16-[3-Methoxy-4-(2-piperidin-1-ylethoxy)benzylidene]-17-oxoandrost-5-en-3β-yl acetate monohydrate
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010202005X/na1582sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010202005X/na1582Isup2.hkl |
CCDC reference: 201282
A mixture of 16-[3-methoxy-4-(2-piperidin-1-ylethoxy)benzylidene]-17-oxo-5-androsten-3β-ol (0.5 g, 0.868 mmol), acetic anhydride (1.0 ml) and dry pyridine (2.0 ml) was heated on steam bath for 2 h. The contents of the reaction were then poured into ice-cold water and basicified with liquid ammonia. The precipitate obtained was filtered, washed with water, dried and crystallized in hexane (333–353 K) to afford crystals of the title compound (code: DPJ-RG-1111) (yield: 0.38 g, 70.5%; m.p. 399–401 K).
The asymmetric unit of (I) contains one molecule of the steroid plus one water molecule. The positions of the water H atoms were determined from a difference Fourier map and refined freely along with their isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and were constrained to ride on their parent non-H atoms, with Uiso(H) = 1.2Ueq(C). Due to the absence of any significant anomalous scatterers in the compound, attempts to confirm the absolute structure by refinement of the Flack (1983) parameter, in the presence of 4331 sets of Friedel equivalents, led to an inconclusive value (Flack & Bernardinelli, 2000) of -0.5 (7). Therefore, the Friedel pairs were merged before the final refinement and the absolute configuration was assigned to correspond with that of a known chiral centre in a precursor molecule which remained unchanged during the synthesis of the title compound. Reflection 002 was partially obscured by the beam stop and was omitted.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64.02; Farrugia, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).
C36H49NO5·H2O | F(000) = 644 |
Mr = 593.78 | Dx = 1.226 Mg m−3 |
Monoclinic, P21 | Melting point: 399 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1726 (1) Å | Cell parameters from 4884 reflections |
b = 14.9068 (2) Å | θ = 2.0–30.0° |
c = 17.6465 (3) Å | µ = 0.08 mm−1 |
β = 97.724 (1)° | T = 160 K |
V = 1608.99 (4) Å3 | Tablet, colourless |
Z = 2 | 0.25 × 0.25 × 0.15 mm |
Nonius KappaCCD diffractometer | 3793 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 sealed tube generator | Rint = 0.062 |
Horizontally mounted graphite crystal monochromator | θmax = 30.0°, θmin = 2.7° |
Detector resolution: 9 pixels mm-1 | h = 0→8 |
ϕ and ω scans with κ offsets | k = −20→20 |
42238 measured reflections | l = −24→24 |
4878 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom & difmap |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.0106P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4878 reflections | Δρmax = 0.24 e Å−3 |
401 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.016 (3) |
C36H49NO5·H2O | V = 1608.99 (4) Å3 |
Mr = 593.78 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.1726 (1) Å | µ = 0.08 mm−1 |
b = 14.9068 (2) Å | T = 160 K |
c = 17.6465 (3) Å | 0.25 × 0.25 × 0.15 mm |
β = 97.724 (1)° |
Nonius KappaCCD diffractometer | 3793 reflections with I > 2σ(I) |
42238 measured reflections | Rint = 0.062 |
4878 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.24 e Å−3 |
4878 reflections | Δρmin = −0.18 e Å−3 |
401 parameters |
