Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009319/vj1164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009319/vj1164Isup2.hkl |
CCDC reference: 192988
Freshly distilled pyrrolidine was added to a refluxing solution of 16-(4-cyanobenzylidene)androst-4-ene-3,17-dione (0.5 g, 1.25 mmol) in methanol (50 ml). After refluxing for 15 min, the precipitate obtained was cooled in ice, filtered and washed with methanol to obtain 16-(4-cyanobenzylidene)-3-pyrrolidinoandrosta-3,5-dien-17-one (0.4 g). This was immediately suspended in methanol (50 ml) and reduced with sodium borohydride (1.0 g), while stirring at room temperature. The stirring was continued for 4 h, excess methanol was removed under reduced pressure and ice-cold water was added. The precipitate obtained was filtered, washed with water, dried and crystallized from acetone to obtain (I) (0.23 g, 56.99%; m.p. 501–507 K). Spectroscopic analysis: UVmax (MeOH): 282.2 nm (log ε = 4.47); IRνmax (KBr, cm-1): 3350, 2980, 2200, 1595; 1H NMR (CDCl3 + DMSO, δ, p.p.m.): 0.69 (s, 3H, 18-CH3), 1.02 (s, 3H, 19-CH3), 2.61 (s, 4H, N-methylene of pyrrolidine function), 4.02 (m, 1H, 3α-H), 5.36 (s, 2H, 6-CH), 6.55 [s, 1H, vinyl H of 16-(4-cyanobenzylidene)], 7.47 (d, 2H, Jo = 8.3 Hz, 2-CH and 6-CH aromatic H), 7.67 (d, 2H, Jo = 8.3 Hz, 3-CH and 5-CH aromatic H); MS: m/z (mass/relative intensity): 456 [M+].
All H atoms were fixed with geometrical considerations (C—H = 0.93–0.98 Å and O—H = 0.82 Å Are these the correct constraints?), except water H atoms, for which the overall displacement parameters were refined.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97.
C31H40N2O·H2O | Dx = 1.168 Mg m−3 |
Mr = 474.67 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 7.2171 (6) Å | θ = 20–30° |
b = 18.541 (3) Å | µ = 0.56 mm−1 |
c = 20.176 (6) Å | T = 293 K |
V = 2699.8 (9) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.25 × 0.10 mm |
F(000) = 1032 |
Enraf-Nonius CAD-4 diffractometer | 2580 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 68.0°, θmin = 3.2° |
ω/2θ scans | h = −8→2 |
Absorption correction: ψ scan (North et al., 1968) | k = −22→9 |
Tmin = 0.850, Tmax = 0.946 | l = −24→10 |
2916 measured reflections | 2 standard reflections every 100 reflections |
2898 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0626P)2 + 0.6312P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.123 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.19 e Å−3 |
2898 reflections | Δρmin = −0.19 e Å−3 |
318 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0021 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 83 Friedel pairs Query |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −1.4 (5) |
C31H40N2O·H2O | V = 2699.8 (9) Å3 |
Mr = 474.67 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 7.2171 (6) Å | µ = 0.56 mm−1 |
b = 18.541 (3) Å | T = 293 K |
c = 20.176 (6) Å | 0.30 × 0.25 × 0.10 mm |
