Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201992X/ci6175sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680201992X/ci6175Isup2.hkl |
CCDC reference: 202326
The title compound was prepared by refluxing 17a-aza-D-homoandrost-4-en-3-one (1 g, 3.48 mmol), allyl bromide (1 ml) and dry methylketone (50 ml) for 15 min, and then adding anhydrous potassium carbonate (1 g). The reaction mixture was refluxed for 4 h with continuous stirring. The slurry obtained was filtered and the solvent was removed under reduced pressure. The residue obtained was crystallized from n-hexane to afford crystals of (I) (0.85 g, 74.63%; m.p.: 403–408 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 atoms and 1.2Ueq(C) for all other H atoms. The absolute configuration was assigned to correspond with that of a known chiral centre in a starting molecule, namely 17a-aza-D-homoandrost-4-en-3-one.
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. |
C22H33NO | F(000) = 720 |
Mr = 327.49 | Dx = 1.136 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 7.358 (2) Å | θ = 10–15° |
b = 12.635 (2) Å | µ = 0.07 mm−1 |
c = 20.596 (10) Å | T = 293 K |
V = 1914.8 (12) Å3 | Plate, green |
Z = 4 | 0.20 × 0.17 × 0.17 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.027 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.6° |
Graphite monochromator | h = 0→8 |
ω–2θ scans | k = −4→15 |
1992 measured reflections | l = −7→24 |
1910 independent reflections | 2 standard reflections every 120 min |
1228 reflections with I > 2σ(I) | 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0623P)2 + 0.1373P] where P = (Fo2 + 2Fc2)/3 |
1910 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C22H33NO | V = 1914.8 (12) Å3 |
Mr = 327.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.358 (2) Å | µ = 0.07 mm−1 |
b = 12.635 (2) Å | T = 293 K |
c = 20.596 (10) Å | 0.20 × 0.17 × 0.17 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.027 |
1992 measured reflections | 2 standard reflections every 120 min |
1910 independent reflections | intensity decay: none |
1228 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.12 e Å−3 |
1910 reflections | Δρmin = −0.15 e Å−3 |
217 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 | 0.5975 (6) | 0.4834 (3) | 0.1364 (2) | 0.0809 (13) | |
H1A | 0.4784 | 0.5162 | 0.1356 | 0.097* | |
H1B | 0.6358 | 0.4730 | 0.0918 | 0.097* | |
C2 | 0.5821 (7) | 0.3755 (3) | 0.1694 (3) | 0.0981 (15) | |
H2A | 0.5252 | 0.3842 | 0.2116 | 0.118* | |
H2B | 0.5051 | 0.3298 | 0.1435 | 0.118* | |
C3 | 0.7632 (7) | 0.3245 (3) | 0.17794 (19) | 0.0846 (13) | |
O3 | 0.7790 (6) | 0.2289 (2) | 0.18108 (16) | 0.1244 (14) | |
C4 | 0.9188 (6) | 0.3950 (3) | 0.18548 (16) | 0.0707 (11) | |
