (17) | 0.0704 (12) | 0.0246 (14) | −0.0003 (11) | −0.0129 (12) |
O30 | 0.142 (2) | 0.113 (2) | 0.0501 (11) | −0.0005 (19) | 0.0162 (14) | 0.0076 (12) |
C1—C2 | 1.516 (4) | C13—C17 | 1.515 (4) |
C1—C10 | 1.531 (4) | C13—C14 | 1.535 (4) |
C1—H1A | 0.9700 | C13—C18 | 1.541 (4) |
C1—H1B | 0.9700 | C14—C15 | 1.539 (3) |
C2—C3 | 1.489 (5) | C14—H14 | 0.9800 |
C2—H2A | 0.9700 | C15—C16 | 1.508 (4) |
C2—H2B | 0.9700 | C15—H15A | 0.9700 |
C3—O30 | 1.214 (4) | C15—H15B | 0.9700 |
C3—C4 | 1.450 (4) | C16—C20 | 1.340 (4) |
C4—C5 | 1.335 (4) | C16—C17 | 1.498 (4) |
C4—H4 | 0.9300 | C17—O29 | 1.212 (3) |
C5—C6 | 1.500 (4) | C18—H18A | 0.9600 |
C5—C10 | 1.519 (4) | C18—H18B | 0.9600 |
C6—C7 | 1.518 (4) | C18—H18C | 0.9600 |
C6—H6A | 0.9700 | C19—H19A | 0.9600 |
C6—H6B | 0.9700 | C19—H19B | 0.9600 |
C7—C8 | 1.514 (4) | C19—H19C | 0.9600 |
C7—H7A | 0.9700 | C20—C21 | 1.457 (4) |
C7—H7B | 0.9700 | C20—H20 | 0.9300 |
C8—C14 | 1.515 (3) | C21—C22 | 1.393 (4) |
C8—C9 | 1.547 (3) | C21—C26 | 1.397 (3) |
C8—H8 | 0.9800 | C22—C23 | 1.372 (4) |
C9—C11 | 1.545 (4) | C22—H22 | 0.9300 |
C9—C10 | 1.564 (3) | C23—C24 | 1.386 (4) |
C9—H9 | 0.9800 | C23—H23 | 0.9300 |
C10—C19 | 1.534 (4) | C24—C25 | 1.378 (4) |
C11—C12 | 1.527 (4) | C24—C27 | 1.442 (4) |
C11—H11A | 0.9700 | C25—C26 | 1.373 (4) |
C11—H11B | 0.9700 | C25—H25 | 0.9300 |
C12—C13 | 1.516 (4) | C26—H26 | 0.9300 |
C12—H12A | 0.9700 | C27—N28 | 1.134 (4) |
C12—H12B | 0.9700 | ||
C2—C1—C10 | 114.2 (3) | C11—C12—H12B | 109.6 |
C2—C1—H1A | 108.7 | H12A—C12—H12B | 108.2 |
C10—C1—H1A | 108.7 | C17—C13—C12 | 118.2 (2) |
C2—C1—H1B | 108.7 | C17—C13—C14 | 101.6 (2) |
C10—C1—H1B | 108.7 | C12—C13—C14 | 108.0 (2) |
H1A—C1—H1B | 107.6 | C17—C13—C18 | 103.4 (2) |
C3—C2—C1 | 112.2 (3) | C12—C13—C18 | 111.8 (2) |
C3—C2—H2A | 109.2 | C14—C13—C18 | 113.6 (2) |
C1—C2—H2A | 109.2 | C8—C14—C13 | 112.8 (2) |
C3—C2—H2B | 109.2 | C8—C14—C15 | 120.5 (2) |
C1—C2—H2B | 109.2 | C13—C14—C15 | 105.1 (2) |
H2A—C2—H2B | 107.9 | C8—C14—H14 | 105.8 |
O30—C3—C4 | 122.2 (3) | C13—C14—H14 | 105.8 |
O30—C3—C2 | 122.1 (3) | C15—C14—H14 | 105.8 |
C4—C3—C2 | 115.6 (3) | C16—C15—C14 | 103.1 (2) |
C5—C4—C3 | 124.8 (3) | C16—C15—H15A | 111.1 |
C5—C4—H4 | 117.6 | C14—C15—H15A | 111.1 |
C3—C4—H4 | 117.6 | C16—C15—H15B | 111.1 |
C4—C5—C6 | 120.4 (3) | C14—C15—H15B | 111.1 |
C4—C5—C10 | 122.7 (3) | H15A—C15—H15B | 109.1 |
C6—C5—C10 | 116.8 (2) | C20—C16—C17 | 119.0 (2) |
C5—C6—C7 | 111.7 (2) | C20—C16—C15 | 132.5 (2) |