Enraf-Nonius CAD-4 diffractometer | 2580 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.850, Tmax = 0.946 | 2 standard reflections every 100 reflections |
2916 measured reflections | intensity decay: none |
2898 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | Δρmax = 0.19 e Å−3 |
S = 1.09 | Δρmin = −0.19 e Å−3 |
2898 reflections | Absolute structure: Flack (1983), 83 Friedel pairs Query |
318 parameters | Absolute structure parameter: −1.4 (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 | −0.4606 (4) | −0.18329 (15) | −0.65575 (18) | 0.0628 (8) | |
H1A | −0.5750 | −0.1940 | −0.6790 | 0.075* | |
H1B | −0.4924 | −0.1707 | −0.6105 | 0.075* | |
C2 | −0.3693 (4) | −0.11851 (15) | −0.68839 (17) | 0.0634 (8) | |
H2A | −0.4521 | −0.0774 | −0.6856 | 0.076* | |
H2B | −0.3486 | −0.1289 | −0.7349 | 0.076* | |
C3 | −0.1842 (5) | −0.09927 (15) | −0.65563 (15) | 0.0582 (7) | |
H3 | −0.2083 | −0.0840 | −0.6099 | 0.070* | |
C4 | −0.0594 (4) | −0.16564 (16) | −0.65401 (18) | 0.0665 (8) | |
H4A | −0.0203 | −0.1771 | −0.6988 | 0.080* | |
H4B | 0.0505 | −0.1549 | −0.6282 | 0.080* | |
C5 | −0.1561 (4) | −0.23056 (15) | −0.62438 (13) | 0.0497 (6) | |
C6 | −0.0748 (4) | −0.26771 (15) | −0.57590 (16) | 0.0613 (8) | |
H6 | 0.0389 | −0.2513 | −0.5604 | 0.074* | |
C7 | −0.1540 (4) | −0.33385 (14) | −0.54483 (14) | 0.0544 (7) | |
H7A | −0.2089 | −0.3213 | −0.5025 | 0.065* | |
H7B | −0.0552 | −0.3682 | −0.5366 | 0.065* | |
C8 | −0.3006 (4) | −0.36886 (13) | −0.58871 (13) | 0.0458 (6) | |
H8 | −0.2395 | −0.3905 | −0.6273 | 0.055* | |
C9 | −0.4363 (4) | −0.31064 (14) | −0.61280 (13) | 0.0482 (6) | |
H9 | −0.4809 | −0.2863 | −0.5728 | 0.058* | |
C10 | −0.3398 (4) | −0.25153 (14) | −0.65485 (13) | 0.0477 (6) | |
C11 | −0.6106 (4) | −0.34276 (17) | −0.64664 (17) | 0.0643 (8) | |
H11A | −0.7000 | −0.3045 | −0.6539 | 0.077* | |
H11B | −0.5759 | −0.3620 | −0.6896 | 0.077* | |
C12 | −0.7016 (4) | −0.40240 (17) | −0.60600 (18) | 0.0655 (8) | |
H12A | −0.7496 | −0.3823 | −0.5651 | 0.079* | |
H12B | −0.8048 | −0.4224 | −0.6307 | 0.079* | |
C13 | −0.5640 (4) | −0.46195 (15) | −0.58998 (13) | 0.0527 (6) | |
C14 | −0.4037 (4) | −0.42741 (14) | −0.55113 (12) | 0.0471 (6) | |
H14 | −0.4604 | −0.4036 | −0.5128 | 0.057* | |
C15 | −0.2960 (4) | −0.49195 (14) | −0.52334 (14) | 0.0522 (7) | |
H15A | −0.2033 | −0.5086 | −0.5546 | 0.063* | |
H15B | −0.2357 | −0.4797 | −0.4819 | 0.063* | |
C16 | −0.4454 (4) | −0.54836 (15) | −0.51294 (13) | 0.0523 (7) | |
C17 | −0.6276 (4) | −0.51696 (17) | −0.53783 (15) | 0.0592 (7) | |
H17 | −0.6832 | −0.4899 | −0.5011 | 0.071* | |
O17 | −0.7552 (4) | −0.57058 (14) | −0.55695 (14) | 0.0925 (9) | |
H17A | −0.8097 | −0.5576 | −0.5906 | 0.139* | |
C18 | −0.4999 (5) | −0.50178 (17) | −0.65225 (14) | 0.0676 (9) | |
H18A | −0.6052 | −0.5225 | −0.6742 | 0.101* | |
H18B | −0.4149 | −0.5393 | −0.6401 | 0.101* | |
H18C | −0.4394 | −0.4685 | −0.6816 | 0.101* | |
C19 | −0.3067 (5) | −0.27759 (17) | −0.72614 (14) | 0.0668 (9) | |