H4 | 1.0329 | 0.3649 | 0.1914 | 0.085* | |
C5 | 0.9067 (5) | 0.5009 (3) | 0.18438 (14) | 0.0573 (9) | |
C6 | 1.0675 (5) | 0.5680 (3) | 0.20174 (17) | 0.0695 (11) | |
H6A | 1.1756 | 0.5241 | 0.2015 | 0.083* | |
H6B | 1.0515 | 0.5946 | 0.2456 | 0.083* | |
C7 | 1.0974 (5) | 0.6615 (3) | 0.15624 (18) | 0.0607 (9) | |
H7A | 1.1365 | 0.6356 | 0.1142 | 0.073* | |
H7B | 1.1930 | 0.7063 | 0.1735 | 0.073* | |
C8 | 0.9236 (4) | 0.7269 (2) | 0.14806 (14) | 0.0458 (8) | |
H8 | 0.8879 | 0.7537 | 0.1908 | 0.055* | |
C9 | 0.7721 (4) | 0.6536 (2) | 0.12345 (15) | 0.0466 (8) | |
H9 | 0.8183 | 0.6222 | 0.0832 | 0.056* | |
C10 | 0.7313 (5) | 0.5589 (2) | 0.16968 (15) | 0.0544 (9) | |
C11 | 0.6011 (4) | 0.7148 (3) | 0.10433 (17) | 0.0586 (9) | |
H11A | 0.5187 | 0.6674 | 0.0819 | 0.070* | |
H11B | 0.5405 | 0.7392 | 0.1434 | 0.070* | |
C12 | 0.6404 (4) | 0.8091 (2) | 0.06113 (16) | 0.0525 (8) | |
H12A | 0.5276 | 0.8462 | 0.0525 | 0.063* | |
H12B | 0.6878 | 0.7839 | 0.0200 | 0.063* | |
C13 | 0.7764 (4) | 0.8864 (2) | 0.09090 (13) | 0.0430 (7) | |
C14 | 0.9527 (4) | 0.8221 (2) | 0.10283 (14) | 0.0425 (7) | |
H14 | 0.9867 | 0.7924 | 0.0606 | 0.051* | |
C15 | 1.1112 (4) | 0.8932 (3) | 0.12316 (17) | 0.0586 (9) | |
H15A | 1.0850 | 0.9252 | 0.1649 | 0.070* | |
H15B | 1.2206 | 0.8510 | 0.1275 | 0.070* | |
C16 | 1.1409 (5) | 0.9786 (3) | 0.07313 (18) | 0.0631 (10) | |
H16A | 1.2349 | 1.0265 | 0.0882 | 0.076* | |
H16B | 1.1821 | 0.9467 | 0.0329 | 0.076* | |
C17 | 0.9700 (5) | 1.0397 (3) | 0.06076 (18) | 0.0609 (9) | |
H17A | 0.9371 | 1.0783 | 0.0997 | 0.073* | |
H17B | 0.9918 | 1.0908 | 0.0265 | 0.073* | |
N17A | 0.8184 (3) | 0.97047 (19) | 0.04182 (12) | 0.0486 (7) | |
C18 | 0.6990 (5) | 0.9333 (3) | 0.15371 (15) | 0.0625 (9) | |
H18A | 0.7861 | 0.9809 | 0.1724 | 0.094* | |
H18B | 0.6735 | 0.8773 | 0.1838 | 0.094* | |
H18C | 0.5890 | 0.9711 | 0.1442 | 0.094* | |
C19 | 0.6499 (6) | 0.5968 (3) | 0.23569 (16) | 0.0778 (12) | |
H19A | 0.5390 | 0.6347 | 0.2279 | 0.117* | |
H19B | 0.7353 | 0.6425 | 0.2571 | 0.117* | |
H19C | 0.6255 | 0.5366 | 0.2627 | 0.117* | |
C20 | 0.6608 (5) | 1.0388 (3) | 0.02664 (18) | 0.0696 (11) | |
H20A | 0.6408 | 1.0872 | 0.0625 | 0.084* | |
H20B | 0.5532 | 0.9950 | 0.0223 | 0.084* | |
C21 | 0.6859 (6) | 1.1007 (3) | −0.03375 (18) | 0.0779 (11) | |
H21 | 0.7089 | 1.0627 | −0.0715 | 0.093* | |
C22 | 0.6790 (8) | 1.2030 (3) | −0.0389 (3) | 0.124 (2) | |
H22A | 0.6564 | 1.2443 | −0.0024 | 0.148* | |
H22B | 0.6966 | 1.2350 | −0.0791 | 0.148* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.084 (3) | 0.060 (2) | 0.099 (3) | −0.019 (2) | −0.013 (2) | 0.018 (2) |
C2 | 0.111 (4) | 0.062 (3) | 0.121 (4) | −0.020 (3) | 0.000 (3) | 0.016 (3) |