Experimental. Solvent used: hexane Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.442 (1) Frames collected: 340 Seconds exposure per frame: 47 Degrees rotation per frame: 1.9 Crystal-Detector distance (mm): 28.0 |
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 | ||
O17 | 0.3416 (2) | 0.55301 (10) | −0.00199 (8) | 0.0328 (3) | |
O23 | 1.2293 (2) | 0.21799 (10) | −0.09286 (9) | 0.0329 (3) | |
O28 | 1.3920 (2) | 0.30874 (10) | −0.19793 (8) | 0.0294 (3) | |
O37 | 0.1940 (3) | 0.04190 (12) | 0.44042 (8) | 0.0374 (4) | |
O38 | −0.1043 (3) | −0.03766 (14) | 0.39813 (10) | 0.0537 (5) | |
N31 | 1.6421 (3) | 0.24250 (12) | −0.33543 (9) | 0.0259 (4) | |
C1 | 0.0745 (3) | 0.24554 (16) | 0.31322 (12) | 0.0320 (5) | |
H1A | 0.0123 | 0.3047 | 0.3238 | 0.038* | |
H1B | −0.0222 | 0.2183 | 0.2700 | 0.038* | |
C2 | 0.0736 (4) | 0.18556 (17) | 0.38408 (12) | 0.0344 (5) | |
H2A | 0.1580 | 0.2148 | 0.4290 | 0.041* | |
H2B | −0.0784 | 0.1772 | 0.3949 | 0.041* | |
C3 | 0.1737 (4) | 0.09540 (16) | 0.37048 (12) | 0.0325 (5) | |
H3 | 0.0815 | 0.0631 | 0.3282 | 0.039* | |
C4 | 0.4041 (3) | 0.10637 (15) | 0.35139 (12) | 0.0303 (5) | |
H4A | 0.4629 | 0.0469 | 0.3397 | 0.036* | |
H4B | 0.4985 | 0.1311 | 0.3963 | 0.036* | |
C5 | 0.4103 (3) | 0.16825 (14) | 0.28354 (11) | 0.0255 (4) | |
C6 | 0.5053 (3) | 0.14215 (14) | 0.22381 (12) | 0.0291 (4) | |
H6 | 0.5616 | 0.0828 | 0.2245 | 0.035* | |
C7 | 0.5303 (3) | 0.19890 (14) | 0.15585 (12) | 0.0285 (4) | |
H7A | 0.4278 | 0.1777 | 0.1115 | 0.034* | |
H7B | 0.6808 | 0.1924 | 0.1430 | 0.034* | |
C8 | 0.4855 (3) | 0.29752 (13) | 0.17028 (10) | 0.0218 (4) | |
H8 | 0.6125 | 0.3229 | 0.2048 | 0.026* | |
C9 | 0.2777 (3) | 0.30771 (14) | 0.20928 (10) | 0.0223 (4) | |
H9 | 0.1588 | 0.2750 | 0.1763 | 0.027* | |
C10 | 0.3041 (3) | 0.26008 (13) | 0.28861 (11) | 0.0234 (4) | |
C11 | 0.2008 (3) | 0.40607 (15) | 0.21296 (12) | 0.0274 (4) | |
H11A | 0.0519 | 0.4063 | 0.2280 | 0.033* | |
H11B | 0.2984 | 0.4372 | 0.2538 | 0.033* | |
C12 | 0.1962 (3) | 0.46024 (14) | 0.13827 (11) | 0.0254 (4) | |
H12A | 0.0768 | 0.4380 | 0.0998 | 0.031* | |
H12B | 0.1682 | 0.5243 | 0.1482 | 0.031* | |
C13 | 0.4150 (3) | 0.45051 (13) | 0.10766 (10) | 0.0214 (4) | |
C14 | 0.4561 (3) | 0.35054 (13) | 0.09595 (10) | 0.0215 (4) | |
H14 | 0.3202 | 0.3268 | 0.0653 | 0.026* | |
C15 | 0.6347 (3) | 0.34502 (13) | 0.04372 (11) | 0.0228 (4) | |
H15A | 0.7821 | 0.3450 | 0.0738 | 0.027* | |
H15B | 0.6177 | 0.2905 | 0.0115 | 0.027* | |
C16 | 0.5971 (3) | 0.42947 (14) | −0.00463 (10) | 0.0230 (4) | |
C17 | 0.4330 (3) | 0.48700 (14) | 0.02766 (11) | 0.0240 (4) | |
C18 | 0.6004 (3) | 0.49816 (14) | 0.15987 (11) | 0.0263 (4) | |
H18A | 0.6077 | 0.4747 | 0.2120 | 0.039* | |
H18B | 0.5715 | 0.5628 | 0.1600 | 0.039* | |
H18C | 0.7399 | 0.4872 | 0.1407 | 0.039* | |
C19 | 0.4460 (3) | 0.31588 (15) | 0.35007 (12) | 0.0298 (4) | |
H19A | 0.4813 | 0.2798 | 0.3965 | 0.045* | |
H19B | 0.3653 | 0.3696 | 0.3619 | 0.045* | |
H19C | 0.5814 | 0.3337 | 0.3309 | 0.045* | |
C20 | 0.6988 (3) | 0.45957 (14) | −0.06290 (10) | 0.0240 (4) | |
H20 | 0.6452 | 0.5148 | −0.0848 | 0.029* | |
C21 | 0.8783 (3) | 0.42009 (14) | −0.09725 (10) | 0.0234 (4) | |
C22 | 0.9681 (3) | 0.33564 (14) | −0.07625 (11) | 0.0240 (4) | |
H22 | 0.9104 | 0.3021 | −0.0378 | 0.029* | |
C23 | 1.1383 (3) | 0.30006 (14) | −0.11007 (11) | 0.0244 (4) | |
C24 | 1.2245 (3) | 0.34927 (14) | −0.16744 (10) | 0.0242 (4) | |
