Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019906/ci6176sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019906/ci6176Isup2.hkl |
CCDC reference: 202325
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.108
- Data-to-parameter ratio = 8.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.96 From the CIF: _reflns_number_total 2172 Count of symmetry unique reflns 2073 Completeness (_total/calc) 104.78% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 99 Fraction of Friedel pairs measured 0.048 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.
The title compound was prepared by dissolving 17-oxo-16-(3-pyridylmethylene)androst-5-en-3β-ol (1 g, 2.66 mmol) in dry toluene (150 ml) under reflux and then adding cyclohexanone (10 ml) to it. 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 (15 ml). The reaction mixture was refluxed for 4 h and left overnight at room temperature. The slurry was filtered and the residue washed thoroughly with dry toluene. The combined filterate and washing were steam distilled until the organic solvent was completely removed. The solid residue was allowed to stand overnight and then filtered, washed, dried and crystallized from methanol to afford crystals of (I) (yield 0.6 g, 59.68%, m.p. 475–481 K).
All H atoms were placed geometrically and refined using a riding model, with C—H = 0.93–0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for all others. The absolute configuration was assigned to correspond with that of a known chiral centre in a starting molecule, namely 17-oxo-16-(3-pyridylmethylene)androst-5-ene-3β-ol.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP97 (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. |
C25H29NO2 | F(000) = 808 |
Mr = 375.49 | Dx = 1.207 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 11.4545 (12) Å | θ = 10–15° |
b = 12.207 (2) Å | µ = 0.08 mm−1 |
c = 14.784 (3) Å | T = 293 K |
V = 2067.2 (6) Å3 | Plate, white |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
Enraf-Nonius CAD4 diffractometer | 1671 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.008 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–2θ scans | h = −2→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −5→14 |
Tmin = 0.993, Tmax = 1.000 | l = −10→17 |
2222 measured reflections | 2 standard reflections every 120 min |
2172 independent reflections | intensity decay: none |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.4599P] where P = (Fo2 + 2Fc2)/3 |