C3 | 0.128 (4) | 0.054 (2) | 0.071 (3) | 0.001 (3) | 0.009 (3) | 0.0096 (19) |
O3 | 0.189 (4) | 0.0567 (16) | 0.128 (3) | 0.004 (2) | 0.002 (3) | 0.0110 (17) |
C4 | 0.087 (3) | 0.066 (2) | 0.059 (2) | 0.014 (2) | 0.012 (2) | 0.0157 (19) |
C5 | 0.066 (2) | 0.062 (2) | 0.0442 (19) | 0.004 (2) | 0.0043 (18) | 0.0170 (16) |
C6 | 0.064 (2) | 0.074 (2) | 0.071 (2) | 0.008 (2) | −0.009 (2) | 0.0214 (19) |
C7 | 0.0471 (19) | 0.067 (2) | 0.068 (2) | 0.0012 (19) | −0.0033 (18) | 0.0148 (19) |
C8 | 0.0377 (17) | 0.0566 (18) | 0.0430 (17) | 0.0025 (16) | −0.0006 (14) | 0.0029 (15) |
C9 | 0.0436 (19) | 0.0506 (17) | 0.0455 (16) | 0.0000 (17) | 0.0010 (15) | 0.0017 (14) |
C10 | 0.056 (2) | 0.0554 (18) | 0.0519 (19) | −0.0034 (19) | 0.0068 (17) | 0.0035 (16) |
C11 | 0.0433 (19) | 0.0593 (19) | 0.073 (2) | −0.0074 (17) | −0.0085 (18) | 0.0037 (18) |
C12 | 0.0430 (18) | 0.0524 (19) | 0.062 (2) | 0.0019 (16) | −0.0111 (16) | 0.0036 (17) |
C13 | 0.0372 (17) | 0.0481 (16) | 0.0435 (16) | 0.0011 (16) | 0.0022 (14) | −0.0004 (15) |
C14 | 0.0368 (17) | 0.0523 (18) | 0.0384 (17) | −0.0015 (15) | −0.0013 (13) | −0.0022 (14) |
C15 | 0.0419 (19) | 0.066 (2) | 0.068 (2) | −0.0050 (18) | −0.0075 (17) | 0.0090 (19) |
C16 | 0.047 (2) | 0.061 (2) | 0.081 (2) | −0.0127 (19) | 0.0003 (17) | 0.0054 (19) |
C17 | 0.063 (2) | 0.0502 (18) | 0.070 (2) | −0.0067 (19) | 0.0008 (19) | 0.0056 (19) |
N17A | 0.0450 (15) | 0.0427 (13) | 0.0582 (15) | 0.0050 (14) | −0.0005 (13) | 0.0057 (13) |
C18 | 0.060 (2) | 0.069 (2) | 0.0588 (19) | 0.007 (2) | 0.0125 (18) | −0.0108 (17) |
C19 | 0.085 (3) | 0.077 (2) | 0.071 (2) | −0.003 (2) | 0.033 (2) | 0.015 (2) |
C20 | 0.061 (2) | 0.063 (2) | 0.085 (3) | 0.009 (2) | −0.004 (2) | 0.006 (2) |
C21 | 0.088 (3) | 0.067 (2) | 0.078 (2) | 0.023 (2) | −0.013 (2) | 0.004 (2) |
C22 | 0.168 (5) | 0.071 (3) | 0.132 (4) | 0.035 (3) | −0.005 (4) | 0.031 (3) |
C1—C2 | 1.528 (5) | C12—H12A | 0.97 |
C1—C10 | 1.532 (5) | C12—H12B | 0.97 |
C1—H1A | 0.97 | C13—N17A | 1.499 (4) |
C1—H1B | 0.97 | C13—C18 | 1.532 (4) |
C2—C3 | 1.490 (6) | C13—C14 | 1.550 (4) |
C2—H2A | 0.97 | C14—C15 | 1.530 (4) |
C2—H2B | 0.97 | C14—H14 | 0.98 |
C3—O3 | 1.215 (4) | C15—C16 | 1.508 (4) |
C3—C4 | 1.460 (6) | C15—H15A | 0.97 |
C4—C5 | 1.340 (5) | C15—H15B | 0.97 |
C4—H4 | 0.93 | C16—C17 | 1.497 (5) |
C5—C6 | 1.500 (5) | C16—H16A | 0.97 |
C5—C10 | 1.515 (5) | C16—H16B | 0.97 |
C6—C7 | 1.523 (4) | C17—N17A | 1.471 (4) |
C6—H6A | 0.97 | C17—H17A | 0.97 |
C6—H6B | 0.97 | C17—H17B | 0.97 |
C7—C8 | 1.532 (4) | N17A—C20 | 1.479 (4) |
C7—H7A | 0.97 | C18—H18A | 0.96 |
C7—H7B | 0.97 | C18—H18B | 0.96 |
C8—C9 | 1.535 (4) | C18—H18C | 0.96 |
C8—C14 | 1.537 (4) | C19—H19A | 0.96 |
C8—H8 | 0.98 | C19—H19B | 0.96 |
C9—C11 | 1.529 (4) | C19—H19C | 0.96 |