C5—C6—H6A | 109.3 | C17—C16—C15 | 108.4 (2) |
C7—C6—H6A | 109.3 | O29—C17—C16 | 125.8 (2) |
C5—C6—H6B | 109.3 | O29—C17—C13 | 126.6 (3) |
C7—C6—H6B | 109.3 | C16—C17—C13 | 107.5 (2) |
H6A—C6—H6B | 107.9 | C13—C18—H18A | 109.5 |
C8—C7—C6 | 111.8 (2) | C13—C18—H18B | 109.5 |
C8—C7—H7A | 109.3 | H18A—C18—H18B | 109.5 |
C6—C7—H7A | 109.3 | C13—C18—H18C | 109.5 |
C8—C7—H7B | 109.3 | H18A—C18—H18C | 109.5 |
C6—C7—H7B | 109.3 | H18B—C18—H18C | 109.5 |
H7A—C7—H7B | 107.9 | C10—C19—H19A | 109.5 |
C7—C8—C14 | 113.2 (2) | C10—C19—H19B | 109.5 |
C7—C8—C9 | 110.1 (2) | H19A—C19—H19B | 109.5 |
C14—C8—C9 | 107.6 (2) | C10—C19—H19C | 109.5 |
C7—C8—H8 | 108.6 | H19A—C19—H19C | 109.5 |
C14—C8—H8 | 108.6 | H19B—C19—H19C | 109.5 |
C9—C8—H8 | 108.6 | C16—C20—C21 | 131.1 (2) |
C11—C9—C8 | 111.5 (2) | C16—C20—H20 | 114.4 |
C11—C9—C10 | 112.5 (2) | C21—C20—H20 | 114.4 |
C8—C9—C10 | 114.0 (2) | C22—C21—C26 | 117.5 (2) |
C11—C9—H9 | 106.0 | C22—C21—C20 | 124.0 (2) |
C8—C9—H9 | 106.0 | C26—C21—C20 | 118.4 (3) |
C10—C9—H9 | 106.0 | C23—C22—C21 | 121.5 (2) |
C5—C10—C1 | 108.9 (2) | C23—C22—H22 | 119.3 |
C5—C10—C19 | 108.2 (2) | C21—C22—H22 | 119.3 |
C1—C10—C19 | 110.1 (2) | C22—C23—C24 | 119.8 (3) |
C5—C10—C9 | 108.9 (2) | C22—C23—H23 | 120.1 |
C1—C10—C9 | 109.0 (2) | C24—C23—H23 | 120.1 |
C19—C10—C9 | 111.8 (2) | C25—C24—C23 | 120.0 (3) |
C12—C11—C9 | 113.7 (2) | C25—C24—C27 | 121.3 (2) |
C12—C11—H11A | 108.8 | C23—C24—C27 | 118.7 (3) |
C9—C11—H11A | 108.8 | C26—C25—C24 | 119.9 (2) |
C12—C11—H11B | 108.8 | C26—C25—H25 | 120.0 |
C9—C11—H11B | 108.8 | C24—C25—H25 | 120.0 |
H11A—C11—H11B | 107.7 | C25—C26—C21 | 121.3 (3) |
C13—C12—C11 | 110.1 (2) | C25—C26—H26 | 119.3 |
C13—C12—H12A | 109.6 | C21—C26—H26 | 119.3 |
C11—C12—H12A | 109.6 | N28—C27—C24 | 177.1 (3) |
C13—C12—H12B | 109.6 | ||
C10—C1—C2—C3 | −54.1 (4) | C17—C13—C14—C8 | 170.9 (2) |
C1—C2—C3—O30 | −152.4 (3) | C12—C13—C14—C8 | −64.0 (3) |
C1—C2—C3—C4 | 30.5 (5) | C18—C13—C14—C8 | 60.6 (3) |
O30—C3—C4—C5 | −179.3 (3) | C17—C13—C14—C15 | 37.8 (3) |
C2—C3—C4—C5 | −2.2 (5) | C12—C13—C14—C15 | 162.9 (2) |
C3—C4—C5—C6 | 171.1 (3) | C18—C13—C14—C15 | −72.5 (3) |
C3—C4—C5—C10 | −4.3 (5) | C8—C14—C15—C16 | −161.7 (2) |
C4—C5—C6—C7 | 132.3 (3) | C13—C14—C15—C16 | −33.1 (3) |
C10—C5—C6—C7 | −52.1 (4) | C14—C15—C16—C20 | −166.8 (3) |
C5—C6—C7—C8 | 54.9 (3) | C14—C15—C16—C17 | 15.3 (3) |
C6—C7—C8—C14 | −176.7 (2) | C20—C16—C17—O29 | 7.9 (4) |
C6—C7—C8—C9 | −56.2 (3) | C15—C16—C17—O29 | −173.9 (3) |