H19A | −0.4228 | −0.2909 | −0.7459 | 0.100* | |
H19B | −0.2255 | −0.3186 | −0.7256 | 0.100* | |
H19C | −0.2510 | −0.2395 | −0.7515 | 0.100* | |
C20 | −0.4363 (5) | −0.61512 (16) | −0.48837 (13) | 0.0569 (7) | |
H20 | −0.5471 | −0.6407 | −0.4894 | 0.068* | |
C21 | −0.2794 (4) | −0.65442 (14) | −0.46009 (13) | 0.0528 (7) | |
C22 | −0.3158 (5) | −0.72049 (15) | −0.42936 (14) | 0.0598 (8) | |
H22 | −0.4360 | −0.7386 | −0.4296 | 0.072* | |
C23 | −0.1783 (5) | −0.75925 (16) | −0.39890 (16) | 0.0634 (8) | |
H23 | −0.2067 | −0.8024 | −0.3778 | 0.076* | |
C24 | 0.0020 (5) | −0.73452 (16) | −0.39943 (15) | 0.0611 (8) | |
C241 | 0.1473 (6) | −0.77506 (19) | −0.36784 (18) | 0.0750 (10) | |
N241 | 0.2620 (5) | −0.80736 (19) | −0.3434 (2) | 0.1058 (12) | |
C25 | 0.0428 (5) | −0.66972 (17) | −0.43081 (16) | 0.0676 (9) | |
H25 | 0.1639 | −0.6525 | −0.4313 | 0.081* | |
C26 | −0.0958 (4) | −0.63103 (16) | −0.46109 (17) | 0.0654 (8) | |
H26 | −0.0665 | −0.5882 | −0.4828 | 0.078* | |
N31 | −0.0956 (4) | −0.03955 (12) | −0.69112 (11) | 0.0545 (6) | |
C32 | 0.0939 (5) | −0.02205 (17) | −0.66792 (18) | 0.0701 (9) | |
H32A | 0.1827 | −0.0574 | −0.6837 | 0.084* | |
H32B | 0.0991 | −0.0203 | −0.6199 | 0.084* | |
C33 | 0.1315 (6) | 0.05102 (18) | −0.69748 (19) | 0.0772 (10) | |
H33A | 0.2127 | 0.0789 | −0.6690 | 0.093* | |
H33B | 0.1888 | 0.0464 | −0.7408 | 0.093* | |
C34 | −0.0552 (6) | 0.08622 (18) | −0.7030 (2) | 0.0827 (11) | |
H34A | −0.0768 | 0.1027 | −0.7480 | 0.099* | |
H34B | −0.0634 | 0.1273 | −0.6733 | 0.099* | |
C35 | −0.1954 (5) | 0.02902 (15) | −0.68384 (18) | 0.0682 (9) | |
H35A | −0.2365 | 0.0357 | −0.6385 | 0.082* | |
H35B | −0.3022 | 0.0306 | −0.7129 | 0.082* | |
O1W | 0.0352 (4) | −0.57104 (17) | −0.67018 (12) | 0.1064 (10) | |
H1W | −0.0346 | −0.6051 | −0.6671 | 0.085* | |
H2W | 0.0372 | −0.5610 | −0.7175 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0479 (16) | 0.0547 (16) | 0.086 (2) | 0.0035 (14) | −0.0014 (16) | 0.0110 (16) |
C2 | 0.0559 (17) | 0.0501 (15) | 0.084 (2) | 0.0012 (14) | −0.0042 (17) | 0.0120 (15) |
C3 | 0.0675 (18) | 0.0512 (15) | 0.0559 (15) | −0.0091 (15) | −0.0007 (15) | 0.0048 (13) |
C4 | 0.0570 (18) | 0.0569 (17) | 0.086 (2) | −0.0087 (16) | −0.0111 (18) | 0.0163 (16) |
C5 | 0.0468 (14) | 0.0495 (14) | 0.0528 (14) | 0.0007 (13) | 0.0010 (13) | 0.0011 (12) |
C6 | 0.0504 (15) | 0.0558 (15) | 0.0778 (19) | −0.0105 (15) | −0.0162 (15) | 0.0103 (15) |
C7 | 0.0502 (15) | 0.0527 (14) | 0.0602 (16) | −0.0014 (13) | −0.0078 (14) | 0.0064 (13) |
C8 | 0.0441 (13) | 0.0466 (13) | 0.0467 (13) | 0.0023 (12) | 0.0006 (12) | 0.0017 (11) |
C9 | 0.0429 (13) | 0.0518 (14) | 0.0498 (14) | 0.0019 (12) | −0.0016 (12) | 0.0006 (12) |
C10 | 0.0474 (14) | 0.0464 (13) | 0.0493 (13) | 0.0020 (12) | −0.0009 (12) | 0.0024 (11) |
C11 | 0.0473 (16) | 0.0638 (17) | 0.082 (2) | −0.0076 (15) | −0.0159 (15) | 0.0191 (16) |