2172 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C25H29NO2 | V = 2067.2 (6) Å3 |
Mr = 375.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.4545 (12) Å | µ = 0.08 mm−1 |
b = 12.207 (2) Å | T = 293 K |
c = 14.784 (3) Å | 0.20 × 0.15 × 0.10 mm |
Enraf-Nonius CAD4 diffractometer | 1671 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.008 |
Tmin = 0.993, Tmax = 1.000 | 2 standard reflections every 120 min |
2222 measured reflections | intensity decay: none |
2172 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.26 e Å−3 |
2172 reflections | Δρmin = −0.18 e Å−3 |
253 parameters |
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 | 0.7002 (3) | 0.3282 (3) | 0.3994 (2) | 0.0555 (9) | |
H1A | 0.6842 | 0.4035 | 0.3825 | 0.067* | |
H1B | 0.6333 | 0.2844 | 0.3818 | 0.067* | |
C2 | 0.7144 (4) | 0.3220 (3) | 0.5016 (2) | 0.0665 (11) | |
H2A | 0.7740 | 0.3734 | 0.5207 | 0.080* | |
H2B | 0.6416 | 0.3428 | 0.5304 | 0.080* | |
C3 | 0.7475 (3) | 0.2098 (3) | 0.5311 (2) | 0.0637 (10) | |
C4 | 0.8229 (3) | 0.1483 (3) | 0.4706 (2) | 0.0615 (9) | |
H4 | 0.8512 | 0.0809 | 0.4902 | 0.074* | |
C5 | 0.8540 (3) | 0.1831 (3) | 0.3878 (2) | 0.0521 (9) | |
C6 | 0.9417 (4) | 0.1197 (3) | 0.3328 (2) | 0.0706 (11) | |
H6A | 0.9574 | 0.0503 | 0.3624 | 0.085* | |
H6B | 1.0142 | 0.1605 | 0.3302 | 0.085* | |
C7 | 0.8987 (3) | 0.0981 (3) | 0.2370 (2) | 0.0580 (9) | |
H7A | 0.9603 | 0.0633 | 0.2024 | 0.070* | |
H7B | 0.8327 | 0.0484 | 0.2391 | 0.070* | |
C8 | 0.8623 (3) | 0.2036 (2) | 0.19031 (19) | 0.0431 (7) | |
H8 | 0.9311 | 0.2507 | 0.1835 | 0.052* | |
C9 | 0.7701 (3) | 0.2646 (2) | 0.24678 (18) | 0.0406 (7) | |
H9 | 0.7035 | 0.2145 | 0.2511 | 0.049* | |
C10 | 0.8079 (3) | 0.2881 (2) | 0.34651 (19) | 0.0457 (7) | |
C11 | 0.7233 (3) | 0.3677 (3) | 0.1983 (2) | 0.0566 (9) | |
H11A | 0.6592 | 0.3978 | 0.2333 | 0.068* | |
H11B | 0.7847 | 0.4224 | 0.1962 | 0.068* | |
C12 | 0.6809 (3) | 0.3451 (3) | 0.10173 (19) | 0.0561 (9) | |
H12A | 0.6115 | 0.2996 | 0.1036 | 0.067* | |
H12B | 0.6607 | 0.4137 | 0.0724 | 0.067* | |
C13 | 0.7758 (3) | 0.2874 (2) | 0.04786 (19) | 0.0457 (8) | |
C14 | 0.8101 (3) | 0.1818 (2) | 0.09692 (18) | 0.0412 (7) | |
H14 | 0.7370 | 0.1421 | 0.1077 | 0.049* | |
C15 | 0.8776 (3) | 0.1141 (2) | 0.02682 (18) | 0.0473 (8) | |
H15A | 0.9595 | 0.1345 | 0.0255 | 0.057* | |
H15B | 0.8711 | 0.0363 | 0.0390 | 0.057* | |
C16 | 0.8166 (3) | 0.1448 (3) | −0.06125 (19) | 0.0461 (7) | |
C17 | 0.7398 (3) | 0.2419 (3) | −0.0438 (2) | 0.0517 (8) | |
C18 | 0.8799 (4) | 0.3637 (3) | 0.0289 (2) | 0.0647 (10) | |
H18A | 0.9384 | 0.3246 | −0.0045 | 0.097* | |
