Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010100912X/vj1136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100912X/vj1136Isup2.hkl |
CCDC reference: 173363
The title compound was prepared by condensing dehydroepiandrosterone (1 g, 3.47 mM) with 2-pyridine carboxaldehyde (1.75 g, 16.34 mM) in the presence of sodium hydroxide (1.75 g, 43.75 mM) in methanol (20 ml). The absolute configuration of the epiandrosterone is already known (Weeks et al., 1971). The reaction mixture was shaken at room temperature for 1 h, and then poured into ice-cold water and allowed to stand overnight. The precipitate was filtered, washed with distilled water and dried under vacuum. The solid residue was crystallized from methanol to afford crystals of (I)·H2O (1.0 g, 72.9%, m.p.: 478–483 K).
All H atoms of the steroid were located from difference Fourier maps and were then included in the structure-factor calculations as riding atoms with C—H distances in the range 0.93–0.98 Å. The H atoms of the water molecule were also obtained from a difference map and were initially refined subject to a free-variable DFIX O—H restraint with a common Uiso free variable. In the final cycles, the water H atoms were then not adjusted (AFIX 1) from the O—H distance (1.01 Å) so obtained. The analysis does not allow the absolute configuration of (I) to be determined, but this was known from the synthesis.
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: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.
C25H31NO2·H2O | F(000) = 428 |
Mr = 395.52 | Dx = 1.251 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.5418 Å |
a = 6.5376 (3) Å | Cell parameters from 25 reflections |
b = 11.8766 (10) Å | θ = 20–30° |
c = 13.5312 (15) Å | µ = 0.64 mm−1 |
β = 91.197 (12)° | T = 293 K |
V = 1050.39 (15) Å3 | Rectangular, colourless |
Z = 2 | 0.3 × 0.2 × 0.1 mm |
Enraf-Nonius CAD-4 diffractometer | 1888 reflections with I > 2s(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 67.9°, θmin = 3.3° |
ω–2θ scans | h = 0→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.800, Tmax = 0.988 | l = −16→16 |
2187 measured reflections | 2 standard reflections every 120 min |
2003 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0724P)2 + 0.1862P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
2003 reflections | Δρmax = 0.27 e Å−3 |
267 parameters | Δρmin = −0.22 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (10) |
C25H31NO2·H2O | V = 1050.39 (15) Å3 |