C7—C8—C9—C11 | −176.7 (2) | C20—C16—C17—C13 | −169.9 (2) |
C14—C8—C9—C11 | −52.9 (3) | C15—C16—C17—C13 | 8.3 (3) |
C7—C8—C9—C10 | 54.5 (3) | C12—C13—C17—O29 | 36.0 (4) |
C14—C8—C9—C10 | 178.3 (2) | C14—C13—C17—O29 | 154.0 (3) |
C4—C5—C10—C1 | −17.7 (4) | C18—C13—C17—O29 | −88.1 (4) |
C6—C5—C10—C1 | 166.8 (2) | C12—C13—C17—C16 | −146.2 (2) |
C4—C5—C10—C19 | 101.9 (3) | C14—C13—C17—C16 | −28.2 (3) |
C6—C5—C10—C19 | −73.6 (3) | C18—C13—C17—C16 | 89.7 (3) |
C4—C5—C10—C9 | −136.4 (3) | C17—C16—C20—C21 | −177.5 (3) |
C6—C5—C10—C9 | 48.0 (3) | C15—C16—C20—C21 | 4.8 (5) |
C2—C1—C10—C5 | 46.1 (4) | C16—C20—C21—C22 | 11.7 (5) |
C2—C1—C10—C19 | −72.3 (4) | C16—C20—C21—C26 | −171.7 (3) |
C2—C1—C10—C9 | 164.8 (3) | C26—C21—C22—C23 | −0.2 (4) |
C11—C9—C10—C5 | −177.2 (2) | C20—C21—C22—C23 | 176.4 (3) |
C8—C9—C10—C5 | −48.9 (3) | C21—C22—C23—C24 | 1.2 (5) |
C11—C9—C10—C1 | 64.2 (3) | C22—C23—C24—C25 | −1.5 (5) |
C8—C9—C10—C1 | −167.6 (2) | C22—C23—C24—C27 | 177.5 (3) |
C11—C9—C10—C19 | −57.7 (3) | C23—C24—C25—C26 | 0.7 (4) |
C8—C9—C10—C19 | 70.6 (3) | C27—C24—C25—C26 | −178.2 (3) |
C8—C9—C11—C12 | 51.8 (3) | C24—C25—C26—C21 | 0.3 (4) |
C10—C9—C11—C12 | −178.6 (2) | C22—C21—C26—C25 | −0.5 (4) |
C9—C11—C12—C13 | −54.0 (3) | C20—C21—C26—C25 | −177.4 (3) |
C11—C12—C13—C17 | 172.1 (2) | C25—C24—C27—N28 | 116 (7) |
C11—C12—C13—C14 | 57.6 (3) | C23—C24—C27—N28 | −63 (7) |
C11—C12—C13—C18 | −68.1 (3) | C17—C16—C20—H20 | 2.5 |
C7—C8—C14—C13 | −177.4 (2) | C15—C16—C20—H20 | −175.2 |
C9—C8—C14—C13 | 60.8 (3) | H8—C8—C9—H9 | 179.5 |
C7—C8—C14—C15 | −52.2 (3) | H14—C14—C13—C18 | 175.8 |
C9—C8—C14—C15 | −174.1 (2) | C19—C10—C13—C18 | 7.4 (2) |
Experimental details
Crystal data | |
Chemical formula | C27H29NO2 |
Mr | 399.51 |
Crystal system, space group | Orthorhombic, P22121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.7638 (10), 8.4584 (10), 33.220 (5) |
V (Å3) | 2181.5 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.30 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.842, 0.943 |
No. of measured, independent and observed [I > 2s(I)] reflections | 2365, 2363, 1957 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.105, 1.11 |
No. of reflections | 2363 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.12 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.9 (5) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), DIRDIF98 (Beurskens et al., 1998), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.