H18B | 0.9123 | 0.3886 | 0.0852 | 0.097* | |
H18C | 0.8539 | 0.4256 | −0.0057 | 0.097* | |
C19 | 0.9056 (4) | 0.3756 (3) | 0.3514 (2) | 0.0711 (11) | |
H19A | 0.8781 | 0.4428 | 0.3252 | 0.107* | |
H19B | 0.9727 | 0.3504 | 0.3186 | 0.107* | |
H19C | 0.9265 | 0.3880 | 0.4135 | 0.107* | |
C20 | 0.8271 (3) | 0.1066 (2) | −0.1461 (2) | 0.0507 (8) | |
H20 | 0.7771 | 0.1389 | −0.1879 | 0.061* | |
C21 | 0.9047 (3) | 0.0222 (2) | −0.1834 (2) | 0.0470 (7) | |
C22 | 0.9693 (3) | −0.0521 (3) | −0.1341 (2) | 0.0568 (9) | |
H22 | 0.9640 | −0.0532 | −0.0713 | 0.068* | |
C23 | 1.0417 (3) | −0.1248 (3) | −0.1782 (3) | 0.0671 (10) | |
H23 | 1.0857 | −0.1757 | −0.1460 | 0.081* | |
C24 | 1.0475 (4) | −0.1204 (4) | −0.2702 (3) | 0.0774 (12) | |
H24 | 1.0972 | −0.1694 | −0.2992 | 0.093* | |
N25 | 0.9868 (3) | −0.0509 (3) | −0.3218 (2) | 0.0773 (10) | |
C26 | 0.9163 (3) | 0.0179 (3) | −0.2770 (2) | 0.0596 (9) | |
H26 | 0.8718 | 0.0664 | −0.3111 | 0.072* | |
O3 | 0.7173 (3) | 0.1743 (3) | 0.60509 (17) | 0.0922 (9) | |
O17 | 0.6663 (2) | 0.2791 (2) | −0.09451 (16) | 0.0810 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.071 (2) | 0.0531 (19) | 0.0425 (16) | 0.0081 (19) | 0.0031 (18) | −0.0037 (16) |
C2 | 0.089 (3) | 0.063 (2) | 0.0475 (19) | 0.006 (2) | 0.0070 (19) | −0.0039 (17) |
C3 | 0.077 (3) | 0.071 (2) | 0.0430 (19) | −0.004 (2) | −0.0034 (19) | 0.0019 (18) |
C4 | 0.080 (2) | 0.0519 (19) | 0.0532 (19) | 0.007 (2) | −0.011 (2) | 0.0030 (17) |
C5 | 0.056 (2) | 0.054 (2) | 0.0456 (18) | 0.0048 (17) | −0.0083 (16) | −0.0015 (15) |
C6 | 0.076 (3) | 0.076 (3) | 0.059 (2) | 0.029 (2) | −0.009 (2) | 0.000 (2) |
C7 | 0.068 (2) | 0.055 (2) | 0.0516 (19) | 0.0205 (18) | −0.0011 (18) | −0.0025 (16) |
C8 | 0.0413 (17) | 0.0419 (16) | 0.0461 (16) | 0.0000 (14) | 0.0063 (14) | −0.0010 (14) |
C9 | 0.0418 (16) | 0.0412 (15) | 0.0387 (15) | −0.0015 (14) | 0.0017 (13) | −0.0032 (13) |
C10 | 0.0497 (18) | 0.0428 (16) | 0.0447 (16) | −0.0014 (16) | −0.0018 (15) | −0.0046 (14) |
C11 | 0.070 (2) | 0.0526 (17) | 0.0469 (17) | 0.0218 (18) | 0.0018 (17) | −0.0007 (15) |
C12 | 0.066 (2) | 0.058 (2) | 0.0442 (16) | 0.0248 (19) | 0.0031 (18) | 0.0026 (16) |
C13 | 0.0544 (19) | 0.0408 (16) | 0.0419 (17) | 0.0082 (15) | 0.0063 (15) | 0.0021 (14) |
C14 | 0.0408 (16) | 0.0402 (16) | 0.0426 (15) | 0.0019 (15) | 0.0061 (15) | −0.0015 (14) |
C15 | 0.0551 (19) | 0.0423 (17) | 0.0445 (17) | 0.0032 (16) | 0.0047 (16) | −0.0022 (15) |
C16 | 0.0492 (18) | 0.0466 (17) | 0.0425 (16) | 0.0013 (16) | 0.0062 (15) | 0.0011 (14) |
