Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108023299/sk3256sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108023299/sk3256Isup2.hkl |
CCDC reference: 703735
For related literature, see: Allen et al. (1987); Altona et al. (1968); Bertolasi et al. (1982); Cepa et al. (2005, 2008); Cremer & Pople (1975); Duax & Norton (1975); Jerslev (1983); Kálmán et al. (1991); Paixão, Andrade, de Almeida, Tavares da Silva, Fernandes Roleira, Sá e Melo & Campos Neves (2001).
To a solution of 5α-androst-3-en-17-one (150 mg, 0.55 mmol) in methanol (7.0 ml), hydroxylamine hydrochloride (49.2 mg, 0.7 mmol) and CH3COONa.3H2O (90 mg, 0.66 mmol) were added. The reaction was stirred at 313 K for 5 h until all the starting material had been consumed. After addition of water (50 ml), the methanol was evaporated and the aqueous phase was extracted with methylene chloride (100 ml). The organic layer was then washed with NaHCO3 10% (2×50 ml), water (3×100 ml), dried over MgSO4, filtered and evaporated to dryness yielding 133.7 mg (84%) of the title oxime. Mp(cyclohexane) 432–434 K; IR νmax(KBr) cm-1: 3281 (O–H), 3013 (? C–H); 1H NMR (300 MHz, DMSO-d6) δ: 0.75 (3H, s, 19-H3), 0.82 (3H, s, 18-H3), 5.27 (1H, ddd, J4,3=9.5, J4,5α=4.5, J4,2α=2.5, 4-H), 5.54 (1H, ddd, J3,4=9.5, J3,2β=6.1, J3,2α=3.1, 3-H), 10.04 (1H, s, NOH); 13C NMR (75.6 MHz, DMSO-d6) δ: 11.7 (C19), 17.3 (C18), 20.2, 22.7, 23.0, 24.7, 26.8, 31.0, 33.5, 34.3, 34.5, 34.6, 43.3, 45.3, (C5), 52.9, 53.5, 125.3, (C3), 131.0 (C4), 167.9 (C17); ESI m/z 288.2 (M+H, 100%).
All H atoms were refined as riding on their parent atoms using SHELXL97 (Sheldrick, 2008). The absolute configuration was not determined from the X-ray data but was known from the synthesis route. Friedel pairs were merged before refinement. The structure contains small solvent accessible voids of 35 Å3 (Spek, 2003). No residual density ws found there.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: PLATON/HELENA (Spek, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C19H29NO | F(000) = 632 |
Mr = 287.43 | Dx = 1.098 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54180 Å |
a = 6.3510 (12) Å | Cell parameters from 25 reflections |
b = 42.306 (6) Å | θ = 8.0–31.9° |
c = 7.1764 (6) Å | µ = 0.51 mm−1 |
β = 115.651 (13)° | T = 293 K |
V = 1738.2 (5) Å3 | Prism, colourless |
Z = 4 | 0.48 × 0.24 × 0.24 mm |
Enraf–Nonius MACH-3 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 72.5°, θmin = 4.2° |
Graphite monochromator | h = 0→7 |
profile data from ω–2θ scans | k = −15→52 |
3820 measured reflections | l = −8→7 |
3472 independent reflections | 3 standard reflections every 240 min |
2868 reflections with I > 2σ(I) | intensity decay: 4.9% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.133 | w = 1/[σ2(Fo2) + (0.0733P)2 + 0.204P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3472 reflections | Δρmax = 0.16 e Å−3 |
386 parameters | Δρmin = −0.13 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (5) |
C19H29NO | V = 1738.2 (5) Å3 |
Mr = 287.43 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 6.3510 (12) Å | µ = 0.51 mm−1 |
b = 42.306 (6) Å | T = 293 K |
c = 7.1764 (6) Å | 0.48 × 0.24 × 0.24 mm |
β = 115.651 (13)° |
Enraf–Nonius MACH-3 diffractometer | Rint = 0.016 |
3820 measured reflections | 3 standard reflections every 240 min |
3472 independent reflections | intensity decay: 4.9% |
2868 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.16 e Å−3 |
3472 reflections | Δρmin = −0.13 e Å−3 |
386 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