C25 | 1.1363 (3) | 0.43208 (14) | −0.18900 (11) | 0.0255 (4) | |
H25 | 1.1924 | 0.4652 | −0.2280 | 0.031* | |
C26 | 0.9664 (3) | 0.46735 (14) | −0.15418 (11) | 0.0256 (4) | |
H26 | 0.9090 | 0.5247 | −0.1694 | 0.031* | |
C27 | 1.1221 (4) | 0.16307 (15) | −0.04338 (12) | 0.0335 (5) | |
H27A | 1.1294 | 0.1919 | 0.0068 | 0.050* | |
H27B | 1.1942 | 0.1044 | −0.0377 | 0.050* | |
H27C | 0.9687 | 0.1551 | −0.0652 | 0.050* | |
C29 | 1.4865 (3) | 0.35858 (15) | −0.25493 (11) | 0.0279 (4) | |
H29A | 1.5285 | 0.4191 | −0.2351 | 0.034* | |
H29B | 1.3775 | 0.3656 | −0.3011 | 0.034* | |
C30 | 1.6859 (3) | 0.31049 (16) | −0.27581 (12) | 0.0299 (4) | |
H30A | 1.7867 | 0.3556 | −0.2928 | 0.036* | |
H30B | 1.7622 | 0.2815 | −0.2292 | 0.036* | |
C32 | 1.5352 (3) | 0.16249 (16) | −0.30828 (12) | 0.0324 (5) | |
H32A | 1.3989 | 0.1805 | −0.2886 | 0.039* | |
H32B | 1.6331 | 0.1344 | −0.2658 | 0.039* | |
C33 | 1.4824 (4) | 0.09524 (18) | −0.37238 (14) | 0.0403 (5) | |
H33A | 1.3734 | 0.1216 | −0.4125 | 0.048* | |
H33B | 1.4166 | 0.0411 | −0.3523 | 0.048* | |
C34 | 1.6855 (4) | 0.06811 (17) | −0.40772 (14) | 0.0429 (6) | |
H34A | 1.7847 | 0.0326 | −0.3704 | 0.051* | |
H34B | 1.6425 | 0.0304 | −0.4534 | 0.051* | |
C35 | 1.8034 (4) | 0.15204 (17) | −0.43027 (13) | 0.0384 (5) | |
H35A | 1.9436 | 0.1346 | −0.4476 | 0.046* | |
H35B | 1.7127 | 0.1822 | −0.4734 | 0.046* | |
C36 | 1.8475 (3) | 0.21648 (16) | −0.36355 (12) | 0.0320 (5) | |
H36A | 1.9461 | 0.1877 | −0.3217 | 0.038* | |
H36B | 1.9213 | 0.2707 | −0.3799 | 0.038* | |
C38 | 0.0522 (3) | −0.02392 (15) | 0.44607 (12) | 0.0294 (4) | |
C39 | 0.1087 (4) | −0.07710 (17) | 0.51726 (12) | 0.0379 (5) | |
H39A | −0.0048 | −0.1223 | 0.5209 | 0.057* | |
H39B | 0.1184 | −0.0371 | 0.5617 | 0.057* | |
H39C | 0.2496 | −0.1070 | 0.5161 | 0.057* | |
O1W | 0.4014 (4) | 0.33450 (18) | 0.53911 (10) | 0.0666 (7) | |
H1W | 0.476 (7) | 0.300 (3) | 0.582 (2) | 0.108 (14)* | |
H2W | 0.302 (8) | 0.374 (4) | 0.569 (3) | 0.133 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O17 | 0.0354 (8) | 0.0297 (9) | 0.0344 (8) | 0.0091 (7) | 0.0082 (6) | 0.0082 (7) |
O23 | 0.0374 (8) | 0.0256 (8) | 0.0383 (8) | 0.0082 (6) | 0.0149 (6) | 0.0061 (7) |
O28 | 0.0309 (7) | 0.0305 (8) | 0.0294 (7) | 0.0034 (6) | 0.0136 (5) | 0.0004 (6) |
O37 | 0.0453 (9) | 0.0381 (9) | 0.0274 (8) | −0.0150 (7) | −0.0009 (6) | 0.0109 (7) |
O38 | 0.0557 (10) | 0.0598 (12) | 0.0418 (10) | −0.0296 (9) | −0.0078 (8) | 0.0173 (9) |
N31 | 0.0248 (8) | 0.0291 (9) | 0.0248 (8) | −0.0017 (7) | 0.0073 (6) | −0.0024 (7) |
C1 | 0.0264 (10) | 0.0376 (13) | 0.0334 (11) | 0.0010 (9) | 0.0096 (8) | 0.0103 (10) |
C2 | 0.0312 (10) | 0.0412 (13) | 0.0321 (11) | −0.0003 (9) | 0.0088 (8) | 0.0122 (10) |
C3 | 0.0395 (11) | 0.0337 (12) | 0.0231 (10) | −0.0097 (10) | 0.0002 (8) | 0.0083 (9) |
C4 | 0.0363 (11) | 0.0260 (11) | 0.0294 (11) | 0.0010 (9) | 0.0074 (9) | 0.0058 (9) |
C5 | 0.0253 (9) | 0.0230 (10) | 0.0283 (10) | −0.0004 (8) | 0.0037 (7) | 0.0038 (8) |
C6 | 0.0356 (10) | 0.0198 (10) | 0.0327 (11) | 0.0014 (8) | 0.0074 (8) | 0.0013 (8) |
C7 | 0.0353 (11) | 0.0237 (11) | 0.0276 (10) | 0.0017 (8) | 0.0087 (8) | 0.0003 (8) |
C8 | 0.0221 (8) | 0.0213 (9) | 0.0225 (9) | 0.0009 (7) | 0.0042 (6) | 0.0001 (8) |
C9 | 0.0207 (8) | 0.0231 (10) | 0.0237 (9) | −0.0003 (7) | 0.0050 (7) | 0.0013 (8) |
C10 | 0.0238 (9) | 0.0224 (10) | 0.0244 (9) | −0.0009 (7) | 0.0043 (7) | 0.0026 (8) |