C9—C10 | 1.559 (4) | C20—C21 | 1.481 (5) |
C9—H9 | 0.98 | C20—H20A | 0.97 |
C10—C19 | 1.561 (5) | C20—H20B | 0.97 |
C11—C12 | 1.515 (4) | C21—C22 | 1.298 (5) |
C11—H11A | 0.97 | C21—H21 | 0.93 |
C11—H11B | 0.97 | C22—H22A | 0.93 |
C12—C13 | 1.527 (4) | C22—H22B | 0.93 |
C2—C1—C10 | 113.8 (4) | C11—C12—H12B | 109.0 |
C2—C1—H1A | 108.8 | C13—C12—H12B | 109.0 |
C10—C1—H1A | 108.8 | H12A—C12—H12B | 107.8 |
C2—C1—H1B | 108.8 | N17A—C13—C12 | 108.5 (2) |
C10—C1—H1B | 108.8 | N17A—C13—C18 | 111.8 (2) |
H1A—C1—H1B | 107.7 | C12—C13—C18 | 110.1 (3) |
C3—C2—C1 | 111.8 (4) | N17A—C13—C14 | 107.8 (2) |
C3—C2—H2A | 109.2 | C12—C13—C14 | 106.1 (2) |
C1—C2—H2A | 109.2 | C18—C13—C14 | 112.3 (2) |
C3—C2—H2B | 109.2 | C15—C14—C8 | 113.6 (2) |
C1—C2—H2B | 109.2 | C15—C14—C13 | 112.0 (2) |
H2A—C2—H2B | 107.9 | C8—C14—C13 | 112.9 (2) |
O3—C3—C4 | 121.8 (5) | C15—C14—H14 | 105.9 |
O3—C3—C2 | 121.5 (5) | C8—C14—H14 | 105.9 |
C4—C3—C2 | 116.7 (3) | C13—C14—H14 | 105.9 |
C5—C4—C3 | 123.8 (4) | C16—C15—C14 | 110.1 (3) |
C5—C4—H4 | 118.1 | C16—C15—H15A | 109.6 |
C3—C4—H4 | 118.1 | C14—C15—H15A | 109.6 |
C4—C5—C6 | 120.6 (4) | C16—C15—H15B | 109.6 |
C4—C5—C10 | 122.9 (4) | C14—C15—H15B | 109.6 |
C6—C5—C10 | 116.5 (3) | H15A—C15—H15B | 108.2 |
C5—C6—C7 | 114.0 (3) | C17—C16—C15 | 111.3 (3) |
C5—C6—H6A | 108.8 | C17—C16—H16A | 109.4 |
C7—C6—H6A | 108.8 | C15—C16—H16A | 109.4 |
C5—C6—H6B | 108.8 | C17—C16—H16B | 109.4 |
C7—C6—H6B | 108.8 | C15—C16—H16B | 109.4 |
H6A—C6—H6B | 107.7 | H16A—C16—H16B | 108.0 |
C6—C7—C8 | 111.4 (3) | N17A—C17—C16 | 112.1 (3) |
C6—C7—H7A | 109.3 | N17A—C17—H17A | 109.2 |
C8—C7—H7A | 109.3 | C16—C17—H17A | 109.2 |
C6—C7—H7B | 109.3 | N17A—C17—H17B | 109.2 |
C8—C7—H7B | 109.3 | C16—C17—H17B | 109.2 |
H7A—C7—H7B | 108.0 | H17A—C17—H17B | 107.9 |
C7—C8—C9 | 108.5 (2) | C17—N17A—C20 | 107.7 (2) |
C7—C8—C14 | 111.9 (2) | C17—N17A—C13 | 113.5 (2) |
C9—C8—C14 | 111.9 (2) | C20—N17A—C13 | 113.3 (2) |
C7—C8—H8 | 108.1 | C13—C18—H18A | 109.5 |
C9—C8—H8 | 108.1 | C13—C18—H18B | 109.5 |
C14—C8—H8 | 108.1 | H18A—C18—H18B | 109.5 |
C11—C9—C8 | 112.2 (2) | C13—C18—H18C | 109.5 |
C11—C9—C10 | 112.8 (3) | H18A—C18—H18C | 109.5 |
C8—C9—C10 | 113.7 (3) | H18B—C18—H18C | 109.5 |
C11—C9—H9 | 105.8 | C10—C19—H19A | 109.5 |
C8—C9—H9 | 105.8 | C10—C19—H19B | 109.5 |
C10—C9—H9 | 105.8 | H19A—C19—H19B | 109.5 |
C5—C10—C1 | 109.6 (3) | C10—C19—H19C | 109.5 |
C5—C10—C9 | 109.2 (3) | H19A—C19—H19C | 109.5 |
C1—C10—C9 | 109.2 (3) | H19B—C19—H19C | 109.5 |
C5—C10—C19 | 107.5 (3) | N17A—C20—C21 | 112.8 (3) |
C1—C10—C19 | 109.5 (3) | N17A—C20—H20A | 109.0 |
C9—C10—C19 | 111.7 (2) | C21—C20—H20A | 109.0 |
C12—C11—C9 | 113.0 (3) | N17A—C20—H20B | 109.0 |
C12—C11—H11A | 109.0 | C21—C20—H20B | 109.0 |