N1 | 0.5622 (5) | 0.75922 (6) | 0.6623 (4) | 0.0639 (6) | |
O1 | 0.5251 (5) | 0.79170 (6) | 0.6116 (4) | 0.0770 (7) | |
H1 | 0.5734 | 0.8022 | 0.7181 | 0.115* | |
C1 | 0.1888 (8) | 0.59646 (9) | 0.6761 (6) | 0.0800 (10) | |
H1A | 0.3252 | 0.6009 | 0.8042 | 0.096* | |
H1B | 0.0578 | 0.6077 | 0.6800 | 0.096* | |
C2 | 0.1383 (10) | 0.56117 (11) | 0.6638 (7) | 0.0986 (13) | |
H2A | 0.2848 | 0.5497 | 0.7161 | 0.118* | |
H2B | 0.0618 | 0.5562 | 0.7515 | 0.118* | |
C3 | −0.0116 (9) | 0.55053 (11) | 0.4502 (8) | 0.0963 (13) | |
H3 | −0.0679 | 0.5299 | 0.4305 | 0.116* | |
C4 | −0.0689 (8) | 0.56874 (10) | 0.2876 (7) | 0.0871 (11) | |
H4 | −0.1615 | 0.5602 | 0.1584 | 0.105* | |
C5 | 0.0056 (6) | 0.60240 (8) | 0.2975 (5) | 0.0689 (8) | |
H5 | −0.1167 | 0.6150 | 0.3107 | 0.083* | |
C6 | 0.0211 (7) | 0.61436 (8) | 0.1051 (5) | 0.0793 (10) | |
H6A | −0.1224 | 0.6094 | −0.0154 | 0.095* | |
H6B | 0.1488 | 0.6039 | 0.0904 | 0.095* | |
C7 | 0.0606 (6) | 0.64983 (8) | 0.1171 (5) | 0.0717 (9) | |
H7A | −0.0766 | 0.6603 | 0.1141 | 0.086* | |
H7B | 0.0808 | 0.6567 | −0.0031 | 0.086* | |
C8 | 0.2745 (5) | 0.65975 (7) | 0.3127 (4) | 0.0551 (6) | |
H8 | 0.4147 | 0.6520 | 0.3027 | 0.066* | |
C9 | 0.2685 (5) | 0.64534 (7) | 0.5088 (4) | 0.0548 (6) | |
H9 | 0.1300 | 0.6543 | 0.5162 | 0.066* | |
C10 | 0.2319 (6) | 0.60912 (7) | 0.4943 (4) | 0.0603 (7) | |
C11 | 0.4782 (6) | 0.65640 (8) | 0.7057 (5) | 0.0705 (8) | |
H11A | 0.4619 | 0.6483 | 0.8252 | 0.085* | |
H11B | 0.6199 | 0.6475 | 0.7076 | 0.085* | |
C12 | 0.5028 (6) | 0.69233 (8) | 0.7230 (4) | 0.0680 (8) | |
H12A | 0.3713 | 0.7013 | 0.7395 | 0.082* | |
H12B | 0.6445 | 0.6979 | 0.8438 | 0.082* | |
C13 | 0.5117 (5) | 0.70604 (7) | 0.5299 (4) | 0.0557 (7) | |
C14 | 0.2935 (5) | 0.69553 (7) | 0.3383 (4) | 0.0535 (6) | |
H14 | 0.1604 | 0.7019 | 0.3644 | 0.064* | |
C15 | 0.2898 (7) | 0.71750 (8) | 0.1690 (5) | 0.0689 (8) | |
H15A | 0.1348 | 0.7185 | 0.0553 | 0.083* | |
H15B | 0.3996 | 0.7105 | 0.1166 | 0.083* | |
C16 | 0.3625 (6) | 0.74974 (8) | 0.2781 (5) | 0.0684 (8) | |
H16A | 0.4656 | 0.7609 | 0.2329 | 0.082* | |
H16B | 0.2268 | 0.7628 | 0.2509 | 0.082* | |
C17 | 0.4877 (5) | 0.74133 (8) | 0.5051 (5) | 0.0588 (7) | |
C18 | 0.7419 (6) | 0.69719 (10) | 0.5206 (7) | 0.0807 (10) | |
H18A | 0.7420 | 0.7056 | 0.3963 | 0.121* | |
H18B | 0.7564 | 0.6746 | 0.5210 | 0.121* | |
H18C | 0.8709 | 0.7059 | 0.6385 | 0.121* | |
C19 | 0.4422 (6) | 0.59183 (9) | 0.4906 (6) | 0.0735 (9) | |
H19A | 0.4887 | 0.6022 | 0.3953 | 0.110* | |
H19B | 0.4002 | 0.5703 | 0.4478 | 0.110* | |
H19C | 0.5696 | 0.5921 | 0.6264 | 0.110* | |
N2 | 0.7478 (5) | 0.79799 (6) | 1.0431 (4) | 0.0625 (6) | |
O2 | 0.7739 (5) | 0.76556 (5) | 1.0955 (4) | 0.0754 (6) | |
H2 | 0.7177 | 0.7549 | 0.9897 | 0.113* | |
C21 | 0.3214 (7) | 0.95799 (9) | 1.0351 (6) | 0.0862 (11) | |
H21A | 0.1940 | 0.9461 | 1.0410 | 0.103* | |
H21B | 0.3238 | 0.9535 | 0.9035 | 0.103* | |
C22 | 0.2755 (10) | 0.99341 (11) | 1.0460 (8) | 0.1069 (15) | |
H22A | 0.3635 | 1.0053 | 0.9879 | 0.128* | |
H22B | 0.1110 | 0.9977 | 0.9626 | 0.128* | |
C23 | 0.3417 (8) | 1.00439 (10) | 1.2611 (8) | 0.0950 (12) | |
H23 | 0.2982 | 1.0247 | 1.2807 | 0.114* | |
C24 | 0.4578 (8) | 0.98696 (10) | 1.4236 (8) | 0.0869 (11) | |
H24 | 0.4968 | 0.9957 | 1.5533 | 0.104* | |
C25 | 0.5323 (7) | 0.95347 (8) | 1.4127 (5) | 0.0704 (8) | |
H25 | 0.4050 | 0.9400 | 1.4093 | 0.085* | |
C26 | 0.7473 (8) | 0.94298 (9) | 1.5986 (5) | 0.0800 (10) | |
H26A | 0.7312 | 0.9480 | 1.7237 | 0.096* | |