C11 | 0.0262 (9) | 0.0276 (11) | 0.0302 (10) | 0.0032 (8) | 0.0103 (7) | 0.0035 (9) |
C12 | 0.0234 (9) | 0.0249 (10) | 0.0293 (10) | 0.0021 (8) | 0.0084 (7) | 0.0041 (8) |
C13 | 0.0208 (8) | 0.0215 (10) | 0.0224 (9) | 0.0000 (7) | 0.0054 (7) | 0.0007 (7) |
C14 | 0.0220 (8) | 0.0215 (9) | 0.0217 (9) | −0.0006 (7) | 0.0053 (7) | −0.0003 (8) |
C15 | 0.0248 (9) | 0.0208 (10) | 0.0235 (9) | 0.0007 (8) | 0.0053 (7) | −0.0008 (8) |
C16 | 0.0238 (9) | 0.0228 (10) | 0.0225 (9) | 0.0003 (8) | 0.0033 (7) | −0.0011 (8) |
C17 | 0.0218 (9) | 0.0246 (10) | 0.0263 (9) | −0.0017 (8) | 0.0054 (7) | 0.0015 (8) |
C18 | 0.0262 (9) | 0.0256 (10) | 0.0282 (10) | −0.0016 (8) | 0.0076 (8) | −0.0020 (8) |
C19 | 0.0354 (10) | 0.0280 (11) | 0.0261 (10) | −0.0020 (9) | 0.0040 (8) | −0.0013 (8) |
C20 | 0.0275 (9) | 0.0218 (10) | 0.0226 (9) | 0.0015 (8) | 0.0033 (7) | 0.0002 (8) |
C21 | 0.0261 (9) | 0.0222 (10) | 0.0224 (9) | −0.0005 (8) | 0.0048 (7) | −0.0019 (8) |
C22 | 0.0269 (9) | 0.0245 (10) | 0.0217 (9) | −0.0005 (8) | 0.0077 (7) | 0.0010 (8) |
C23 | 0.0260 (9) | 0.0237 (10) | 0.0234 (9) | 0.0023 (8) | 0.0038 (7) | 0.0008 (8) |
C24 | 0.0228 (9) | 0.0284 (10) | 0.0223 (9) | −0.0017 (8) | 0.0064 (7) | −0.0040 (8) |
C25 | 0.0269 (9) | 0.0246 (10) | 0.0258 (9) | −0.0034 (8) | 0.0065 (7) | 0.0016 (8) |
C26 | 0.0282 (9) | 0.0221 (10) | 0.0270 (9) | −0.0010 (8) | 0.0054 (7) | 0.0013 (8) |
C27 | 0.0435 (12) | 0.0242 (11) | 0.0349 (11) | 0.0060 (9) | 0.0130 (9) | 0.0050 (9) |
C29 | 0.0298 (10) | 0.0297 (11) | 0.0256 (10) | −0.0025 (8) | 0.0088 (8) | −0.0011 (8) |
C30 | 0.0246 (9) | 0.0358 (12) | 0.0301 (10) | −0.0019 (9) | 0.0069 (7) | −0.0057 (9) |
C32 | 0.0333 (11) | 0.0336 (12) | 0.0319 (11) | −0.0041 (9) | 0.0100 (8) | 0.0012 (9) |
C33 | 0.0442 (13) | 0.0350 (13) | 0.0430 (13) | −0.0067 (10) | 0.0103 (10) | −0.0061 (11) |
C34 | 0.0552 (15) | 0.0359 (14) | 0.0393 (13) | 0.0034 (11) | 0.0126 (10) | −0.0048 (11) |
C35 | 0.0453 (13) | 0.0391 (13) | 0.0334 (12) | 0.0069 (10) | 0.0151 (10) | −0.0012 (10) |
C36 | 0.0281 (10) | 0.0359 (12) | 0.0341 (11) | 0.0020 (9) | 0.0118 (8) | 0.0003 (10) |
C38 | 0.0330 (10) | 0.0266 (11) | 0.0293 (10) | −0.0037 (9) | 0.0069 (8) | 0.0010 (8) |
C39 | 0.0472 (12) | 0.0332 (12) | 0.0335 (11) | −0.0032 (11) | 0.0060 (9) | 0.0077 (10) |
O1W | 0.0801 (14) | 0.0879 (17) | 0.0315 (9) | 0.0451 (13) | 0.0060 (9) | 0.0021 (10) |
O17—C17 | 1.217 (2) | C15—H15A | 0.9900 |
O23—C23 | 1.363 (3) | C15—H15B | 0.9900 |
O23—C27 | 1.423 (3) | C16—C20 | 1.351 (3) |
O28—C24 | 1.368 (2) | C16—C17 | 1.497 (3) |
O28—C29 | 1.436 (2) | C18—H18A | 0.9800 |
O37—C38 | 1.328 (3) | C18—H18B | 0.9800 |
O37—C3 | 1.461 (2) | C18—H18C | 0.9800 |
O38—C38 | 1.213 (3) | C19—H19A | 0.9800 |
N31—C30 | 1.460 (3) | C19—H19B | 0.9800 |
N31—C32 | 1.474 (3) | C19—H19C | 0.9800 |
N31—C36 | 1.474 (2) | C20—C21 | 1.457 (3) |
C1—C2 | 1.538 (3) | C20—H20 | 0.9500 |
C1—C10 | 1.553 (3) | C21—C26 | 1.396 (3) |
C1—H1A | 0.9900 | C21—C22 | 1.405 (3) |
C1—H1B | 0.9900 | C22—C23 | 1.382 (3) |
C2—C3 | 1.512 (3) | C22—H22 | 0.9500 |
C2—H2A | 0.9900 | C23—C24 | 1.411 (3) |
C2—H2B | 0.9900 | C24—C25 | 1.382 (3) |
C3—C4 | 1.514 (3) | C25—C26 | 1.388 (3) |
C3—H3 | 1.0000 | C25—H25 | 0.9500 |
C4—C5 | 1.516 (3) | C26—H26 | 0.9500 |
C4—H4A | 0.9900 | C27—H27A | 0.9800 |
C4—H4B | 0.9900 | C27—H27B | 0.9800 |
C5—C6 | 1.332 (3) | C27—H27C | 0.9800 |
C5—C10 | 1.525 (3) | C29—C30 | 1.512 (3) |