C17 | 0.056 (2) | 0.0546 (19) | 0.0442 (18) | 0.0070 (18) | 0.0055 (17) | 0.0007 (16) |
C18 | 0.088 (3) | 0.0456 (18) | 0.061 (2) | −0.0004 (19) | 0.014 (2) | 0.0084 (17) |
C19 | 0.072 (2) | 0.072 (2) | 0.069 (2) | −0.018 (2) | −0.013 (2) | −0.006 (2) |
C20 | 0.0541 (19) | 0.0508 (19) | 0.0472 (17) | −0.0027 (17) | 0.0003 (16) | −0.0006 (15) |
C21 | 0.0482 (17) | 0.0429 (17) | 0.0501 (18) | −0.0073 (16) | 0.0034 (16) | −0.0089 (15) |
C22 | 0.066 (2) | 0.051 (2) | 0.053 (2) | −0.0014 (19) | −0.0037 (18) | −0.0115 (16) |
C23 | 0.064 (2) | 0.049 (2) | 0.088 (3) | 0.0075 (19) | −0.010 (2) | −0.017 (2) |
C24 | 0.071 (3) | 0.071 (3) | 0.090 (3) | 0.000 (2) | 0.016 (2) | −0.038 (3) |
N25 | 0.082 (2) | 0.077 (2) | 0.073 (2) | −0.002 (2) | 0.017 (2) | −0.0260 (19) |
C26 | 0.068 (2) | 0.060 (2) | 0.051 (2) | −0.006 (2) | 0.0080 (18) | −0.0147 (18) |
O3 | 0.118 (2) | 0.100 (2) | 0.0584 (15) | 0.007 (2) | 0.0156 (17) | 0.0191 (15) |
O17 | 0.0878 (19) | 0.102 (2) | 0.0530 (13) | 0.0429 (18) | −0.0105 (15) | −0.0059 (14) |
C1—C2 | 1.523 (4) | C12—H12B | 0.97 |
C1—C10 | 1.539 (4) | C13—C17 | 1.521 (4) |
C1—H1A | 0.97 | C13—C14 | 1.531 (4) |
C1—H1B | 0.97 | C13—C18 | 1.539 (5) |
C2—C3 | 1.487 (5) | C14—C15 | 1.534 (4) |
C2—H2A | 0.97 | C14—H14 | 0.98 |
C2—H2B | 0.97 | C15—C16 | 1.525 (4) |
C3—O3 | 1.226 (4) | C15—H15A | 0.97 |
C3—C4 | 1.453 (5) | C15—H15B | 0.97 |
C4—C5 | 1.343 (4) | C16—C20 | 1.343 (4) |
C4—H4 | 0.93 | C16—C17 | 1.499 (4) |
C5—C6 | 1.506 (5) | C17—O17 | 1.215 (4) |
C5—C10 | 1.515 (4) | C18—H18A | 0.96 |
C6—C7 | 1.522 (4) | C18—H18B | 0.96 |
C6—H6A | 0.97 | C18—H18C | 0.96 |
C6—H6B | 0.97 | C19—H19A | 0.96 |
C7—C8 | 1.519 (4) | C19—H19B | 0.96 |
C7—H7A | 0.97 | C19—H19C | 0.96 |
C7—H7B | 0.97 | C20—C21 | 1.469 (4) |
C8—C14 | 1.528 (4) | C20—H20 | 0.93 |
C8—C9 | 1.539 (4) | C21—C22 | 1.380 (4) |
C8—H8 | 0.98 | C21—C26 | 1.391 (4) |
C9—C11 | 1.545 (4) | C22—C23 | 1.380 (5) |
C9—C10 | 1.563 (4) | C22—H22 | 0.93 |
C9—H9 | 0.98 | C23—C24 | 1.363 (5) |
C10—C19 | 1.549 (5) | C23—H23 | 0.93 |
C11—C12 | 1.533 (4) | C24—N25 | 1.336 (5) |
C11—H11A | 0.97 | C24—H24 | 0.93 |
C11—H11B | 0.97 | N25—C26 | 1.339 (4) |
C12—C13 | 1.521 (4) | C26—H26 | 0.93 |
C12—H12A | 0.97 | ||
C2—C1—C10 | 113.8 (3) | C11—C12—H12A | 109.6 |
C2—C1—H1A | 108.8 | C13—C12—H12B | 109.6 |
C10—C1—H1A | 108.8 | C11—C12—H12B | 109.6 |
C2—C1—H1B | 108.8 | H12A—C12—H12B | 108.1 |
C10—C1—H1B | 108.8 | C12—C13—C17 | 116.2 (3) |
H1A—C1—H1B | 107.7 | C12—C13—C14 | 109.0 (2) |
C3—C2—C1 | 111.4 (3) | C17—C13—C14 | 100.6 (2) |