Mr = 395.52 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 6.5376 (3) Å | µ = 0.64 mm−1 |
b = 11.8766 (10) Å | T = 293 K |
c = 13.5312 (15) Å | 0.3 × 0.2 × 0.1 mm |
β = 91.197 (12)° |
Enraf-Nonius CAD-4 diffractometer | 1888 reflections with I > 2s(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.023 |
Tmin = 0.800, Tmax = 0.988 | 2 standard reflections every 120 min |
2187 measured reflections | intensity decay: none |
2003 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 3 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.27 e Å−3 |
2003 reflections | Δρmin = −0.22 e Å−3 |
267 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 | ||
O3 | −0.2397 (4) | 0.7248 (3) | −0.28994 (15) | 0.0603 (7) | |
H3 | −0.1564 | 0.7538 | −0.3265 | 0.090* | |
O17 | 0.3275 (3) | 0.6155 (2) | 0.46889 (15) | 0.0523 (6) | |
N26 | 0.9804 (4) | 0.8130 (2) | 0.54939 (17) | 0.0432 (6) | |
C1 | −0.1706 (4) | 0.6331 (3) | −0.02775 (19) | 0.0351 (6) | |
H1A | −0.2176 | 0.5653 | 0.0047 | 0.042* | |
H1B | −0.2349 | 0.6968 | 0.0040 | 0.042* | |
C2 | −0.2407 (4) | 0.6297 (3) | −0.1358 (2) | 0.0411 (7) | |
H2A | −0.1876 | 0.5624 | −0.1668 | 0.049* | |
H2B | −0.3889 | 0.6265 | −0.1397 | 0.049* | |
C3 | −0.1671 (4) | 0.7322 (3) | −0.19021 (19) | 0.0387 (6) | |
H3A | −0.2273 | 0.7991 | −0.1600 | 0.046* | |
C4 | 0.0656 (4) | 0.7417 (3) | −0.18152 (19) | 0.0380 (6) | |
H4A | 0.1272 | 0.6805 | −0.2178 | 0.046* | |
H4B | 0.1086 | 0.8119 | −0.2113 | 0.046* | |
C5 | 0.1415 (4) | 0.7380 (2) | −0.07507 (18) | 0.0299 (5) | |
C6 | 0.2728 (4) | 0.8155 (2) | −0.04007 (19) | 0.0331 (6) | |
H6 | 0.3135 | 0.8718 | −0.0832 | 0.040* | |
C7 | 0.3592 (4) | 0.8183 (2) | 0.06345 (19) | 0.0349 (6) | |
H7A | 0.2949 | 0.8790 | 0.0993 | 0.042* | |
H7B | 0.5045 | 0.8342 | 0.0612 | 0.042* | |
C8 | 0.3279 (4) | 0.7087 (2) | 0.11905 (18) | 0.0276 (5) | |
H8 | 0.4249 | 0.6524 | 0.0953 | 0.033* | |
C9 | 0.1071 (4) | 0.6658 (2) | 0.09947 (18) | 0.0279 (5) | |
H9 | 0.0165 | 0.7280 | 0.1173 | 0.033* | |
C10 | 0.0638 (4) | 0.6425 (2) | −0.01221 (18) | 0.0286 (5) | |
C11 | 0.0480 (4) | 0.5661 (3) | 0.16598 (19) | 0.0357 (6) | |
H11A | −0.0978 | 0.5526 | 0.1580 | 0.043* | |
H11B | 0.1184 | 0.4992 | 0.1434 | 0.043* | |
C12 | 0.0980 (4) | 0.5828 (3) | 0.27624 (19) | 0.0367 (6) | |
H12A | 0.0116 | 0.6413 | 0.3028 | 0.044* | |
H12B | 0.0723 | 0.5136 | 0.3120 | 0.044* | |
C13 | 0.3226 (4) | 0.6160 (2) | 0.28874 (18) | 0.0309 (6) | |
C14 | 0.3600 (4) | 0.7239 (2) | 0.23019 (18) | 0.0289 (5) | |
H14 | 0.2547 | 0.7772 | 0.2508 | 0.035* | |
C15 | 0.5654 (4) | 0.7707 (3) | 0.27197 (18) | 0.0346 (6) | |