C6—C7 | 1.492 (3) | C29—H29A | 0.9900 |
C6—H6 | 0.9500 | C29—H29B | 0.9900 |
C7—C8 | 1.524 (3) | C30—H30A | 0.9900 |
C7—H7A | 0.9900 | C30—H30B | 0.9900 |
C7—H7B | 0.9900 | C32—C33 | 1.514 (3) |
C8—C14 | 1.521 (3) | C32—H32A | 0.9900 |
C8—C9 | 1.543 (2) | C32—H32B | 0.9900 |
C8—H8 | 1.0000 | C33—C34 | 1.528 (3) |
C9—C11 | 1.545 (3) | C33—H33A | 0.9900 |
C9—C10 | 1.559 (3) | C33—H33B | 0.9900 |
C9—H9 | 1.0000 | C34—C35 | 1.527 (4) |
C10—C19 | 1.542 (3) | C34—H34A | 0.9900 |
C11—C12 | 1.543 (3) | C34—H34B | 0.9900 |
C11—H11A | 0.9900 | C35—C36 | 1.516 (3) |
C11—H11B | 0.9900 | C35—H35A | 0.9900 |
C12—C13 | 1.527 (2) | C35—H35B | 0.9900 |
C12—H12A | 0.9900 | C36—H36A | 0.9900 |
C12—H12B | 0.9900 | C36—H36B | 0.9900 |
C13—C14 | 1.530 (3) | C38—C39 | 1.487 (3) |
C13—C17 | 1.531 (3) | C39—H39A | 0.9800 |
C13—C18 | 1.543 (3) | C39—H39B | 0.9800 |
C14—C15 | 1.531 (3) | C39—H39C | 0.9800 |
C14—H14 | 1.0000 | O1W—H1W | 0.97 (5) |
C15—C16 | 1.521 (3) | O1W—H2W | 1.04 (5) |
C23—O23—C27 | 116.17 (16) | O17—C17—C13 | 126.66 (18) |
C24—O28—C29 | 116.52 (16) | C16—C17—C13 | 106.51 (15) |
C38—O37—C3 | 118.97 (16) | C13—C18—H18A | 109.5 |
C30—N31—C32 | 112.03 (16) | C13—C18—H18B | 109.5 |
C30—N31—C36 | 109.94 (15) | H18A—C18—H18B | 109.5 |
C32—N31—C36 | 109.83 (17) | C13—C18—H18C | 109.5 |
C2—C1—C10 | 114.32 (17) | H18A—C18—H18C | 109.5 |
C2—C1—H1A | 108.7 | H18B—C18—H18C | 109.5 |
C10—C1—H1A | 108.7 | C10—C19—H19A | 109.5 |
C2—C1—H1B | 108.7 | C10—C19—H19B | 109.5 |
C10—C1—H1B | 108.7 | H19A—C19—H19B | 109.5 |
H1A—C1—H1B | 107.6 | C10—C19—H19C | 109.5 |
C3—C2—C1 | 109.97 (17) | H19A—C19—H19C | 109.5 |
C3—C2—H2A | 109.7 | H19B—C19—H19C | 109.5 |
C1—C2—H2A | 109.7 | C16—C20—C21 | 129.76 (19) |
C3—C2—H2B | 109.7 | C16—C20—H20 | 115.1 |
C1—C2—H2B | 109.7 | C21—C20—H20 | 115.1 |
H2A—C2—H2B | 108.2 | C26—C21—C22 | 117.65 (18) |
O37—C3—C2 | 109.98 (17) | C26—C21—C20 | 119.16 (18) |
O37—C3—C4 | 105.69 (16) | C22—C21—C20 | 123.20 (18) |
C2—C3—C4 | 110.83 (18) | C23—C22—C21 | 121.73 (18) |
O37—C3—H3 | 110.1 | C23—C22—H22 | 119.1 |
C2—C3—H3 | 110.1 | C21—C22—H22 | 119.1 |
C4—C3—H3 | 110.1 | O23—C23—C22 | 124.24 (18) |
C3—C4—C5 | 111.44 (16) | O23—C23—C24 | 116.25 (17) |
C3—C4—H4A | 109.3 | C22—C23—C24 | 119.50 (18) |
C5—C4—H4A | 109.3 | O28—C24—C25 | 125.23 (18) |
C3—C4—H4B | 109.3 | O28—C24—C23 | 115.50 (18) |
C5—C4—H4B | 109.3 | C25—C24—C23 | 119.27 (17) |
H4A—C4—H4B | 108.0 | C24—C25—C26 | 120.65 (18) |
C6—C5—C4 | 120.53 (19) | C24—C25—H25 | 119.7 |
C6—C5—C10 | 123.17 (18) | C26—C25—H25 | 119.7 |
C4—C5—C10 | 116.30 (17) | C25—C26—C21 | 121.19 (19) |
C5—C6—C7 | 125.07 (19) | C25—C26—H26 | 119.4 |
C5—C6—H6 | 117.5 | C21—C26—H26 | 119.4 |
C7—C6—H6 | 117.5 | O23—C27—H27A | 109.5 |
C6—C7—C8 | 111.84 (17) | O23—C27—H27B | 109.5 |
C6—C7—H7A | 109.2 | H27A—C27—H27B | 109.5 |
C8—C7—H7A | 109.2 | O23—C27—H27C | 109.5 |
C6—C7—H7B | 109.2 | H27A—C27—H27C | 109.5 |
C8—C7—H7B | 109.2 | H27B—C27—H27C | 109.5 |
H7A—C7—H7B | 107.9 | O28—C29—C30 | 110.24 (18) |
C14—C8—C7 | 111.13 (16) | O28—C29—H29A | 109.6 |
C14—C8—C9 | 108.88 (14) | C30—C29—H29A | 109.6 |
C7—C8—C9 | 110.49 (16) | O28—C29—H29B | 109.6 |
C14—C8—H8 | 108.8 | C30—C29—H29B | 109.6 |
C7—C8—H8 | 108.8 | H29A—C29—H29B | 108.1 |
C9—C8—H8 | 108.8 | N31—C30—C29 | 115.28 (16) |
C8—C9—C11 | 112.99 (16) | N31—C30—H30A | 108.5 |
C8—C9—C10 | 111.27 (14) | C29—C30—H30A | 108.5 |
C11—C9—C10 | 112.97 (15) | N31—C30—H30B | 108.5 |