C12 | 0.0458 (16) | 0.0712 (19) | 0.080 (2) | −0.0097 (15) | −0.0128 (16) | 0.0149 (17) |
C13 | 0.0519 (15) | 0.0563 (15) | 0.0500 (14) | −0.0069 (14) | −0.0034 (13) | 0.0113 (12) |
C14 | 0.0463 (14) | 0.0507 (14) | 0.0443 (13) | −0.0018 (12) | 0.0022 (12) | 0.0028 (11) |
C15 | 0.0503 (16) | 0.0543 (15) | 0.0519 (14) | −0.0008 (13) | 0.0019 (13) | 0.0078 (12) |
C16 | 0.0549 (16) | 0.0573 (15) | 0.0445 (13) | −0.0045 (14) | 0.0032 (13) | 0.0047 (12) |
C17 | 0.0517 (16) | 0.0663 (17) | 0.0597 (16) | −0.0104 (14) | 0.0011 (14) | 0.0135 (15) |
O17 | 0.0824 (17) | 0.0945 (17) | 0.1007 (19) | −0.0428 (15) | −0.0277 (15) | 0.0444 (15) |
C18 | 0.085 (2) | 0.0681 (19) | 0.0492 (15) | −0.0183 (18) | −0.0041 (17) | 0.0040 (14) |
C19 | 0.084 (2) | 0.0638 (17) | 0.0528 (15) | −0.0094 (18) | 0.0033 (17) | −0.0033 (14) |
C20 | 0.0590 (17) | 0.0598 (16) | 0.0517 (14) | −0.0082 (15) | 0.0025 (14) | 0.0039 (13) |
C21 | 0.0680 (18) | 0.0485 (14) | 0.0421 (13) | −0.0022 (14) | 0.0054 (13) | 0.0033 (12) |
C22 | 0.073 (2) | 0.0488 (15) | 0.0581 (16) | −0.0101 (16) | 0.0020 (16) | 0.0020 (13) |
C23 | 0.083 (2) | 0.0481 (15) | 0.0588 (17) | 0.0005 (16) | 0.0033 (17) | 0.0078 (13) |
C24 | 0.072 (2) | 0.0526 (16) | 0.0585 (16) | 0.0085 (16) | 0.0051 (16) | 0.0011 (14) |
C241 | 0.082 (2) | 0.0639 (19) | 0.079 (2) | 0.013 (2) | 0.004 (2) | 0.0117 (17) |
N241 | 0.102 (3) | 0.093 (2) | 0.122 (3) | 0.027 (2) | −0.012 (2) | 0.024 (2) |
C25 | 0.0620 (19) | 0.0616 (17) | 0.079 (2) | 0.0029 (17) | 0.0050 (18) | 0.0144 (16) |
C26 | 0.0650 (19) | 0.0549 (16) | 0.0761 (19) | −0.0010 (15) | 0.0116 (17) | 0.0177 (16) |
N31 | 0.0630 (15) | 0.0452 (11) | 0.0553 (13) | −0.0029 (12) | −0.0031 (12) | 0.0001 (10) |
C32 | 0.071 (2) | 0.0632 (18) | 0.076 (2) | −0.0159 (17) | −0.0082 (18) | 0.0068 (16) |
C33 | 0.093 (3) | 0.0611 (18) | 0.077 (2) | −0.019 (2) | 0.002 (2) | 0.0012 (17) |
C34 | 0.100 (3) | 0.0546 (17) | 0.094 (2) | −0.012 (2) | −0.008 (2) | 0.0097 (18) |
C35 | 0.085 (2) | 0.0445 (14) | 0.075 (2) | 0.0007 (16) | −0.0017 (19) | −0.0044 (14) |
O1W | 0.119 (2) | 0.136 (2) | 0.0643 (13) | −0.069 (2) | −0.0188 (15) | 0.0232 (15) |
C1—C2 | 1.520 (4) | C16—C20 | 1.335 (4) |
C1—C10 | 1.536 (4) | C16—C17 | 1.523 (4) |
C1—H1A | 0.9700 | C17—O17 | 1.409 (4) |
C1—H1B | 0.9700 | C17—H17 | 0.9800 |
C2—C3 | 1.533 (4) | O17—H17A | 0.8200 |
C2—H2A | 0.9700 | C18—H18A | 0.9600 |
C2—H2B | 0.9700 | C18—H18B | 0.9600 |
C3—N31 | 1.466 (3) | C18—H18C | 0.9600 |
C3—C4 | 1.525 (4) | C19—H19A | 0.9600 |
C3—H3 | 0.9800 | C19—H19B | 0.9600 |
C4—C5 | 1.514 (4) | C19—H19C | 0.9600 |
C4—H4A | 0.9700 | C20—C21 | 1.462 (4) |
C4—H4B | 0.9700 | C20—H20 | 0.9300 |
C5—C6 | 1.332 (4) | C21—C26 | 1.394 (4) |
C5—C10 | 1.513 (4) | C21—C22 | 1.398 (4) |
C6—C7 | 1.491 (4) | C22—C23 | 1.371 (4) |
C6—H6 | 0.9300 | C22—H22 | 0.9300 |
C7—C8 | 1.525 (4) | C23—C24 | 1.380 (5) |
C7—H7A | 0.9700 | C23—H23 | 0.9300 |
C7—H7B | 0.9700 | C24—C25 | 1.390 (4) |
C8—C14 | 1.519 (3) | C24—C241 | 1.439 (5) |