H15A | 0.6808 | 0.7380 | 0.2384 | 0.042* | |
H15B | 0.5712 | 0.8521 | 0.2660 | 0.042* | |
C16 | 0.5625 (4) | 0.7348 (3) | 0.37945 (19) | 0.0354 (6) | |
C17 | 0.3912 (4) | 0.6510 (3) | 0.39193 (19) | 0.0363 (6) | |
C18 | 0.4657 (4) | 0.5173 (3) | 0.2622 (2) | 0.0411 (7) | |
H18A | 0.6052 | 0.5385 | 0.2758 | 0.062* | |
H18B | 0.4489 | 0.4996 | 0.1933 | 0.062* | |
H18C | 0.4320 | 0.4525 | 0.3010 | 0.062* | |
C19 | 0.1667 (5) | 0.5319 (3) | −0.0459 (2) | 0.0409 (7) | |
H19A | 0.1563 | 0.5259 | −0.1166 | 0.061* | |
H19B | 0.0994 | 0.4688 | −0.0164 | 0.061* | |
H19C | 0.3083 | 0.5323 | −0.0256 | 0.061* | |
C20 | 0.6861 (4) | 0.7582 (3) | 0.4573 (2) | 0.0370 (6) | |
H20 | 0.6468 | 0.7262 | 0.5167 | 0.044* | |
C21 | 0.8725 (4) | 0.8259 (3) | 0.46345 (19) | 0.0361 (6) | |
C22 | 0.9409 (5) | 0.8958 (3) | 0.3895 (2) | 0.0481 (8) | |
H22 | 0.8645 | 0.9042 | 0.3312 | 0.058* | |
C23 | 1.1231 (5) | 0.9531 (3) | 0.4025 (3) | 0.0550 (9) | |
H23 | 1.1685 | 1.0024 | 0.3543 | 0.066* | |
C24 | 1.2368 (5) | 0.9358 (3) | 0.4881 (3) | 0.0520 (8) | |
H24 | 1.3632 | 0.9704 | 0.4977 | 0.062* | |
C25 | 1.1584 (5) | 0.8666 (3) | 0.5585 (2) | 0.0514 (9) | |
H25 | 1.2345 | 0.8562 | 0.6166 | 0.062* | |
O27 | −0.5891 (4) | 0.5797 (3) | −0.32162 (17) | 0.0683 (8) | |
H27A | −0.5206 | 0.6560 | −0.3215 | 0.097* | |
H27B | −0.6254 | 0.5933 | −0.3937 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0610 (14) | 0.0865 (18) | 0.0325 (11) | −0.0300 (14) | −0.0179 (9) | 0.0169 (12) |
O17 | 0.0450 (12) | 0.0773 (17) | 0.0343 (11) | −0.0175 (11) | −0.0037 (8) | 0.0114 (11) |
N26 | 0.0373 (12) | 0.0582 (16) | 0.0338 (11) | −0.0091 (12) | −0.0068 (9) | −0.0016 (12) |
C1 | 0.0306 (13) | 0.0449 (16) | 0.0295 (13) | −0.0093 (11) | −0.0031 (10) | 0.0048 (12) |
C2 | 0.0380 (15) | 0.0509 (17) | 0.0339 (14) | −0.0121 (13) | −0.0075 (11) | 0.0051 (13) |
C3 | 0.0421 (15) | 0.0436 (15) | 0.0301 (13) | −0.0036 (13) | −0.0094 (11) | 0.0033 (12) |
C4 | 0.0423 (14) | 0.0438 (15) | 0.0277 (12) | −0.0097 (13) | −0.0014 (10) | 0.0040 (12) |
C5 | 0.0288 (11) | 0.0312 (13) | 0.0296 (12) | 0.0009 (10) | 0.0003 (9) | 0.0006 (11) |
C6 | 0.0360 (13) | 0.0306 (13) | 0.0327 (13) | −0.0028 (11) | −0.0012 (10) | 0.0054 (11) |
C7 | 0.0347 (13) | 0.0334 (13) | 0.0365 (13) | −0.0046 (11) | −0.0048 (10) | 0.0032 (12) |
C8 | 0.0224 (11) | 0.0298 (12) | 0.0307 (12) | −0.0007 (10) | −0.0013 (9) | 0.0007 (10) |
C9 | 0.0262 (12) | 0.0303 (13) | 0.0270 (12) | −0.0017 (10) | −0.0023 (9) | 0.0005 (10) |