C8—C9—H9 | 106.3 | C29—C30—H30B | 108.5 |
C11—C9—H9 | 106.3 | H30A—C30—H30B | 107.5 |
C10—C9—H9 | 106.3 | N31—C32—C33 | 110.72 (18) |
C5—C10—C19 | 108.51 (16) | N31—C32—H32A | 109.5 |
C5—C10—C1 | 107.86 (16) | C33—C32—H32A | 109.5 |
C19—C10—C1 | 109.39 (17) | N31—C32—H32B | 109.5 |
C5—C10—C9 | 110.49 (15) | C33—C32—H32B | 109.5 |
C19—C10—C9 | 111.53 (16) | H32A—C32—H32B | 108.1 |
C1—C10—C9 | 108.99 (15) | C32—C33—C34 | 111.97 (19) |
C12—C11—C9 | 115.56 (16) | C32—C33—H33A | 109.2 |
C12—C11—H11A | 108.4 | C34—C33—H33A | 109.2 |
C9—C11—H11A | 108.4 | C32—C33—H33B | 109.2 |
C12—C11—H11B | 108.4 | C34—C33—H33B | 109.2 |
C9—C11—H11B | 108.4 | H33A—C33—H33B | 107.9 |
H11A—C11—H11B | 107.5 | C35—C34—C33 | 109.6 (2) |
C13—C12—C11 | 109.67 (15) | C35—C34—H34A | 109.8 |
C13—C12—H12A | 109.7 | C33—C34—H34A | 109.8 |
C11—C12—H12A | 109.7 | C35—C34—H34B | 109.8 |
C13—C12—H12B | 109.7 | C33—C34—H34B | 109.8 |
C11—C12—H12B | 109.7 | H34A—C34—H34B | 108.2 |
H12A—C12—H12B | 108.2 | C36—C35—C34 | 111.04 (18) |
C12—C13—C14 | 108.12 (15) | C36—C35—H35A | 109.4 |
C12—C13—C17 | 118.01 (15) | C34—C35—H35A | 109.4 |
C14—C13—C17 | 100.81 (15) | C36—C35—H35B | 109.4 |
C12—C13—C18 | 111.44 (15) | C34—C35—H35B | 109.4 |
C14—C13—C18 | 113.93 (15) | H35A—C35—H35B | 108.0 |
C17—C13—C18 | 104.30 (15) | N31—C36—C35 | 110.83 (17) |
C8—C14—C13 | 113.09 (15) | N31—C36—H36A | 109.5 |
C8—C14—C15 | 118.63 (15) | C35—C36—H36A | 109.5 |
C13—C14—C15 | 106.24 (15) | N31—C36—H36B | 109.5 |
C8—C14—H14 | 106.0 | C35—C36—H36B | 109.5 |
C13—C14—H14 | 106.0 | H36A—C36—H36B | 108.1 |
C15—C14—H14 | 106.0 | O38—C38—O37 | 122.95 (19) |
C16—C15—C14 | 103.03 (15) | O38—C38—C39 | 125.0 (2) |
C16—C15—H15A | 111.2 | O37—C38—C39 | 112.05 (18) |
C14—C15—H15A | 111.2 | C38—C39—H39A | 109.5 |
C16—C15—H15B | 111.2 | C38—C39—H39B | 109.5 |
C14—C15—H15B | 111.2 | H39A—C39—H39B | 109.5 |
H15A—C15—H15B | 109.1 | C38—C39—H39C | 109.5 |
C20—C16—C17 | 120.45 (18) | H39A—C39—H39C | 109.5 |
C20—C16—C15 | 130.56 (18) | H39B—C39—H39C | 109.5 |
C17—C16—C15 | 108.70 (15) | H1W—O1W—H2W | 99 (3) |
O17—C17—C16 | 126.70 (18) | ||
C10—C1—C2—C3 | −56.8 (2) | C13—C14—C15—C16 | −30.15 (18) |
C38—O37—C3—C2 | 103.5 (2) | C14—C15—C16—C20 | −177.2 (2) |
C38—O37—C3—C4 | −136.8 (2) | C14—C15—C16—C17 | 9.26 (19) |
C1—C2—C3—O37 | 174.05 (16) | C20—C16—C17—O17 | 16.5 (3) |
C1—C2—C3—C4 | 57.5 (2) | C15—C16—C17—O17 | −169.15 (19) |
O37—C3—C4—C5 | −174.74 (18) | C20—C16—C17—C13 | −159.53 (17) |
C2—C3—C4—C5 | −55.6 (2) | C15—C16—C17—C13 | 14.81 (19) |
C3—C4—C5—C6 | −127.3 (2) | C12—C13—C17—O17 | 34.2 (3) |
C3—C4—C5—C10 | 53.0 (2) | C14—C13—C17—O17 | 151.60 (19) |
C4—C5—C6—C7 | −176.92 (19) | C18—C13—C17—O17 | −90.1 (2) |
C10—C5—C6—C7 | 2.7 (3) | C12—C13—C17—C16 | −149.76 (17) |
C5—C6—C7—C8 | 14.0 (3) | C14—C13—C17—C16 | −32.36 (18) |
C6—C7—C8—C14 | −165.99 (16) | C18—C13—C17—C16 | 85.99 (18) |
C6—C7—C8—C9 | −45.0 (2) | C17—C16—C20—C21 | 172.55 (17) |
C14—C8—C9—C11 | −47.8 (2) | C15—C16—C20—C21 | −0.4 (3) |
C7—C8—C9—C11 | −170.13 (17) | C16—C20—C21—C26 | −175.67 (19) |
C14—C8—C9—C10 | −176.14 (16) | C16—C20—C21—C22 | 4.7 (3) |
C7—C8—C9—C10 | 61.5 (2) | C26—C21—C22—C23 | 0.3 (3) |
C6—C5—C10—C19 | −110.0 (2) | C20—C21—C22—C23 | 179.91 (17) |
C4—C5—C10—C19 | 69.6 (2) | C27—O23—C23—C22 | 7.6 (3) |
C6—C5—C10—C1 | 131.6 (2) | C27—O23—C23—C24 | −171.17 (17) |
C4—C5—C10—C1 | −48.8 (2) | C21—C22—C23—O23 | −178.90 (17) |