C1—C2 | 1.516 (4) | C17—O29 | 1.212 (3) |
C3—O30 | 1.214 (4) | ||
C2—C1—C10 | 114.2 (3) | O30—C3—C4 | 122.2 (3) |
C10—C1—C2—C3 | −54.1 (4) | C3—C4—C5—C10 | −4.3 (5) |
C1—C2—C3—C4 | 30.5 (5) | C4—C5—C10—C1 | −17.7 (4) |
C2—C3—C4—C5 | −2.2 (5) | C2—C1—C10—C5 | 46.1 (4) |
The structure determination of the title compound, (I), was undertaken to investigate the conformation of the fused-ring system and the configuration of the 16-(4-cyanobenzylidene) functionality with respect to the carbonyl group at position 17. Compound (I), an androgen derivative, is a steroid with the normal 8β,9α,10β,13β,14α configuration. The absolute configuration of (I) is based on the known configuration of the starting material, namely androstenedione (Busetta et al., 1972). \sch
Ring A adopts a sofa conformation with C1 in the α-position, as is evident from the deviation of C1 by -0.600 (5) Å from the mean plane of C2/C3/O30/C4/C5/C10. The puckering amplitudes (Cremer & Pople, 1975) are Q = 0.435 (3) Å, θ = 54.5 (4)° and ϕ = 11.2 (6)°. The C2—C3 bond distance of 1.489 (5) Å is comparable with the reported value of 1.492 Å in a related structure (Cowe et al., 1982), in which ring A also has the 1α-sofa conformation.
Rings B and C adopt normal chair conformations. The C4—C5 distance of 1.335 (4) Å confirms the localization of a double bond at this position. In a few typical related steroid structures (Cowe et al., 1982; Bhadbhade & Venkatesan 1984; Galdecki et al., 1990), the C4—C5 bond distance is in the range 1.309 (8)–1.363 (3) Å.
The conformation of ring D can be expressed by two parameters, a pseudorotation angle, Δ, and a maximum torsion angle, ϕm (Altona et al., 1968). For a perfect envelope (Cs symmetry), Δ is 36°, whereas it is 0° for a half chair. In (I), ring D exhibits a slightly distorted 13β,14α half-chair conformation (Δ = 11.4° and ϕm = 38.1°).
The C17—C16—C20—C21 torsion angle of -177.5 (3)° indicates that the 4-cyanobenzylidene ring has an E configuration with respect to the carbonyl group at position 17. Atom H20 is Z with respect to this carbonyl group. The exocyclic C15—C16—C20 angle [132.5 (2)°] is found to be significantly higher than the normal value and this may be due to the steric repulsion between atoms H15B and H22 [2.0531 (2) Å].
The pseudo torsion angle of C19—C10···C13—C18 is observed to be 7.4 (2)°. The C27—N28 bond length [1.134 (4) Å] and the C24—C27—N28 angle [177.1 (3)°] confirm the C—N triple bond. Atoms O29 and O30 are both equatorially substituted at C17 and C3, respectively. The dihedral angle between the cyanobenzylidene ring and the androstenedione moiety is 11.86 (8)°. The geometry of the rings is trans at the B/C and C/D ring junctions. The molecules are found to pack in antiparallel arrangements.