C3—C2—H2A | 109.4 | C12—C13—C18 | 111.6 (3) |
C1—C2—H2A | 109.4 | C17—C13—C18 | 105.6 (2) |
C3—C2—H2B | 109.4 | C14—C13—C18 | 113.4 (3) |
C1—C2—H2B | 109.4 | C8—C14—C13 | 112.5 (2) |
H2A—C2—H2B | 108.0 | C8—C14—C15 | 120.4 (2) |
O3—C3—C4 | 122.3 (3) | C13—C14—C15 | 105.2 (2) |
O3—C3—C2 | 121.0 (4) | C8—C14—H14 | 105.9 |
C4—C3—C2 | 116.6 (3) | C13—C14—H14 | 105.9 |
C5—C4—C3 | 123.7 (3) | C15—C14—H14 | 105.9 |
C5—C4—H4 | 118.1 | C16—C15—C14 | 102.3 (2) |
C3—C4—H4 | 118.1 | C16—C15—H15A | 111.3 |
C4—C5—C6 | 120.4 (3) | C14—C15—H15A | 111.3 |
C4—C5—C10 | 122.8 (3) | C16—C15—H15B | 111.3 |
C6—C5—C10 | 116.7 (3) | C14—C15—H15B | 111.3 |
C5—C6—C7 | 112.0 (3) | H15A—C15—H15B | 109.2 |
C5—C6—H6A | 109.2 | C20—C16—C17 | 119.2 (3) |
C7—C6—H6A | 109.2 | C20—C16—C15 | 132.1 (3) |
C5—C6—H6B | 109.2 | C17—C16—C15 | 108.4 (2) |
C7—C6—H6B | 109.2 | O17—C17—C16 | 126.5 (3) |
H6A—C6—H6B | 107.9 | O17—C17—C13 | 127.0 (3) |
C8—C7—C6 | 111.4 (3) | C16—C17—C13 | 106.5 (3) |
C8—C7—H7A | 109.3 | C13—C18—H18A | 109.5 |
C6—C7—H7A | 109.3 | C13—C18—H18B | 109.5 |
C8—C7—H7B | 109.3 | H18A—C18—H18B | 109.5 |
C6—C7—H7B | 109.3 | C13—C18—H18C | 109.5 |
H7A—C7—H7B | 108.0 | H18A—C18—H18C | 109.5 |
C7—C8—C14 | 111.8 (2) | H18B—C18—H18C | 109.5 |
C7—C8—C9 | 110.6 (2) | C10—C19—H19A | 109.5 |
C14—C8—C9 | 107.8 (2) | C10—C19—H19B | 109.5 |
C7—C8—H8 | 108.9 | H19A—C19—H19B | 109.5 |
C14—C8—H8 | 108.9 | C10—C19—H19C | 109.5 |
C9—C8—H8 | 108.9 | H19A—C19—H19C | 109.5 |
C8—C9—C11 | 112.4 (2) | H19B—C19—H19C | 109.5 |
C8—C9—C10 | 114.3 (2) | C16—C20—C21 | 130.4 (3) |
C11—C9—C10 | 112.5 (2) | C16—C20—H20 | 114.8 |
C8—C9—H9 | 105.6 | C21—C20—H20 | 114.8 |
C11—C9—H9 | 105.6 | C22—C21—C26 | 116.7 (3) |
C10—C9—H9 | 105.6 | C22—C21—C20 | 126.0 (3) |
C5—C10—C1 | 110.1 (3) | C26—C21—C20 | 117.3 (3) |
C5—C10—C19 | 108.2 (3) | C21—C22—C23 | 119.7 (3) |
C1—C10—C19 | 109.6 (3) | C21—C22—H22 | 120.2 |
C5—C10—C9 | 108.7 (2) | C23—C22—H22 | 120.2 |
C1—C10—C9 | 108.4 (3) | C24—C23—C22 | 118.4 (4) |
C19—C10—C9 | 111.8 (3) | C24—C23—H23 | 120.8 |
C12—C11—C9 | 113.3 (3) | C22—C23—H23 | 120.8 |
C12—C11—H11A | 108.9 | N25—C24—C23 | 124.7 (4) |
C9—C11—H11A | 108.9 | N25—C24—H24 | 117.6 |
C12—C11—H11B | 108.9 | C23—C24—H24 | 117.6 |
C9—C11—H11B | 108.9 | C24—N25—C26 | 115.4 (3) |
H11A—C11—H11B | 107.7 | N25—C26—C21 | 125.0 (4) |
C13—C12—C11 | 110.1 (3) | N25—C26—H26 | 117.5 |
C13—C12—H12A | 109.6 | C21—C26—H26 | 117.5 |
C10—C1—C2—C3 | −54.5 (5) | C9—C8—C14—C15 | −175.3 (2) |
C1—C2—C3—O3 | −149.2 (4) | C12—C13—C14—C8 | −62.9 (3) |