C6—C5—C10—C9 | 12.6 (3) | C21—C22—C23—C24 | −0.2 (3) |
C4—C5—C10—C9 | −167.80 (16) | C29—O28—C24—C25 | 2.3 (3) |
C2—C1—C10—C5 | 50.5 (2) | C29—O28—C24—C23 | −178.35 (16) |
C2—C1—C10—C19 | −67.3 (2) | O23—C23—C24—O28 | −1.0 (2) |
C2—C1—C10—C9 | 170.48 (18) | C22—C23—C24—O28 | −179.76 (16) |
C8—C9—C10—C5 | −43.7 (2) | O23—C23—C24—C25 | 178.46 (16) |
C11—C9—C10—C5 | −172.04 (15) | C22—C23—C24—C25 | −0.3 (3) |
C8—C9—C10—C19 | 77.1 (2) | O28—C24—C25—C26 | −179.84 (17) |
C11—C9—C10—C19 | −51.3 (2) | C23—C24—C25—C26 | 0.8 (3) |
C8—C9—C10—C1 | −162.05 (17) | C24—C25—C26—C21 | −0.7 (3) |
C11—C9—C10—C1 | 69.6 (2) | C22—C21—C26—C25 | 0.2 (3) |
C8—C9—C11—C12 | 46.0 (2) | C20—C21—C26—C25 | −179.46 (16) |
C10—C9—C11—C12 | 173.43 (15) | C24—O28—C29—C30 | 173.01 (15) |
C9—C11—C12—C13 | −50.4 (2) | C32—N31—C30—C29 | −71.2 (2) |
C11—C12—C13—C14 | 57.3 (2) | C36—N31—C30—C29 | 166.39 (18) |
C11—C12—C13—C17 | 170.73 (17) | O28—C29—C30—N31 | 86.3 (2) |
C11—C12—C13—C18 | −68.6 (2) | C30—N31—C32—C33 | 177.31 (18) |
C7—C8—C14—C13 | −178.91 (16) | C36—N31—C32—C33 | −60.2 (2) |
C9—C8—C14—C13 | 59.16 (19) | N31—C32—C33—C34 | 56.5 (3) |
C7—C8—C14—C15 | −53.5 (2) | C32—C33—C34—C35 | −52.2 (3) |
C9—C8—C14—C15 | −175.45 (16) | C33—C34—C35—C36 | 52.6 (3) |
C12—C13—C14—C8 | −65.04 (19) | C30—N31—C36—C35 | −175.00 (18) |
C17—C13—C14—C8 | 170.53 (14) | C32—N31—C36—C35 | 61.3 (2) |
C18—C13—C14—C8 | 59.4 (2) | C34—C35—C36—N31 | −58.1 (2) |
C12—C13—C14—C15 | 163.14 (14) | C3—O37—C38—O38 | −5.7 (3) |
C17—C13—C14—C15 | 38.71 (17) | C3—O37—C38—C39 | 174.4 (2) |
C18—C13—C14—C15 | −72.39 (19) | C19—C10—C13—C18 | 12.53 (15) |
C8—C14—C15—C16 | −158.80 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N31i | 0.97 (5) | 1.88 (5) | 2.847 (3) | 174 (4) |
O1W—H2W···O38ii | 1.04 (5) | 1.94 (5) | 2.961 (3) | 167 (4) |
Symmetry codes: (i) x−1, y, z+1; (ii) −x, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C36H49NO5·H2O |
Mr | 593.78 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 160 |
a, b, c (Å) | 6.1726 (1), 14.9068 (2), 17.6465 (3) |
β (°) | 97.724 (1) |
V (Å3) | 1608.99 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42238, 4878, 3793 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.105, 1.03 |
No. of reflections | 4878 |
No. of parameters | 401 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 |
Computer programs: COLLECT (Nonius, 2000), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), WinGX (Version 1.64.02; Farrugia, 1999), SHELXL97 and PLATON (Spek, 2002).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N31i | 0.97 (5) | 1.88 (5) | 2.847 (3) | 174 (4) |
O1W—H2W···O38ii | 1.04 (5) | 1.94 (5) | 2.961 (3) | 167 (4) |
Symmetry codes: (i) x−1, y, z+1; (ii) −x, y+1/2, −z+1. |
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The present study of the title compound, (I), is the 11t h in our series of X-ray crystal structure analyses of new synthetic androstene derivatives (Vasuki et al., 2001; Hema et al., 2002; Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a; Vasuki, Thamotharan, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002c; Vasuki, Parthasarathi, Ramamurthi, Piplani & Jindal, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002b). In our studies, we are particularly interested in the conformational flexibilities of the steroids resulting from variations in the substituents at the C3, C16 and C17 positions.