H26B | 0.8828 | 0.9541 | 1.6028 | 0.096* | |
C27 | 0.7814 (8) | 0.90735 (8) | 1.5877 (5) | 0.0771 (10) | |
H27A | 0.9252 | 0.9011 | 1.7039 | 0.093* | |
H27B | 0.6536 | 0.8963 | 1.5993 | 0.093* | |
C28 | 0.7913 (5) | 0.89752 (7) | 1.3874 (4) | 0.0556 (6) | |
H28 | 0.9355 | 0.9059 | 1.3881 | 0.067* | |
C29 | 0.5821 (5) | 0.91081 (7) | 1.1966 (4) | 0.0559 (7) | |
H29 | 0.4424 | 0.9011 | 1.1973 | 0.067* | |
C30 | 0.5511 (6) | 0.94693 (7) | 1.2093 (5) | 0.0603 (7) | |
C31 | 0.5894 (7) | 0.89993 (8) | 0.9952 (5) | 0.0705 (8) | |
H31A | 0.4498 | 0.9073 | 0.8787 | 0.085* | |
H31B | 0.7230 | 0.9095 | 0.9855 | 0.085* | |
C32 | 0.6059 (6) | 0.86397 (8) | 0.9809 (4) | 0.0665 (8) | |
H32A | 0.4635 | 0.8543 | 0.9723 | 0.080* | |
H32B | 0.6224 | 0.8585 | 0.8566 | 0.080* | |
C33 | 0.8128 (5) | 0.85132 (7) | 1.1681 (4) | 0.0558 (7) | |
C34 | 0.7914 (5) | 0.86164 (7) | 1.3648 (4) | 0.0546 (6) | |
H34 | 0.6363 | 0.8546 | 1.3457 | 0.066* | |
C35 | 0.9650 (7) | 0.84048 (9) | 1.5344 (5) | 0.0706 (8) | |
H35A | 0.9274 | 0.8392 | 1.6516 | 0.085* | |
H35B | 1.1235 | 0.8482 | 1.5812 | 0.085* | |
C36 | 0.9343 (7) | 0.80801 (8) | 1.4264 (5) | 0.0705 (8) | |
H36A | 1.0837 | 0.7975 | 1.4678 | 0.085* | |
H36B | 0.8319 | 0.7944 | 1.4591 | 0.085* | |
C37 | 0.8265 (5) | 0.81600 (8) | 1.1984 (4) | 0.0583 (7) | |
C38 | 1.0450 (7) | 0.86152 (10) | 1.1668 (7) | 0.0821 (11) | |
H38A | 1.1731 | 0.8533 | 1.2873 | 0.123* | |
H38B | 1.0537 | 0.8842 | 1.1673 | 0.123* | |
H38C | 1.0529 | 0.8534 | 1.0450 | 0.123* | |
C39 | 0.7545 (7) | 0.96533 (8) | 1.2004 (6) | 0.0762 (9) | |
H39A | 0.8997 | 0.9559 | 1.2936 | 0.114* | |
H39B | 0.7493 | 0.9869 | 1.2398 | 0.114* | |
H39C | 0.7419 | 0.9647 | 1.0622 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0652 (15) | 0.0652 (16) | 0.0618 (14) | −0.0069 (12) | 0.0280 (12) | −0.0147 (12) |
O1 | 0.0887 (17) | 0.0652 (14) | 0.0729 (15) | −0.0087 (12) | 0.0311 (13) | −0.0143 (11) |
C1 | 0.096 (2) | 0.081 (2) | 0.072 (2) | −0.009 (2) | 0.0441 (19) | −0.0028 (17) |
C2 | 0.129 (4) | 0.085 (3) | 0.093 (3) | −0.018 (3) | 0.058 (3) | 0.004 (2) |
C3 | 0.106 (3) | 0.076 (3) | 0.107 (3) | −0.020 (2) | 0.046 (3) | −0.006 (2) |
C4 | 0.084 (3) | 0.081 (3) | 0.085 (3) | −0.0165 (19) | 0.026 (2) | −0.013 (2) |
C5 | 0.0620 (18) | 0.068 (2) | 0.0656 (19) | −0.0043 (14) | 0.0172 (15) | −0.0102 (15) |
C6 | 0.091 (3) | 0.074 (2) | 0.0451 (15) | −0.0070 (18) | 0.0035 (15) | −0.0109 (15) |
C7 | 0.082 (2) | 0.070 (2) | 0.0407 (15) | −0.0057 (16) | 0.0054 (14) | −0.0080 (14) |
C8 | 0.0554 (15) | 0.0636 (17) | 0.0417 (13) | −0.0003 (12) | 0.0166 (11) | −0.0082 (11) |
C9 | 0.0526 (14) | 0.0632 (16) | 0.0471 (14) | 0.0029 (12) | 0.0201 (11) | −0.0068 (12) |
C10 | 0.0626 (17) | 0.0655 (18) | 0.0520 (15) | 0.0007 (14) | 0.0241 (13) | −0.0054 (13) |
C11 | 0.077 (2) | 0.072 (2) | 0.0459 (15) | −0.0012 (16) | 0.0110 (14) | −0.0033 (14) |
C12 | 0.0707 (18) | 0.076 (2) | 0.0420 (14) | −0.0019 (15) | 0.0104 (13) | −0.0124 (13) |
C13 | 0.0479 (14) | 0.0663 (17) | 0.0499 (15) | 0.0001 (12) | 0.0184 (11) | −0.0137 (13) |
C14 | 0.0517 (14) | 0.0646 (17) | 0.0410 (13) | 0.0007 (12) | 0.0171 (11) | −0.0092 (11) |
C15 | 0.080 (2) | 0.074 (2) | 0.0516 (16) | −0.0072 (16) | 0.0276 (15) | −0.0088 (14) |
C16 | 0.074 (2) | 0.075 (2) | 0.0541 (16) | −0.0096 (16) | 0.0259 (15) | −0.0099 (14) |
C17 | 0.0530 (15) | 0.0674 (18) | 0.0583 (16) | −0.0073 (13) | 0.0263 (13) | −0.0140 (13) |
C18 | 0.0522 (16) | 0.095 (3) | 0.094 (3) | −0.0005 (16) | 0.0300 (16) | −0.022 (2) |
C19 | 0.0689 (19) | 0.070 (2) | 0.079 (2) | 0.0092 (16) | 0.0297 (17) | −0.0021 (16) |