C1—C2—C3—C4 | 34.6 (5) | C17—C13—C14—C8 | 174.5 (2) |
O3—C3—C4—C5 | 177.4 (4) | C18—C13—C14—C8 | 62.1 (3) |
C2—C3—C4—C5 | −6.4 (5) | C12—C13—C14—C15 | 164.2 (2) |
C3—C4—C5—C6 | 174.1 (3) | C17—C13—C14—C15 | 41.6 (3) |
C3—C4—C5—C10 | −3.6 (5) | C18—C13—C14—C15 | −70.7 (3) |
C4—C5—C6—C7 | 130.3 (4) | C8—C14—C15—C16 | −161.8 (3) |
C10—C5—C6—C7 | −51.9 (4) | C13—C14—C15—C16 | −33.6 (3) |
C5—C6—C7—C8 | 53.8 (4) | C14—C15—C16—C20 | −173.2 (3) |
C6—C7—C8—C14 | −175.5 (3) | C14—C15—C16—C17 | 12.3 (3) |
C6—C7—C8—C9 | −55.4 (4) | C20—C16—C17—O17 | 15.6 (5) |
C7—C8—C9—C11 | −175.5 (3) | C15—C16—C17—O17 | −169.0 (3) |
C14—C8—C9—C11 | −53.0 (3) | C20—C16—C17—C13 | −161.9 (3) |
C7—C8—C9—C10 | 54.7 (3) | C15—C16—C17—C13 | 13.5 (3) |
C14—C8—C9—C10 | 177.1 (2) | C12—C13—C17—O17 | 31.7 (5) |
C4—C5—C10—C1 | −15.5 (4) | C14—C13—C17—O17 | 149.2 (3) |
C6—C5—C10—C1 | 166.8 (3) | C18—C13—C17—O17 | −92.7 (4) |
C4—C5—C10—C19 | 104.3 (4) | C12—C13—C17—C16 | −150.8 (3) |
C6—C5—C10—C19 | −73.4 (4) | C14—C13—C17—C16 | −33.4 (3) |
C4—C5—C10—C9 | −134.1 (3) | C18—C13—C17—C16 | 84.8 (3) |
C6—C5—C10—C9 | 48.2 (4) | C17—C16—C20—C21 | 172.5 (3) |
C2—C1—C10—C5 | 44.0 (4) | C15—C16—C20—C21 | −1.6 (6) |
C2—C1—C10—C19 | −74.9 (4) | C16—C20—C21—C22 | 13.7 (6) |
C2—C1—C10—C9 | 162.8 (3) | C16—C20—C21—C26 | −164.9 (3) |
C8—C9—C10—C5 | −49.4 (3) | C26—C21—C22—C23 | 0.7 (5) |
C11—C9—C10—C5 | −179.2 (3) | C20—C21—C22—C23 | −177.9 (3) |
C8—C9—C10—C1 | −169.1 (2) | C21—C22—C23—C24 | 0.2 (5) |
C11—C9—C10—C1 | 61.2 (3) | C22—C23—C24—N25 | −0.6 (7) |
C8—C9—C10—C19 | 70.0 (3) | C23—C24—N25—C26 | −0.1 (6) |
C11—C9—C10—C19 | −59.8 (4) | C24—N25—C26—C21 | 1.2 (5) |
C8—C9—C11—C12 | 51.8 (4) | C22—C21—C26—N25 | −1.5 (5) |
C10—C9—C11—C12 | −177.5 (3) | C20—C21—C26—N25 | 177.2 (3) |
C9—C11—C12—C13 | −53.0 (4) | C17—C16—C20—H20 | −7.5 |
C11—C12—C13—C17 | 169.7 (3) | C15—C16—C20—H20 | 178.4 |
C11—C12—C13—C14 | 57.0 (3) | C22—C21—C20—H20 | −166.3 |
C11—C12—C13—C18 | −69.0 (3) | C26—C21—C20—H20 | 15.1 |
C7—C8—C14—C13 | −178.5 (3) | C18—C13—C14—H14 | 177.4 |
C9—C8—C14—C13 | 59.7 (3) | H9—C9—C8—H8 | 179.5 |
C7—C8—C14—C15 | −53.6 (4) | C19—C10—C13—C18 | 6.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C25H29NO2 |
Mr | 375.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 11.4545 (12), 12.207 (2), 14.784 (3) |
V (Å3) | 2067.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.993, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2222, 2172, 1671 |
Rint | 0.008 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.108, 1.12 |