C8—C9 | 1.536 (4) | C241—N241 | 1.135 (5) |
C8—H8 | 0.9800 | C25—C26 | 1.374 (4) |
C9—C11 | 1.551 (4) | C25—H25 | 0.9300 |
C9—C10 | 1.551 (4) | C26—H26 | 0.9300 |
C9—H9 | 0.9800 | N31—C35 | 1.469 (4) |
C10—C19 | 1.536 (4) | N31—C32 | 1.481 (4) |
C11—C12 | 1.525 (4) | C32—C33 | 1.505 (4) |
C11—H11A | 0.9700 | C32—H32A | 0.97 |
C11—H11B | 0.9700 | C32—H32B | 0.97 |
C12—C13 | 1.519 (4) | C33—C34 | 1.501 (5) |
C12—H12A | 0.9700 | C33—H33A | 0.97 |
C12—H12B | 0.9700 | C33—H33B | 0.97 |
C13—C18 | 1.529 (4) | C34—C35 | 1.516 (5) |
C13—C17 | 1.536 (4) | C34—H34A | 0.97 |
C13—C14 | 1.538 (4) | C34—H34B | 0.97 |
C14—C15 | 1.533 (4) | C35—H35A | 0.97 |
C14—H14 | 0.9800 | C35—H35B | 0.97 |
C15—C16 | 1.517 (4) | O1W—H1W | 0.81 |
C15—H15A | 0.9700 | O1W—H2W | 0.97 |
C15—H15B | 0.9700 | ||
C2—C1—C10 | 114.2 (2) | C16—C15—C14 | 103.2 (2) |
C2—C1—H1A | 108.7 | C16—C15—H15A | 111.1 |
C10—C1—H1A | 108.7 | C14—C15—H15A | 111.1 |
C2—C1—H1B | 108.7 | C16—C15—H15B | 111.1 |
C10—C1—H1B | 108.7 | C14—C15—H15B | 111.1 |
H1A—C1—H1B | 107.6 | H15A—C15—H15B | 109.1 |
C1—C2—C3 | 112.0 (3) | C20—C16—C15 | 131.0 (3) |
C1—C2—H2A | 109.2 | C20—C16—C17 | 121.3 (3) |
C3—C2—H2A | 109.2 | C15—C16—C17 | 107.7 (2) |
C1—C2—H2B | 109.2 | O17—C17—C16 | 112.6 (2) |
C3—C2—H2B | 109.2 | O17—C17—C13 | 118.4 (3) |
H2A—C2—H2B | 107.9 | C16—C17—C13 | 102.8 (2) |
N31—C3—C4 | 111.3 (3) | O17—C17—H17 | 107.5 |
N31—C3—C2 | 110.2 (2) | C16—C17—H17 | 107.5 |
C4—C3—C2 | 109.6 (2) | C13—C17—H17 | 107.5 |
N31—C3—H3 | 108.6 | C17—O17—H17A | 109.5 |
C4—C3—H3 | 108.6 | C13—C18—H18A | 109.5 |
C2—C3—H3 | 108.6 | C13—C18—H18B | 109.5 |
C5—C4—C3 | 112.2 (3) | H18A—C18—H18B | 109.5 |
C5—C4—H4A | 109.2 | C13—C18—H18C | 109.5 |
C3—C4—H4A | 109.2 | H18A—C18—H18C | 109.5 |
C5—C4—H4B | 109.2 | H18B—C18—H18C | 109.5 |
C3—C4—H4B | 109.2 | C10—C19—H19A | 109.5 |
H4A—C4—H4B | 107.9 | C10—C19—H19B | 109.5 |
C6—C5—C10 | 123.5 (3) | H19A—C19—H19B | 109.5 |
C6—C5—C4 | 119.9 (3) | C10—C19—H19C | 109.5 |
C10—C5—C4 | 116.6 (2) | H19A—C19—H19C | 109.5 |
C5—C6—C7 | 124.4 (3) | H19B—C19—H19C | 109.5 |
C5—C6—H6 | 117.8 | C16—C20—C21 | 130.2 (3) |
C7—C6—H6 | 117.8 | C16—C20—H20 | 114.9 |
C6—C7—C8 | 111.8 (2) | C21—C20—H20 | 114.9 |
C6—C7—H7A | 109.2 | C26—C21—C22 | 117.2 (3) |
C8—C7—H7A | 109.2 | C26—C21—C20 | 125.1 (3) |
C6—C7—H7B | 109.2 | C22—C21—C20 | 117.7 (3) |
C8—C7—H7B | 109.2 | C23—C22—C21 | 121.5 (3) |
H7A—C7—H7B | 107.9 | C23—C22—H22 | 119.3 |
C14—C8—C7 | 110.8 (2) | C21—C22—H22 | 119.3 |
C14—C8—C9 | 110.4 (2) | C22—C23—C24 | 120.3 (3) |
C7—C8—C9 | 109.1 (2) | C22—C23—H23 | 119.8 |
C14—C8—H8 | 108.9 | C24—C23—H23 | 119.8 |
C7—C8—H8 | 108.9 | C23—C24—C25 | 119.4 (3) |
C9—C8—H8 | 108.9 | C23—C24—C241 | 120.7 (3) |
C8—C9—C11 | 112.7 (2) | C25—C24—C241 | 120.0 (3) |
C8—C9—C10 | 112.6 (2) | N241—C241—C24 | 179.4 (5) |
C11—C9—C10 | 113.2 (2) | C26—C25—C24 | 120.0 (3) |
C8—C9—H9 | 105.8 | C26—C25—H25 | 120.0 |
C11—C9—H9 | 105.8 | C24—C25—H25 | 120.0 |