N2 | 0.0638 (14) | 0.0642 (16) | 0.0630 (15) | −0.0063 (12) | 0.0307 (12) | −0.0147 (12) |
O2 | 0.0868 (16) | 0.0646 (14) | 0.0722 (15) | −0.0004 (11) | 0.0319 (13) | −0.0151 (11) |
C21 | 0.088 (3) | 0.070 (2) | 0.082 (2) | 0.0029 (18) | 0.019 (2) | −0.0028 (18) |
C22 | 0.111 (3) | 0.075 (3) | 0.106 (3) | 0.015 (2) | 0.020 (3) | −0.003 (2) |
C23 | 0.097 (3) | 0.069 (2) | 0.121 (4) | 0.009 (2) | 0.049 (3) | −0.007 (2) |
C24 | 0.096 (3) | 0.076 (2) | 0.104 (3) | 0.000 (2) | 0.057 (3) | −0.017 (2) |
C25 | 0.083 (2) | 0.0665 (19) | 0.076 (2) | −0.0034 (16) | 0.0472 (18) | −0.0099 (16) |
C26 | 0.119 (3) | 0.072 (2) | 0.0547 (17) | 0.006 (2) | 0.0424 (19) | −0.0125 (15) |
C27 | 0.115 (3) | 0.069 (2) | 0.0494 (16) | 0.0047 (19) | 0.0374 (17) | −0.0072 (15) |
C28 | 0.0617 (16) | 0.0613 (17) | 0.0464 (14) | −0.0072 (12) | 0.0260 (12) | −0.0097 (12) |
C29 | 0.0579 (15) | 0.0613 (17) | 0.0510 (14) | −0.0091 (12) | 0.0259 (12) | −0.0062 (12) |
C30 | 0.0645 (17) | 0.0590 (17) | 0.0595 (16) | −0.0064 (13) | 0.0288 (14) | −0.0054 (13) |
C31 | 0.095 (2) | 0.069 (2) | 0.0465 (15) | −0.0045 (17) | 0.0301 (16) | −0.0059 (14) |
C32 | 0.082 (2) | 0.072 (2) | 0.0455 (14) | −0.0113 (16) | 0.0278 (14) | −0.0128 (13) |
C33 | 0.0574 (16) | 0.0647 (17) | 0.0523 (15) | −0.0128 (12) | 0.0304 (13) | −0.0151 (13) |
C34 | 0.0582 (15) | 0.0634 (17) | 0.0442 (13) | −0.0047 (13) | 0.0240 (12) | −0.0084 (12) |
C35 | 0.077 (2) | 0.074 (2) | 0.0484 (16) | 0.0025 (16) | 0.0149 (14) | −0.0092 (14) |
C36 | 0.077 (2) | 0.072 (2) | 0.0602 (18) | 0.0041 (16) | 0.0271 (16) | −0.0077 (15) |
C37 | 0.0507 (15) | 0.0706 (19) | 0.0581 (16) | −0.0044 (13) | 0.0277 (13) | −0.0131 (14) |
C38 | 0.079 (2) | 0.091 (3) | 0.100 (3) | −0.0212 (19) | 0.061 (2) | −0.023 (2) |
C39 | 0.095 (2) | 0.0624 (19) | 0.087 (2) | −0.0158 (17) | 0.055 (2) | −0.0096 (16) |
N1—C17 | 1.268 (4) | N2—C37 | 1.261 (4) |
N1—O1 | 1.415 (4) | N2—O2 | 1.413 (3) |
O1—H1 | 0.8200 | O2—H2 | 0.8200 |
C1—C2 | 1.522 (6) | C21—C30 | 1.527 (5) |
C1—C10 | 1.541 (5) | C21—C22 | 1.535 (5) |
C1—H1A | 0.9700 | C21—H21A | 0.9700 |
C1—H1B | 0.9700 | C21—H21B | 0.9700 |
C2—C3 | 1.481 (7) | C22—C23 | 1.488 (7) |
C2—H2A | 0.9700 | C22—H22A | 0.9700 |
C2—H2B | 0.9700 | C22—H22B | 0.9700 |
C3—C4 | 1.312 (6) | C23—C24 | 1.305 (6) |
C3—H3 | 0.9300 | C23—H23 | 0.9300 |
C4—C5 | 1.493 (5) | C24—C25 | 1.506 (5) |
C4—H4 | 0.9300 | C24—H24 | 0.9300 |
C5—C6 | 1.513 (5) | C25—C26 | 1.504 (6) |
C5—C10 | 1.544 (4) | C25—C30 | 1.541 (4) |
C5—H5 | 0.9800 | C25—H25 | 0.9800 |
C6—C7 | 1.517 (5) | C26—C27 | 1.530 (5) |
C6—H6A | 0.9700 | C26—H26A | 0.9700 |
C6—H6B | 0.9700 | C26—H26B | 0.9700 |
C7—C8 | 1.530 (4) | C27—C28 | 1.524 (4) |
C7—H7A | 0.9700 | C27—H27A | 0.9700 |
C7—H7B | 0.9700 | C27—H27B | 0.9700 |
C8—C14 | 1.523 (4) | C28—C34 | 1.527 (4) |
C8—C9 | 1.549 (4) | C28—C29 | 1.543 (4) |
C8—H8 | 0.9800 | C28—H28 | 0.9800 |
C9—C11 | 1.536 (4) | C29—C31 | 1.537 (4) |
C9—C10 | 1.547 (4) | C29—C30 | 1.548 (4) |
C9—H9 | 0.9800 | C29—H29 | 0.9800 |
C10—C19 | 1.533 (4) | C30—C39 | 1.533 (4) |
C11—C12 | 1.528 (5) | C31—C32 | 1.531 (5) |
C11—H11A | 0.9700 | C31—H31A | 0.9700 |
C11—H11B | 0.9700 | C31—H31B | 0.9700 |
C12—C13 | 1.525 (4) | C32—C33 | 1.513 (5) |
C12—H12A | 0.9700 | C32—H32A | 0.9700 |
C12—H12B | 0.9700 | C32—H32B | 0.9700 |
C13—C17 | 1.503 (4) | C33—C37 | 1.507 (4) |
C13—C14 | 1.536 (4) | C33—C34 | 1.538 (4) |
C13—C18 | 1.539 (4) | C33—C38 | 1.541 (4) |
C14—C15 | 1.522 (4) | C34—C35 | 1.529 (5) |
C14—H14 | 0.9800 | C34—H34 | 0.9800 |