C9—C11—H11A | 109.0 | H20A—C20—H20B | 107.8 |
C12—C11—H11B | 109.0 | C22—C21—C20 | 126.2 (4) |
C9—C11—H11B | 109.0 | C22—C21—H21 | 116.9 |
H11A—C11—H11B | 107.8 | C20—C21—H21 | 116.9 |
C11—C12—C13 | 113.1 (3) | C21—C22—H22A | 120.0 |
C11—C12—H12A | 109.0 | C21—C22—H22B | 120.0 |
C13—C12—H12A | 109.0 | H22A—C22—H22B | 120.0 |
C10—C1—C2—C3 | −53.3 (5) | C9—C11—C12—C13 | −56.0 (3) |
C1—C2—C3—O3 | −153.6 (4) | C11—C12—C13—N17A | 174.7 (2) |
C1—C2—C3—C4 | 29.3 (6) | C11—C12—C13—C18 | −62.6 (3) |
O3—C3—C4—C5 | −177.8 (4) | C11—C12—C13—C14 | 59.1 (3) |
C2—C3—C4—C5 | −0.8 (6) | C7—C8—C14—C15 | −54.1 (3) |
C3—C4—C5—C6 | 171.3 (3) | C9—C8—C14—C15 | −176.1 (3) |
C3—C4—C5—C10 | −5.1 (6) | C7—C8—C14—C13 | 177.1 (3) |
C4—C5—C6—C7 | 136.2 (3) | C9—C8—C14—C13 | 55.0 (3) |
C10—C5—C6—C7 | −47.2 (4) | N17A—C13—C14—C15 | 55.3 (3) |
C5—C6—C7—C8 | 51.6 (4) | C12—C13—C14—C15 | 171.4 (2) |
C6—C7—C8—C9 | −56.7 (3) | C18—C13—C14—C15 | −68.3 (3) |
C6—C7—C8—C14 | 179.4 (3) | N17A—C13—C14—C8 | −175.0 (2) |
C7—C8—C9—C11 | −171.6 (3) | C12—C13—C14—C8 | −58.9 (3) |
C14—C8—C9—C11 | −47.7 (3) | C18—C13—C14—C8 | 61.4 (3) |
C7—C8—C9—C10 | 59.0 (3) | C8—C14—C15—C16 | 174.9 (3) |
C14—C8—C9—C10 | −177.1 (2) | C13—C14—C15—C16 | −55.8 (3) |
C4—C5—C10—C1 | −17.9 (5) | C14—C15—C16—C17 | 54.4 (4) |
C6—C5—C10—C1 | 165.5 (3) | C15—C16—C17—N17A | −55.3 (4) |
C4—C5—C10—C9 | −137.5 (3) | C16—C17—N17A—C20 | −176.3 (3) |
C6—C5—C10—C9 | 45.9 (4) | C16—C17—N17A—C13 | 57.4 (3) |
C4—C5—C10—C19 | 101.1 (4) | C12—C13—N17A—C17 | −170.5 (2) |
C6—C5—C10—C19 | −75.5 (3) | C18—C13—N17A—C17 | 67.9 (3) |
C2—C1—C10—C5 | 46.5 (5) | C14—C13—N17A—C17 | −56.0 (3) |
C2—C1—C10—C9 | 166.1 (3) | C12—C13—N17A—C20 | 66.3 (3) |
C2—C1—C10—C19 | −71.2 (4) | C18—C13—N17A—C20 | −55.3 (3) |
C11—C9—C10—C5 | 178.2 (3) | C14—C13—N17A—C20 | −179.2 (2) |
C8—C9—C10—C5 | −52.6 (3) | C17—N17A—C20—C21 | 69.7 (4) |
C11—C9—C10—C1 | 58.4 (3) | C13—N17A—C20—C21 | −163.9 (3) |
C8—C9—C10—C1 | −172.5 (3) | N17A—C20—C21—C22 | −122.6 (5) |
C11—C9—C10—C19 | −62.9 (4) | H14—C14—C13—C18 | 176.8 |
C8—C9—C10—C19 | 66.2 (4) | H8—C8—C9—H9 | −173.8 |
C8—C9—C11—C12 | 48.3 (4) | H9—C9—C10—C19 | −178.1 |
C10—C9—C11—C12 | 178.2 (3) | C19—C10—C13—C18 | 0.4 (3) |
Experimental details
Crystal data | |
Chemical formula | C22H33NO |
Mr | 327.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.358 (2), 12.635 (2), 20.596 (10) |
V (Å3) | 1914.8 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.20 × 0.17 × 0.17 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1992, 1910, 1228 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.120, 1.03 |
No. of reflections | 1910 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.15 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP97 (Zsolnai, 1997), SHELXL97.