The crystals of (I) are enantiomerically pure. However, due to the absence of significant anomalous scatterers in the compound, the absolute configuration of the molecule has not been determined by the X-ray diffraction experiment. The enantiomer used in the refinement was assigned to correspond with the configuration of a known chiral centre in a precursor molecule which remained unchanged during the synthesis of (I).
Fig. 1 shows the asymmetric unit of (I) with the steroid numbering scheme and ring labels. Among the few conformational options, both methyl groups of the steroid nucleus adopt the expected staggered arrangements. The geometry of the rings is trans at the B/C and C/D ring junctions. The distance between the terminal C atoms, C39 and C34, is 20.213 (3) Å. The C5—C6 distance of 1.332 (3) Å confirms the presence of a localized double bond at this position (Kalman et al., 1992; Vasuki et al., 2001; Hema et al., 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a; Vasuki, Thamotharan, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002b). Rings A and C are slightly flattened, the mean values of their ring torsion angles being 53.68 (8) and 54.53 (8)°, respectively. Both ring conformations are close to that of a chair, as shown by the values of the Cremer & Pople (1975) puckering parameters [ring A: Q = 0.548 (2) Å, θ = 5.7 (2)° and ϕ = 85 (2)° for the atom sequence C1—C2—C3—C4—C5—C10; ring C: Q = 0.568 (2) Å, θ = 11.9 (2)° and ϕ = 266.4 (10)° for the atom sequence C8—C9—C11—C12—C13—C14]. Thus, the presence of the acetoxy group bonded to atom C3 does not disturb the usual chair conformation of ring A of the steroid nucleus. The 3β-acetoxy group bonded to ring A is planar. The C3—O37 bond is oriented equatorially and (-)antiperiplanar to the C3—C4 bond. The dihedral angle between the plane of the acetoxy group and the steroid nucleus plane is 83.45 (12)°.
Due to the C5═C6 double bond, the environment of atom C5 is planar, and hence ring B adopts the 8β,9α-half-chair conformation generally found in steroids with a C5═C6 double bond (Caira et al., 1995; Andrade et al., 2001; Vasuki et al., 2001; Hema et al., 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a; Vasuki, Thamotharan, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002b), with puckering parameters Q = 0.494 (2) Å, θ = 51.7 (2)° and ϕ = 209.2 (3)° for the atom sequence C5—C6—C7—C8—C9—C10. The five-membered ring D exhibits a distorted 13β,14α-half-chair conformation [Δ = 3.9° and ϕm = 38.8 (1)° for the atom sequence C13—C14—C15—C16—C17; Altona et al., 1968]. The piperidine ring adopts a chair conformation, as is evident from the puckering parameters [Q = 0.576 (2) Å, θ = 4.6 (2)° and ϕ = 345 (3)°] for the atom sequence N31—C32—C33—C34—C35—C36. Atoms N31 and C34 are on opposite sides of the C32/C33/C35/C36 plane and displaced from it by 0.691 (2) and 0.649 (3) Å, respectively.
The C17—C16—C20—C21 torsion angle of 172.55 (17)° indicates that the methoxybenzylidene moiety has an E configuration with respect to the carbonyl group at position 17. The C15—C16—C20 exocyclic angle of 130.56 (18)° is significantly larger than the normal value of 120°, and this may be due to the steric repulsion between atoms H15A and H22 (2.31 Å) and that between atoms H15B and H22 (2.12 Å).
The pseudo-torsion angle C19—C10···C13—C18 has a value of 12.53 (15)°. The steroid nucleus and the average plane of the piperidine ring are oriented at angles of 6.38 (4) and 68.93 (8)°, respectively, with respect to the 3-methoxybenzylidene ring. In (I), the angles C8—C14—C15 of 118.63 (15)° and C14—C13—C17 of 100.81 (15)° are close to the expected values of 119.3 and 99.2°, respectively (Duax et al., 1976). [In Hema et al. (2002), we inadvertently gave the upper limit for these angles, instead of expected values.]
The water molecule forms an intermolecular hydrogen bond with the N atom of the piperidine ring of a neighbouring steroid molecule, as well as with the carbonyl O atom of the ester group of a different neighbouring steroid molecule (Table 1). These interactions link the steroid and water molecules alternately into chains, which run parallel to the y axis and have a binary graph-set motif (Bernstein et al., 1995) of C22(24).