C15—C16 | 1.541 (4) | C35—C36 | 1.547 (5) |
C15—H15A | 0.9700 | C35—H35A | 0.9700 |
C15—H15B | 0.9700 | C35—H35B | 0.9700 |
C16—C17 | 1.514 (5) | C36—C37 | 1.514 (4) |
C16—H16A | 0.9700 | C36—H36A | 0.9700 |
C16—H16B | 0.9700 | C36—H36B | 0.9700 |
C18—H18A | 0.9600 | C38—H38A | 0.9600 |
C18—H18B | 0.9600 | C38—H38B | 0.9600 |
C18—H18C | 0.9600 | C38—H38C | 0.9600 |
C19—H19A | 0.9600 | C39—H39A | 0.9600 |
C19—H19B | 0.9600 | C39—H39B | 0.9600 |
C19—H19C | 0.9600 | C39—H39C | 0.9600 |
C17—N1—O1 | 113.2 (3) | C37—N2—O2 | 113.3 (3) |
N1—O1—H1 | 109.5 | N2—O2—H2 | 109.5 |
C2—C1—C10 | 113.7 (3) | C30—C21—C22 | 113.1 (3) |
C2—C1—H1A | 108.8 | C30—C21—H21A | 109.0 |
C10—C1—H1A | 108.8 | C22—C21—H21A | 109.0 |
C2—C1—H1B | 108.8 | C30—C21—H21B | 109.0 |
C10—C1—H1B | 108.8 | C22—C21—H21B | 109.0 |
H1A—C1—H1B | 107.7 | H21A—C21—H21B | 107.8 |
C3—C2—C1 | 112.5 (4) | C23—C22—C21 | 112.5 (4) |
C3—C2—H2A | 109.1 | C23—C22—H22A | 109.1 |
C1—C2—H2A | 109.1 | C21—C22—H22A | 109.1 |
C3—C2—H2B | 109.1 | C23—C22—H22B | 109.1 |
C1—C2—H2B | 109.1 | C21—C22—H22B | 109.1 |
H2A—C2—H2B | 107.8 | H22A—C22—H22B | 107.8 |
C4—C3—C2 | 123.3 (4) | C24—C23—C22 | 123.2 (4) |
C4—C3—H3 | 118.4 | C24—C23—H23 | 118.4 |
C2—C3—H3 | 118.4 | C22—C23—H23 | 118.4 |
C3—C4—C5 | 123.9 (4) | C23—C24—C25 | 123.6 (4) |
C3—C4—H4 | 118.0 | C23—C24—H24 | 118.2 |
C5—C4—H4 | 118.0 | C25—C24—H24 | 118.2 |
C4—C5—C6 | 114.9 (3) | C26—C25—C24 | 114.6 (3) |
C4—C5—C10 | 111.7 (3) | C26—C25—C30 | 112.0 (3) |
C6—C5—C10 | 111.8 (3) | C24—C25—C30 | 111.9 (3) |
C4—C5—H5 | 105.9 | C26—C25—H25 | 105.9 |
C6—C5—H5 | 105.9 | C24—C25—H25 | 105.9 |
C10—C5—H5 | 105.9 | C30—C25—H25 | 105.9 |
C5—C6—C7 | 110.7 (3) | C25—C26—C27 | 109.8 (3) |
C5—C6—H6A | 109.5 | C25—C26—H26A | 109.7 |
C7—C6—H6A | 109.5 | C27—C26—H26A | 109.7 |
C5—C6—H6B | 109.5 | C25—C26—H26B | 109.7 |
C7—C6—H6B | 109.5 | C27—C26—H26B | 109.7 |
H6A—C6—H6B | 108.1 | H26A—C26—H26B | 108.2 |
C6—C7—C8 | 112.5 (3) | C28—C27—C26 | 112.4 (3) |
C6—C7—H7A | 109.1 | C28—C27—H27A | 109.1 |
C8—C7—H7A | 109.1 | C26—C27—H27A | 109.1 |
C6—C7—H7B | 109.1 | C28—C27—H27B | 109.1 |
C8—C7—H7B | 109.1 | C26—C27—H27B | 109.1 |
H7A—C7—H7B | 107.8 | H27A—C27—H27B | 107.9 |
C14—C8—C7 | 112.1 (2) | C27—C28—C34 | 112.0 (2) |
C14—C8—C9 | 108.2 (2) | C27—C28—C29 | 111.5 (3) |
C7—C8—C9 | 111.3 (3) | C34—C28—C29 | 107.9 (2) |
C14—C8—H8 | 108.4 | C27—C28—H28 | 108.5 |
C7—C8—H8 | 108.4 | C34—C28—H28 | 108.5 |
C9—C8—H8 | 108.4 | C29—C28—H28 | 108.5 |
C11—C9—C10 | 114.1 (2) | C31—C29—C28 | 111.1 (3) |
C11—C9—C8 | 111.3 (3) | C31—C29—C30 | 114.0 (2) |
C10—C9—C8 | 113.0 (2) | C28—C29—C30 | 112.9 (2) |
C11—C9—H9 | 105.9 | C31—C29—H29 | 106.0 |
C10—C9—H9 | 105.9 | C28—C29—H29 | 106.0 |
C8—C9—H9 | 105.9 | C30—C29—H29 | 106.0 |
C19—C10—C1 | 108.9 (3) | C21—C30—C39 | 109.5 (3) |
C19—C10—C5 | 111.7 (3) | C21—C30—C25 | 106.4 (3) |
C1—C10—C5 | 105.9 (3) | C39—C30—C25 | 111.2 (3) |
C19—C10—C9 | 111.5 (3) | C21—C30—C29 | 110.8 (3) |
C1—C10—C9 | 111.4 (2) | C39—C30—C29 | 111.6 (3) |
C5—C10—C9 | 107.3 (2) | C25—C30—C29 | 107.3 (2) |
C12—C11—C9 | 113.3 (2) | C32—C31—C29 | 113.0 (3) |
C12—C11—H11A | 108.9 | C32—C31—H31A | 109.0 |
C9—C11—H11A | 108.9 | C29—C31—H31A | 109.0 |
C12—C11—H11B | 108.9 | C32—C31—H31B | 109.0 |
C9—C11—H11B | 108.9 | C29—C31—H31B | 109.0 |
H11A—C11—H11B | 107.7 | H31A—C31—H31B | 107.8 |
C13—C12—C11 | 110.3 (2) | C33—C32—C31 | 110.5 (3) |
C13—C12—H12A | 109.6 | C33—C32—H32A | 109.5 |
C11—C12—H12A | 109.6 | C31—C32—H32A | 109.5 |
C13—C12—H12B | 109.6 | C33—C32—H32B | 109.5 |
C11—C12—H12B | 109.6 | C31—C32—H32B | 109.5 |