C10 | 0.0278 (13) | 0.0311 (13) | 0.0268 (12) | −0.0006 (10) | −0.0011 (9) | −0.0011 (10) |
C11 | 0.0309 (13) | 0.0430 (16) | 0.0330 (13) | −0.0092 (11) | −0.0037 (10) | 0.0058 (12) |
C12 | 0.0303 (13) | 0.0495 (16) | 0.0303 (12) | −0.0083 (12) | −0.0024 (10) | 0.0077 (12) |
C13 | 0.0251 (13) | 0.0373 (15) | 0.0301 (12) | −0.0008 (10) | −0.0018 (9) | 0.0040 (11) |
C14 | 0.0238 (11) | 0.0316 (13) | 0.0311 (12) | 0.0000 (10) | −0.0029 (9) | −0.0004 (11) |
C15 | 0.0293 (13) | 0.0413 (14) | 0.0329 (13) | −0.0065 (11) | −0.0084 (10) | 0.0037 (11) |
C16 | 0.0294 (12) | 0.0426 (15) | 0.0339 (13) | −0.0015 (12) | −0.0048 (10) | 0.0015 (12) |
C17 | 0.0298 (13) | 0.0454 (16) | 0.0333 (14) | −0.0004 (12) | −0.0048 (10) | 0.0041 (12) |
C18 | 0.0385 (15) | 0.0373 (15) | 0.0474 (16) | 0.0039 (12) | −0.0041 (12) | 0.0063 (12) |
C19 | 0.0481 (16) | 0.0347 (15) | 0.0400 (15) | 0.0058 (13) | 0.0011 (12) | −0.0051 (12) |
C20 | 0.0324 (13) | 0.0474 (16) | 0.0311 (12) | −0.0031 (12) | −0.0034 (10) | 0.0003 (12) |
C21 | 0.0331 (13) | 0.0438 (15) | 0.0312 (13) | −0.0005 (12) | −0.0058 (10) | −0.0053 (12) |
C22 | 0.0483 (17) | 0.0561 (19) | 0.0393 (15) | −0.0109 (15) | −0.0101 (13) | 0.0037 (14) |
C23 | 0.056 (2) | 0.056 (2) | 0.0530 (18) | −0.0196 (17) | −0.0007 (15) | 0.0053 (16) |
C24 | 0.0416 (17) | 0.063 (2) | 0.0511 (18) | −0.0140 (15) | −0.0045 (14) | −0.0101 (16) |
C25 | 0.0421 (16) | 0.071 (2) | 0.0408 (16) | −0.0119 (16) | −0.0121 (12) | −0.0073 (17) |
O27 | 0.0637 (16) | 0.095 (2) | 0.0463 (13) | −0.0181 (16) | −0.0069 (11) | 0.0013 (14) |
O3—C3 | 1.424 (3) | C11—H11B | 0.97 |
O3—H3 | 0.82 | C12—C13 | 1.526 (3) |
O17—C17 | 1.206 (3) | C12—H12A | 0.97 |
N26—C25 | 1.330 (4) | C12—H12B | 0.97 |
N26—C21 | 1.356 (3) | C13—C17 | 1.516 (3) |
C1—C2 | 1.523 (3) | C13—C14 | 1.529 (4) |
C1—C10 | 1.546 (3) | C13—C18 | 1.547 (4) |
C1—H1A | 0.97 | C14—C15 | 1.550 (3) |
C1—H1B | 0.97 | C14—H14 | 0.98 |
C2—C3 | 1.507 (4) | C15—C16 | 1.516 (4) |
C2—H2A | 0.97 | C15—H15A | 0.97 |
C2—H2B | 0.97 | C15—H15B | 0.97 |
C3—C4 | 1.528 (4) | C16—C20 | 1.343 (4) |
C3—H3A | 0.98 | C16—C17 | 1.510 (4) |
C4—C5 | 1.514 (3) | C18—H18A | 0.96 |
C4—H4A | 0.97 | C18—H18B | 0.96 |
C4—H4B | 0.97 | C18—H18C | 0.96 |
C5—C6 | 1.338 (4) | C19—H19A | 0.96 |
C5—C10 | 1.512 (4) | C19—H19B | 0.96 |
C6—C7 | 1.500 (3) | C19—H19C | 0.96 |
C6—H6 | 0.93 | C20—C21 | 1.461 (4) |
C7—C8 | 1.519 (4) | C20—H20 | 0.93 |
C7—H7A | 0.97 | C21—C22 | 1.382 (4) |
C7—H7B | 0.97 | C22—C23 | 1.379 (5) |
C8—C14 | 1.525 (3) | C22—H22 | 0.93 |
C8—C9 | 1.549 (3) | C23—C24 | 1.379 (5) |