C10—C9—H9 | 105.8 | C25—C26—C21 | 121.5 (3) |
C5—C10—C19 | 108.9 (2) | C25—C26—H26 | 119.2 |
C5—C10—C1 | 106.9 (2) | C21—C26—H26 | 119.2 |
C19—C10—C1 | 109.7 (2) | C3—N31—C35 | 113.0 (2) |
C5—C10—C9 | 110.7 (2) | C3—N31—C32 | 114.4 (2) |
C19—C10—C9 | 111.1 (2) | C35—N31—C32 | 103.4 (2) |
C1—C10—C9 | 109.5 (2) | N31—C32—C33 | 103.8 (3) |
C12—C11—C9 | 113.0 (2) | N31—C32—H32A | 111.0 |
C12—C11—H11A | 109.0 | C33—C32—H32A | 111.0 |
C9—C11—H11A | 109.0 | N31—C32—H32B | 111.0 |
C12—C11—H11B | 109.0 | C33—C32—H32B | 111.0 |
C9—C11—H11B | 109.0 | H32A—C32—H32B | 109.0 |
H11A—C11—H11B | 107.8 | C34—C33—C32 | 105.0 (3) |
C13—C12—C11 | 111.1 (2) | C34—C33—H33A | 110.7 |
C13—C12—H12A | 109.4 | C32—C33—H33A | 110.7 |
C11—C12—H12A | 109.4 | C34—C33—H33B | 110.7 |
C13—C12—H12B | 109.4 | C32—C33—H33B | 110.7 |
C11—C12—H12B | 109.4 | H33A—C33—H33B | 108.8 |
H12A—C12—H12B | 108.0 | C33—C34—C35 | 106.0 (3) |
C12—C13—C18 | 112.0 (2) | C33—C34—H34A | 110.5 |
C12—C13—C17 | 115.7 (2) | C35—C34—H34A | 110.5 |
C18—C13—C17 | 109.4 (2) | C33—C34—H34B | 110.5 |
C12—C13—C14 | 107.3 (2) | C35—C34—H34B | 110.5 |
C18—C13—C14 | 113.1 (2) | H34A—C34—H34B | 108.7 |
C17—C13—C14 | 98.8 (2) | N31—C35—C34 | 104.6 (3) |
C8—C14—C15 | 119.5 (2) | N31—C35—H35A | 110.8 |
C8—C14—C13 | 114.3 (2) | C34—C35—H35A | 110.8 |
C15—C14—C13 | 104.1 (2) | N31—C35—H35B | 110.8 |
C8—C14—H14 | 106.0 | C34—C35—H35B | 110.8 |
C15—C14—H14 | 106.0 | H35A—C35—H35B | 108.9 |
C13—C14—H14 | 106.0 | H1W—O1W—H2W | 104 |
C10—C1—C2—C3 | −56.9 (4) | C18—C13—C14—C15 | −68.6 (3) |
C1—C2—C3—N31 | 176.5 (3) | C17—C13—C14—C15 | 46.9 (3) |
C1—C2—C3—C4 | 53.7 (4) | C8—C14—C15—C16 | −160.3 (2) |
N31—C3—C4—C5 | −173.6 (2) | C13—C14—C15—C16 | −31.3 (3) |
C2—C3—C4—C5 | −51.5 (4) | C14—C15—C16—C20 | −178.2 (3) |
C3—C4—C5—C6 | −128.9 (3) | C14—C15—C16—C17 | 2.9 (3) |
C3—C4—C5—C10 | 53.9 (4) | C20—C16—C17—O17 | −24.1 (4) |
C10—C5—C6—C7 | −0.7 (5) | C15—C16—C17—O17 | 154.9 (3) |
C4—C5—C6—C7 | −177.7 (3) | C20—C16—C17—C13 | −152.7 (3) |
C5—C6—C7—C8 | 19.5 (4) | C15—C16—C17—C13 | 26.3 (3) |
C6—C7—C8—C14 | −169.5 (2) | C12—C13—C17—O17 | 76.9 (4) |
C6—C7—C8—C9 | −47.9 (3) | C18—C13—C17—O17 | −50.6 (4) |
C14—C8—C9—C11 | −47.3 (3) | C14—C13—C17—O17 | −169.0 (3) |
C7—C8—C9—C11 | −169.2 (2) | C12—C13—C17—C16 | −158.1 (3) |
C14—C8—C9—C10 | −176.9 (2) | C18—C13—C17—C16 | 74.3 (3) |
C7—C8—C9—C10 | 61.2 (3) | C14—C13—C17—C16 | −44.1 (3) |
C6—C5—C10—C19 | −110.6 (3) | C15—C16—C20—C21 | 3.6 (5) |
C4—C5—C10—C19 | 66.5 (3) | C17—C16—C20—C21 | −177.7 (3) |
C6—C5—C10—C1 | 131.0 (3) | C16—C20—C21—C26 | −8.7 (5) |
C4—C5—C10—C1 | −51.9 (3) | C16—C20—C21—C22 | 171.0 (3) |
C6—C5—C10—C9 | 11.9 (4) | C26—C21—C22—C23 | 2.8 (4) |
C4—C5—C10—C9 | −171.1 (2) | C20—C21—C22—C23 | −176.9 (3) |
C2—C1—C10—C5 | 52.9 (3) | C21—C22—C23—C24 | −1.7 (5) |
C2—C1—C10—C19 | −65.0 (4) | C22—C23—C24—C25 | 0.4 (5) |
C2—C1—C10—C9 | 172.8 (3) | C22—C23—C24—C241 | −179.7 (3) |
C8—C9—C10—C5 | −42.0 (3) | C23—C24—C241—N241 | 87 (52) |