H12A—C12—H12B | 108.1 | H32A—C32—H32B | 108.1 |
C17—C13—C12 | 116.3 (2) | C37—C33—C32 | 116.9 (2) |
C17—C13—C14 | 100.1 (2) | C37—C33—C34 | 99.9 (2) |
C12—C13—C14 | 109.2 (2) | C32—C33—C34 | 109.1 (2) |
C17—C13—C18 | 106.6 (3) | C37—C33—C38 | 106.4 (3) |
C12—C13—C18 | 110.9 (3) | C32—C33—C38 | 111.2 (3) |
C14—C13—C18 | 113.4 (2) | C34—C33—C38 | 113.0 (2) |
C15—C14—C8 | 122.5 (2) | C28—C34—C35 | 122.1 (2) |
C15—C14—C13 | 103.5 (2) | C28—C34—C33 | 112.6 (2) |
C8—C14—C13 | 112.9 (2) | C35—C34—C33 | 104.2 (2) |
C15—C14—H14 | 105.5 | C28—C34—H34 | 105.6 |
C8—C14—H14 | 105.5 | C35—C34—H34 | 105.6 |
C13—C14—H14 | 105.5 | C33—C34—H34 | 105.6 |
C14—C15—C16 | 103.7 (2) | C34—C35—C36 | 103.3 (2) |
C14—C15—H15A | 111.0 | C34—C35—H35A | 111.1 |
C16—C15—H15A | 111.0 | C36—C35—H35A | 111.1 |
C14—C15—H15B | 111.0 | C34—C35—H35B | 111.1 |
C16—C15—H15B | 111.0 | C36—C35—H35B | 111.1 |
H15A—C15—H15B | 109.0 | H35A—C35—H35B | 109.1 |
C17—C16—C15 | 103.9 (3) | C37—C36—C35 | 104.1 (3) |
C17—C16—H16A | 111.0 | C37—C36—H36A | 110.9 |
C15—C16—H16A | 111.0 | C35—C36—H36A | 110.9 |
C17—C16—H16B | 111.0 | C37—C36—H36B | 110.9 |
C15—C16—H16B | 111.0 | C35—C36—H36B | 110.9 |
H16A—C16—H16B | 109.0 | H36A—C36—H36B | 109.0 |
N1—C17—C13 | 120.5 (3) | N2—C37—C33 | 119.7 (3) |
N1—C17—C16 | 129.6 (3) | N2—C37—C36 | 129.9 (3) |
C13—C17—C16 | 109.9 (2) | C33—C37—C36 | 110.4 (2) |
C13—C18—H18A | 109.5 | C33—C38—H38A | 109.5 |
C13—C18—H18B | 109.5 | C33—C38—H38B | 109.5 |
H18A—C18—H18B | 109.5 | H38A—C38—H38B | 109.5 |
C13—C18—H18C | 109.5 | C33—C38—H38C | 109.5 |
H18A—C18—H18C | 109.5 | H38A—C38—H38C | 109.5 |
H18B—C18—H18C | 109.5 | H38B—C38—H38C | 109.5 |
C10—C19—H19A | 109.5 | C30—C39—H39A | 109.5 |
C10—C19—H19B | 109.5 | C30—C39—H39B | 109.5 |
H19A—C19—H19B | 109.5 | H39A—C39—H39B | 109.5 |
C10—C19—H19C | 109.5 | C30—C39—H39C | 109.5 |
H19A—C19—H19C | 109.5 | H39A—C39—H39C | 109.5 |
H19B—C19—H19C | 109.5 | H39B—C39—H39C | 109.5 |
C10—C1—C2—C3 | −39.3 (5) | C21—C22—C23—C24 | 9.7 (7) |
C1—C2—C3—C4 | 8.2 (7) | C22—C23—C24—C25 | −1.9 (8) |
C2—C3—C4—C5 | −1.1 (8) | C23—C24—C25—C26 | 152.8 (4) |
C3—C4—C5—C6 | 153.1 (4) | C23—C24—C25—C30 | 23.9 (6) |
C3—C4—C5—C10 | 24.4 (6) | C24—C25—C26—C27 | 170.2 (3) |
C4—C5—C6—C7 | 171.1 (3) | C30—C25—C26—C27 | −61.0 (4) |
C10—C5—C6—C7 | −60.3 (4) | C25—C26—C27—C28 | 55.5 (4) |
C5—C6—C7—C8 | 54.8 (4) | C26—C27—C28—C34 | −172.1 (3) |
C6—C7—C8—C14 | −172.1 (3) | C26—C27—C28—C29 | −51.1 (4) |
C6—C7—C8—C9 | −50.7 (4) | C27—C28—C29—C31 | −178.2 (3) |
C14—C8—C9—C11 | −54.1 (3) | C34—C28—C29—C31 | −54.9 (3) |
C7—C8—C9—C11 | −177.7 (3) | C27—C28—C29—C30 | 52.2 (3) |
C14—C8—C9—C10 | 176.0 (2) | C34—C28—C29—C30 | 175.5 (2) |
C7—C8—C9—C10 | 52.3 (3) | C22—C21—C30—C39 | −59.3 (5) |
C2—C1—C10—C19 | −59.8 (4) | C22—C21—C30—C25 | 60.9 (5) |
C2—C1—C10—C5 | 60.5 (4) | C22—C21—C30—C29 | 177.2 (4) |
C2—C1—C10—C9 | 176.8 (3) | C26—C25—C30—C21 | 178.9 (3) |
C4—C5—C10—C19 | 67.4 (4) | C24—C25—C30—C21 | −50.9 (4) |
C6—C5—C10—C19 | −62.8 (4) | C26—C25—C30—C39 | −62.0 (4) |
C4—C5—C10—C1 | −51.0 (4) | C24—C25—C30—C39 | 68.2 (4) |
C6—C5—C10—C1 | 178.7 (3) | C26—C25—C30—C29 | 60.3 (4) |
C4—C5—C10—C9 | −170.1 (3) | C24—C25—C30—C29 | −169.5 (3) |
C6—C5—C10—C9 | 59.7 (3) | C31—C29—C30—C21 | 60.9 (4) |
C11—C9—C10—C19 | −61.6 (3) | C28—C29—C30—C21 | −171.0 (3) |
C8—C9—C10—C19 | 66.9 (3) | C31—C29—C30—C39 | −61.4 (4) |
C11—C9—C10—C1 | 60.3 (4) | C28—C29—C30—C39 | 66.7 (3) |
C8—C9—C10—C1 | −171.2 (3) | C31—C29—C30—C25 | 176.6 (3) |
C11—C9—C10—C5 | 175.8 (3) | C28—C29—C30—C25 | −55.3 (3) |