The X-ray investigation of the title compound, (I), was undertaken as part of a 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,c; Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan et al., 2002a,b). Compound (I), consisting of four six-membered fused rings, is a steroid with the normal 8β, 9α, 10β, 13β and 14α configuration. We are particularly interested to study the conformational flexibility of the steroid due to the substitution of the allyl moiety at position 17a.
In (I), ring A adopts a sofa conformation, with atom C1 in the α-position, as is evident from the deviation of C1 by 0.571 (4) Å from the mean C2/C3/C4/C5/C10 plane. Rings B and C adopt slightly distorted chair conformations, with Cremer & Pople (1975) puckering parameters Q = 0.538 (5) Å, θ = 10.4 (5)° and ϕ =188.1 (7)° for ring B, and Q = 0.561 (5) Å, θ = 9.1 (5)° and ϕ = 241.7 (8)° for ring C. Ring D adopts a normal chair conformation, with Q = 0.564 (5) Å, θ = 1.8 (5)° and ϕ = 98.4 (6)°. The allyl group at N17A shows a β-orientation. The C13—N17A—C20—C21 torsion angle is −163.9 (3)°; thus, the allyl moiety is antiperiplanar with respect to the C13—N17A bond. The B/C and C/D ring junctions are all trans. The widening of the exocyclic angle C13—N17A—C20 [113.3 (2)°] may be due to the steric interactions between atoms H12A and H20B (H12A···H20B = 1.99 Å). The C2—C3 (Csp3—Csp2) bond distance of 1.490 (6) Å is comparable with the reported value of 1.489 (5) Å in a related structure (Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002), which also shows a 1α-sofa conformation for the ring A. The C4—C5 (Csp2—Csp2) distance of 1.340 (5) Å confirms the localization of a double bond at this position. The mean Csp3—Csp3 bond length in (I) is calculated as 1.528 (2) Å. However, the C10—C9 (Csp3—Csp3) distance of 1.559 (4) Å has the largest deviation from the mean value. A similar larger value for this bond has been observed in some related structures, e.g. 1.567 (2) (Duax & Norton, 1975), 1.559 (3) (Paixao et al., 1998), 1.564 (3) (Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a), and 1.560 (3) and 1.556 (3) Å in two independent molecules (Vasuki, Thamotharan et al., 2002b). The C3···C16 distance of 8.98 Å, which is a measure of the length of the steroid nucleus, indicates that the molecule is in a completely extended form (Isabella, 1970). The pseudo-torsion angle C19—C10··· C13—C18 in (I) is 0.4 (3)°. A short intermolecular C—H···O contact is observed between atoms C6 and O3i, with an H6B···O3i distance of 2.59 Å [symmetry code: (i) −x, 1/2 + y, 1/2 − z]. The structure is stabilized by van der Walls interactions.