C11—C9—C10—C5 | −171.4 (2) | C25—C24—C241—N241 | −93 (52) |
C8—C9—C10—C19 | 79.2 (3) | C23—C24—C25—C26 | −0.2 (5) |
C11—C9—C10—C19 | −50.2 (3) | C241—C24—C25—C26 | 179.9 (3) |
C8—C9—C10—C1 | −159.6 (2) | C24—C25—C26—C21 | 1.3 (5) |
C11—C9—C10—C1 | 71.1 (3) | C22—C21—C26—C25 | −2.6 (5) |
C8—C9—C11—C12 | 49.0 (3) | C20—C21—C26—C25 | 177.1 (3) |
C10—C9—C11—C12 | 178.3 (3) | C4—C3—N31—C35 | −169.8 (3) |
C9—C11—C12—C13 | −55.6 (4) | C2—C3—N31—C35 | 68.4 (3) |
C11—C12—C13—C18 | −65.7 (3) | C4—C3—N31—C32 | −51.8 (3) |
C11—C12—C13—C17 | 168.1 (3) | C2—C3—N31—C32 | −173.6 (3) |
C11—C12—C13—C14 | 59.0 (3) | C3—N31—C32—C33 | −165.0 (3) |
C7—C8—C14—C15 | −60.1 (3) | C35—N31—C32—C33 | −41.6 (3) |
C9—C8—C14—C15 | 179.0 (2) | N31—C32—C33—C34 | 29.3 (4) |
C7—C8—C14—C13 | 175.8 (2) | C32—C33—C34—C35 | −6.4 (4) |
C9—C8—C14—C13 | 54.9 (3) | C3—N31—C35—C34 | 161.7 (3) |
C12—C13—C14—C8 | −60.5 (3) | C32—N31—C35—C34 | 37.4 (3) |
C18—C13—C14—C8 | 63.4 (3) | C33—C34—C35—N31 | −19.1 (4) |
C17—C13—C14—C8 | 179.0 (2) | C19—C10—C13—C18 | 12.4 (3) |
C12—C13—C14—C15 | 167.4 (2) | H8—C8—C9—H9 | −172.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N241i | 0.81 | 2.20 | 3.008 (5) | 176 |
O1W—H2W···N31ii | 0.97 | 1.93 | 2.892 (3) | 168 |
O17—H17A···O1Wiii | 0.82 | 1.97 | 2.740 (4) | 155 |
Symmetry codes: (i) x−1/2, −y−3/2, −z−1; (ii) −x, y−1/2, −z−3/2; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C31H40N2O·H2O |
Mr | 474.67 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2171 (6), 18.541 (3), 20.176 (6) |
V (Å3) | 2699.8 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.56 |
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 | 0.850, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2916, 2898, 2580 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.09 |
No. of reflections | 2898 |
No. of parameters | 318 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.19 |
Absolute structure | Flack (1983), 83 Friedel pairs Query |
Absolute structure parameter | −1.4 (5) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), DIRDIF99 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N241i | 0.81 | 2.20 | 3.008 (5) | 176 |
O1W—H2W···N31ii | 0.97 | 1.93 | 2.892 (3) | 168 |
O17—H17A···O1Wiii | 0.82 | 1.97 | 2.740 (4) | 155 |
Symmetry codes: (i) x−1/2, −y−3/2, −z−1; (ii) −x, y−1/2, −z−3/2; (iii) x−1, y, z. |
The X-ray investigation of the title compound, (I), was undertaken as part of our study of the structure and conformation of new synthetic steroid derivatives. We are particularly interested in the conformational flexibilities of steroids due to various possible substitutions at the C3, C16 and C17 positions, as it is well known that steroid receptors are able to modify the mode of binding at ring D to accommodate several different types of C17 substitution (Duax & Norton, 1975). The absolute configuration of (I) was not determined from the X-ray data, but is based on the known chirality of the starting material used in the synthesis of (I), namely, 16-(4-cyanobenzylidene)androst-4-ene-3,17-dione. \sch