C8—C9—C10—C5 | −55.7 (3) | C28—C29—C31—C32 | 54.3 (4) |
C10—C9—C11—C12 | −176.6 (3) | C30—C29—C31—C32 | −176.7 (3) |
C8—C9—C11—C12 | 54.0 (4) | C29—C31—C32—C33 | −54.7 (4) |
C9—C11—C12—C13 | −54.7 (4) | C31—C32—C33—C37 | 168.4 (2) |
C11—C12—C13—C17 | 168.3 (3) | C31—C32—C33—C34 | 56.1 (3) |
C11—C12—C13—C14 | 55.9 (3) | C31—C32—C33—C38 | −69.1 (3) |
C11—C12—C13—C18 | −69.7 (3) | C27—C28—C34—C35 | −52.4 (4) |
C7—C8—C14—C15 | −53.3 (4) | C29—C28—C34—C35 | −175.4 (3) |
C9—C8—C14—C15 | −176.4 (3) | C27—C28—C34—C33 | −177.4 (3) |
C7—C8—C14—C13 | −178.1 (3) | C29—C28—C34—C33 | 59.6 (3) |
C9—C8—C14—C13 | 58.7 (3) | C37—C33—C34—C28 | 175.9 (2) |
C17—C13—C14—C15 | 42.3 (3) | C32—C33—C34—C28 | −61.0 (3) |
C12—C13—C14—C15 | 164.9 (3) | C38—C33—C34—C28 | 63.2 (4) |
C18—C13—C14—C15 | −70.9 (4) | C37—C33—C34—C35 | 41.6 (3) |
C17—C13—C14—C8 | 176.9 (2) | C32—C33—C34—C35 | 164.7 (3) |
C12—C13—C14—C8 | −60.5 (3) | C38—C33—C34—C35 | −71.1 (3) |
C18—C13—C14—C8 | 63.7 (4) | C28—C34—C35—C36 | −168.5 (3) |
C8—C14—C15—C16 | −169.0 (3) | C33—C34—C35—C36 | −39.7 (3) |
C13—C14—C15—C16 | −40.1 (3) | C34—C35—C36—C37 | 21.1 (4) |
C14—C15—C16—C17 | 21.1 (3) | O2—N2—C37—C33 | 179.7 (2) |
O1—N1—C17—C13 | −179.8 (3) | O2—N2—C37—C36 | −2.3 (5) |
O1—N1—C17—C16 | −1.9 (5) | C32—C33—C37—N2 | 32.3 (4) |
C12—C13—C17—N1 | 31.2 (4) | C34—C33—C37—N2 | 149.7 (3) |
C14—C13—C17—N1 | 148.7 (3) | C38—C33—C37—N2 | −92.6 (3) |
C18—C13—C17—N1 | −93.0 (3) | C32—C33—C37—C36 | −146.1 (3) |
C12—C13—C17—C16 | −147.0 (3) | C34—C33—C37—C36 | −28.7 (3) |
C14—C13—C17—C16 | −29.6 (3) | C38—C33—C37—C36 | 89.0 (3) |
C18—C13—C17—C16 | 88.7 (3) | C35—C36—C37—N2 | −173.1 (3) |
C15—C16—C17—N1 | −172.4 (3) | C35—C36—C37—C33 | 5.1 (4) |
C15—C16—C17—C13 | 5.7 (3) | C18—C13—C10—C19 | 2.1 (3) |
C30—C21—C22—C23 | −40.6 (6) | C38—C33—C30—C39 | 2.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.82 | 2.11 | 2.805 (4) | 142 |
O2—H2···N1 | 0.82 | 2.13 | 2.815 (3) | 142 |
C16—H16A···O2i | 0.97 | 2.55 | 3.458 (4) | 155 |
C16—H16B···O2ii | 0.97 | 2.60 | 3.449 (5) | 147 |
C36—H36A···O1iii | 0.97 | 2.55 | 3.465 (5) | 158 |
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z−1; (iii) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H29NO |
Mr | 287.43 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.3510 (12), 42.306 (6), 7.1764 (6) |
β (°) | 115.651 (13) |
V (Å3) | 1738.2 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.51 |
Crystal size (mm) | 0.48 × 0.24 × 0.24 |
Data collection | |
Diffractometer | Enraf–Nonius MACH-3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3820, 3472, 2868 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.133, 1.08 |
No. of reflections | 3472 |
No. of parameters | 386 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.13 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), PLATON/HELENA (Spek, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.82 | 2.11 | 2.805 (4) | 142.1 |
O2—H2···N1 | 0.82 | 2.13 | 2.815 (3) | 141.6 |
C16—H16A···O2i | 0.97 | 2.55 | 3.458 (4) | 155.3 |
C16—H16B···O2ii | 0.97 | 2.60 | 3.449 (5) | 146.5 |
C36—H36A···O1iii | 0.97 | 2.55 | 3.465 (5) | 158.2 |
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z−1; (iii) x+1, y, z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Following on from our previous work focused on the structure–activity relationships (SAR) of new steroidal aromatase inhibitors (Cepa et al., 2005), several D-ring derivatives of the potent aromatase inhibitor 5α-androst-3-en-17-one (structural studies by Paixão et al., 2001) have been recently prepared and evaluated.