C8—H8 | 0.98 | C23—H23 | 0.93 |
C9—C11 | 1.542 (4) | C24—C25 | 1.366 (5) |
C9—C10 | 1.556 (3) | C24—H24 | 0.93 |
C9—H9 | 0.98 | C25—H25 | 0.93 |
C10—C19 | 1.549 (4) | O27—H27A | 1.01 |
C11—C12 | 1.534 (3) | O27—H27B | 1.01 |
C11—H11A | 0.97 | ||
C3—O3—H3 | 109.5 | C13—C12—C11 | 109.0 (2) |
C25—N26—C21 | 117.6 (3) | C13—C12—H12A | 109.9 |
C2—C1—C10 | 114.2 (2) | C11—C12—H12A | 109.9 |
C2—C1—H1A | 108.7 | C13—C12—H12B | 109.9 |
C10—C1—H1A | 108.7 | C11—C12—H12B | 109.9 |
C2—C1—H1B | 108.7 | H12A—C12—H12B | 108.3 |
C10—C1—H1B | 108.7 | C17—C13—C12 | 116.0 (2) |
H1A—C1—H1B | 107.6 | C17—C13—C14 | 101.5 (2) |
C3—C2—C1 | 110.8 (2) | C12—C13—C14 | 108.9 (2) |
C3—C2—H2A | 109.5 | C17—C13—C18 | 104.7 (2) |
C1—C2—H2A | 109.5 | C12—C13—C18 | 111.3 (2) |
C3—C2—H2B | 109.5 | C14—C13—C18 | 114.2 (2) |
C1—C2—H2B | 109.5 | C8—C14—C13 | 113.1 (2) |
H2A—C2—H2B | 108.1 | C8—C14—C15 | 120.2 (2) |
O3—C3—C2 | 108.1 (2) | C13—C14—C15 | 105.0 (2) |
O3—C3—C4 | 112.9 (2) | C8—C14—H14 | 105.9 |
C2—C3—C4 | 110.5 (2) | C13—C14—H14 | 105.9 |
O3—C3—H3A | 108.4 | C15—C14—H14 | 105.9 |
C2—C3—H3A | 108.4 | C16—C15—C14 | 102.7 (2) |
C4—C3—H3A | 108.4 | C16—C15—H15A | 111.2 |
C5—C4—C3 | 112.1 (2) | C14—C15—H15A | 111.2 |
C5—C4—H4A | 109.2 | C16—C15—H15B | 111.2 |
C3—C4—H4A | 109.2 | C14—C15—H15B | 111.2 |
C5—C4—H4B | 109.2 | H15A—C15—H15B | 109.1 |
C3—C4—H4B | 109.2 | C20—C16—C17 | 118.9 (2) |
H4A—C4—H4B | 107.9 | C20—C16—C15 | 132.4 (3) |
C6—C5—C10 | 122.5 (2) | C17—C16—C15 | 108.5 (2) |
C6—C5—C4 | 120.8 (2) | O17—C17—C16 | 126.7 (2) |
C10—C5—C4 | 116.7 (2) | O17—C17—C13 | 126.8 (3) |
C5—C6—C7 | 124.9 (2) | C16—C17—C13 | 106.5 (2) |
C5—C6—H6 | 117.6 | C13—C18—H18A | 109.5 |
C7—C6—H6 | 117.6 | C13—C18—H18B | 109.5 |
C6—C7—C8 | 113.1 (2) | H18A—C18—H18B | 109.5 |
C6—C7—H7A | 109.0 | C13—C18—H18C | 109.5 |
C8—C7—H7A | 109.0 | H18A—C18—H18C | 109.5 |
C6—C7—H7B | 109.0 | H18B—C18—H18C | 109.5 |
C8—C7—H7B | 109.0 | C10—C19—H19A | 109.5 |
H7A—C7—H7B | 107.8 | C10—C19—H19B | 109.5 |
C7—C8—C14 | 111.7 (2) | H19A—C19—H19B | 109.5 |
C7—C8—C9 | 109.4 (2) | C10—C19—H19C | 109.5 |
C14—C8—C9 | 108.44 (18) | H19A—C19—H19C | 109.5 |
C7—C8—H8 | 109.1 | H19B—C19—H19C | 109.5 |
C14—C8—H8 | 109.1 | C16—C20—C21 | 130.2 (3) |
C9—C8—H8 | 109.1 | C16—C20—H20 | 114.9 |
C11—C9—C8 | 113.38 (19) | C21—C20—H20 | 114.9 |
C11—C9—C10 | 112.8 (2) | N26—C21—C22 | 121.3 (3) |
C8—C9—C10 | 111.99 (19) | N26—C21—C20 | 113.9 (3) |
C11—C9—H9 | 106.0 | C22—C21—C20 | 124.9 (2) |
C8—C9—H9 | 106.0 | C23—C22—C21 | 119.7 (3) |