The C5—C6 distance of 1.332 (4) Å confirms the localization of a double bond at this position (Kálmán et al., 1992; Vasuki et al., 2001). The puckering parameters [ring A: Q = 0.542 (3) Å, θ = 2.7 (3)° and Φ = 42.8 (7)°; ring C: Q = 0.562 (3) Å, θ = 8.6 (3)° and Φ = 235.0 (2)°; Cremer & Pople, 1975] show that rings A and C adopt chair conformations. The presence of the pyrrolidine group bonded to C3 does not disturb the usual chair conformation of ring A of the steroidal nucleus. Due to the C5—C6 double bond, the environment of atom C5 is planar, and hence ring B adopts the half-chair conformation generally found in steroids with a C5—C6 double bond (Caira et al., 1995; Andrade et al., 2001), with puckering parameters Q = 0.490 (3) Å, θ = 49.4 (4)° and Φ = 202.5 (5)°.
The conformation of ring D can be expressed by two parameters, a pseudo rotation angle, Δ, and a maximum torsion angle, ϕm (Altona et al., 1968). In compound (I), ring D exhibits a 13β-envelope conformation, with Δ = 28.5° and ϕm = 48.2 (2)°.
Atoms C8 and C9 are displaced to opposite sides by 0.2631 (3) and 0.2155 (3) Å, respectively, from the mean C10/C5/C6/C7 plane. The C17—C16—C20—C21 torsion angle of -177.7 (3)° indicates that the cyanobenzylidene moiety has an E configuration with respect to the hydroxyl group at position 17. The C15—C16—C20 exocyclic angle of 131.0 (3)° is significantly larger than the normal value, and this may be due to the steric repulsion between atoms H15A and H26 [2.293 Å] and H15B and H26 [2.354 Å].
The pseudotorsion angle of C19—C10···C13—C18 is 12.41 (3)°. The 4-cyanobenzylidene group is oriented at an angle of 11.14 (10)° with respect to the central steroid nucleus. The equatorially substituted pyrrolidine group at C3 is oriented at an angle of 22.64 (12)° with respect to the central steroid nucleus. The geometry of the rings is trans at ring junctions B/C and C/D. In (I), the valency angles C8—C14—C15 [119.5 (2)°] and C14—C13—C17 [98.8 (2)°] are close to the expected values of 121.2° and 101.4°, respectively (Duax & Norton, 1975).
The 17β-OH is equatorially attached at C17 and the pyrrolidine is equatorially substituted at C3. The structure of (I) is stabilized by a network of O—H···O and O—H···N intermolecular hydrogen bonds (Table 1). The hydroxyl O atoms take part in the intermolecular hydrogen bonds as donors, with the O atoms of the water molecules as acceptors. The water molecule links three different steroid molecules, acting as a hydrogen-bond acceptor from O17 of one steroid molecule and as a donor to the N atoms of the pyrrolidine and 4-cyanobenzylidene of two other steroid molecules. In Fig. 2, we see that the steroid molecules are aligned parallel to the b axis, forming a closed loop through hydrogen bonds linked via water molecules.