The title compound, (I) (Fig. 1), a C17 oxime derivative, has almost zero inhibitory activity. Hence, it was important, from the point of view of SAR studies, to understand this change of behaviour. X-ray studies indicate that this compound crystallizes with two independent molecules which have almost identical geometry. The internal degree of structural similarity between the two molecules (Kálmán et al., 1991) can be inferred from the values ID(24) (distances)= 99.0% and ID(23) (valency angles)= 99.7%. Ring bond lengths and angles are within expected values (Allen et al., 1987).
Due to the C═C double bond, ring A adopts a conformation intermediate between 10β-sofa and 1,10-half chair [asymmetry parameters (Duax & Norton, 1975): ΔCs(3)=10.9 (6) and 12.1 (5), ΔC2(3,4)=14.3 (7) and 12.4 (7), and ΔC2(1,2)=51.2 (7) and 50.2 (7)°, respectively, for molecules 1 and 2; puckering parameters (Cremer & Pople, 1975), calculated using the atom sequence C1—C10: q2=0.387 (5) and 0.380 (5) Å, and ϕ2= 313.1 (7) and 315.1 (8)°, respectively, for molecules 1 and 2]. Rings B and C have slightly flattened chair conformations. The five membered D-ring adopts a 14α-envelope conformation, slightly distorted towards 13β,14α-half chair [pseudo-rotation (Altona et al., 1968) and asymmetry parameters (Duax & Norton, 1975): Δ=–22.0 (5) and –23.5 (6), ϕm=43.6 (2) and 43.0 (2), ΔCs(14)=6.2 (4) and 5.5 (4), and ΔC2(13,14)=13.2 (4) and 13.8 (4) °, for molecules 1 and 2]. Due to the existence of only trans ring junctions, both molecules in the asymmetric unit have an almost planar distribution of the ring atoms (r.m.s. deviation 0.2466 and 0.2505, respectively, for molecules 1 and 2), with the planes being almost parallel to each other [angle between planes 4.50 (4)°].
The oxime moiety of both molecules lies on the plane of the D-ring 14α-envelope, as evidenced by the r.m.s. deviation of C13,C15—C17,O1,N1 of 0.0430 and 0.0384 for molecules 1 and 2, respectively. Two strong O—H···N hydrogen bonds lead to a crystal packing built up of dimers, with a six-membered ring O1—H1···N2—O2—H2···N1 (Fig. 2). These hydrogen bonds, in which the O atom acts as a donor, are almost parallel with the c axis. There are three additional C—H···O hydrogen bonds linking molecules along the a axis (Fig. 3), in which the same O atoms act as acceptors. The oxime C—N and N—O bond lengths are slightly smaller and significantly larger, respectively, than the values reported by Allen et al. (1987). These differences may be due to the special features of oxime moieties and their involvement in hydrogen bonds. In fact, the values determined fit well with the work of Jerslev (1983), who studied the correlations between these bond lengths in several oximes.
According to his work, the values obtained in the present study imply a certain degree of conjugation between the oxime moiety and the D-ring electronic distribution. Following Bertolasi et al. (1982), the large values obtained for the N—O bonds can be further related to the multiple hydrogen bonds in which the oxime group participates. The hydrogen bonding scheme determined in this study is, eventually, responsible for the almost total loss of aromatase inhibition behaviour. In fact, by replacing the C17 ketone with the C17 oxime group, the dual acceptor/donor hydrogen-bonding ability of this group can probably destabilize the structure of the receptor by hydrogen bonding to specific residues (Cepa et al., 2008).