No. of reflections | 2172 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.18 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP97 (Zsolnai, 1997), SHELXL97.
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The X-ray investigation of the title compound, (I), was undertaken as a part of our study on the structure and conformation of new synthetic steroid derivatives (Hema et al., 2002; Vasuki et al., 2001; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a,b; Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan et al., 2002a,b). We are particularly interested in studying the conformational flexibilities of the steroids due to various possible substitutions at the C3, C16 and C17 positions, as it is well known that the steroid-receptors are able to modify the mode of binding at ring D to accommodate several different types of C17 substitution (Duax & Norton, 1975).
In (I), ring A has a slightly distorted half-chair conformation, with asymmetry parameters (Duax & Norton, 1975) ΔC2(C1—C2) = 9.2 (5)° and ΔCs(C1) = 13.83°, as observed in a similar androstene derivative (Galdecki et al., 1990). Rings B and C adopt chair conformations, while ring D adopts a 13β,14α-half-chair conformation, with pseudo-rotational parameters Δ = 1.2° and ϕm = 41.5 (3)° (Altona et al., 1968). The geometry of the rings is trans at the B/C and C/D ring junctions. The C17—C16—C20—C21 torsion angle of 172.5 (3)° indicates that the 3-pyridyl ring has an E configuration with respect to the carbonyl group at position 17. The larger exocyclic angle C15—C16—C20 [132.1 (3)°] compared with C17—C16—C20 [119.2 (3)°] might be a consequence of the steric repulsion between H15B and H22 (H15B···H22 = 2.23 Å). The dihedral angle between the plane of the pyridine ring and the average molecular plane comprising rings A, B, C and D is 5.27 (1)°. The values of the C8—C14—C15 [120.4 (2)°] and C14—C13—C17 [100.6 (2)°] angles are close to the expected values of 119.3 and 99.2°, respectively (Duax & Norton, 1975). The pseudo-torsion angle C19—C10···C13—C18 is observed to be 6.3 (3)°. The C4—C5 (Csp2—Csp2) distance of 1.343 (4) Å confirms the localization of a double bond at this position (Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan et al., 2002a). A short intramolecular C—H···O contact is observed between C20 and O17, with an H20···O17 distance of 2.54 Å. An intermolecular C—H···O contact is observed between C26 and O3i, with an H26···O3i distance of 2.53 Å [symmetry code: (i) x, y, z − 1]. The structure is stabilized by van der Waals interactions.