C10—C9—H9 | 106.0 | C23—C22—H22 | 120.1 |
C5—C10—C1 | 108.8 (2) | C21—C22—H22 | 120.1 |
C5—C10—C19 | 108.5 (2) | C24—C23—C22 | 118.8 (3) |
C1—C10—C19 | 109.5 (2) | C24—C23—H23 | 120.6 |
C5—C10—C9 | 110.9 (2) | C22—C23—H23 | 120.6 |
C1—C10—C9 | 107.72 (18) | C25—C24—C23 | 118.1 (3) |
C19—C10—C9 | 111.4 (2) | C25—C24—H24 | 120.9 |
C12—C11—C9 | 114.7 (2) | C23—C24—H24 | 120.9 |
C12—C11—H11A | 108.6 | N26—C25—C24 | 124.3 (3) |
C9—C11—H11A | 108.6 | N26—C25—H25 | 117.8 |
C12—C11—H11B | 108.6 | C24—C25—H25 | 117.8 |
C9—C11—H11B | 108.6 | H27A—O27—H27B | 87.3 |
H11A—C11—H11B | 107.6 | ||
C10—C1—C2—C3 | −57.1 (3) | C7—C8—C14—C13 | 178.1 (2) |
C1—C2—C3—O3 | −179.2 (2) | C9—C8—C14—C13 | 57.4 (3) |
C1—C2—C3—C4 | 56.8 (3) | C7—C8—C14—C15 | −57.0 (3) |
O3—C3—C4—C5 | −174.4 (3) | C9—C8—C14—C15 | −177.6 (2) |
C2—C3—C4—C5 | −53.3 (3) | C17—C13—C14—C8 | 172.93 (19) |
C3—C4—C5—C6 | −130.4 (3) | C12—C13—C14—C8 | −64.2 (3) |
C3—C4—C5—C10 | 50.4 (3) | C18—C13—C14—C8 | 60.9 (3) |
C10—C5—C6—C7 | 0.1 (4) | C17—C13—C14—C15 | 40.1 (3) |
C4—C5—C6—C7 | −179.1 (3) | C12—C13—C14—C15 | 163.0 (2) |
C5—C6—C7—C8 | 14.8 (4) | C18—C13—C14—C15 | −71.9 (3) |
C6—C7—C8—C14 | −163.7 (2) | C8—C14—C15—C16 | −161.1 (2) |
C6—C7—C8—C9 | −43.6 (3) | C13—C14—C15—C16 | −32.4 (3) |
C7—C8—C9—C11 | −170.3 (2) | C14—C15—C16—C20 | −172.7 (3) |
C14—C8—C9—C11 | −48.3 (3) | C14—C15—C16—C17 | 12.0 (3) |
C7—C8—C9—C10 | 60.6 (3) | C20—C16—C17—O17 | 13.9 (5) |
C14—C8—C9—C10 | −177.3 (2) | C15—C16—C17—O17 | −170.0 (3) |
C6—C5—C10—C1 | 133.7 (3) | C20—C16—C17—C13 | −163.2 (3) |
C4—C5—C10—C1 | −47.1 (3) | C15—C16—C17—C13 | 12.8 (3) |
C6—C5—C10—C19 | −107.3 (3) | C12—C13—C17—O17 | 32.7 (4) |
C4—C5—C10—C19 | 72.0 (3) | C14—C13—C17—O17 | 150.5 (3) |
C6—C5—C10—C9 | 15.4 (3) | C18—C13—C17—O17 | −90.4 (3) |
C4—C5—C10—C9 | −165.4 (2) | C12—C13—C17—C16 | −150.1 (2) |
C2—C1—C10—C5 | 50.1 (3) | C14—C13—C17—C16 | −32.3 (3) |
C2—C1—C10—C19 | −68.3 (3) | C18—C13—C17—C16 | 86.8 (3) |
C2—C1—C10—C9 | 170.4 (2) | C17—C16—C20—C21 | 173.2 (3) |
C11—C9—C10—C5 | −174.9 (2) | C15—C16—C20—C21 | −1.7 (6) |
C8—C9—C10—C5 | −45.5 (3) | C25—N26—C21—C22 | −2.5 (5) |
C11—C9—C10—C1 | 66.2 (3) | C25—N26—C21—C20 | 176.1 (3) |
C8—C9—C10—C1 | −164.4 (2) | C16—C20—C21—N26 | −167.4 (3) |
C11—C9—C10—C19 | −53.9 (3) | C16—C20—C21—C22 | 11.2 (5) |
C8—C9—C10—C19 | 75.5 (3) | N26—C21—C22—C23 | 0.5 (5) |
C8—C9—C11—C12 | 48.4 (3) | C20—C21—C22—C23 | −177.9 (3) |
C10—C9—C11—C12 | 177.0 (2) | C21—C22—C23—C24 | 2.3 (6) |
C9—C11—C12—C13 | −52.6 (3) | C22—C23—C24—C25 | −3.0 (6) |
C11—C12—C13—C17 | 172.1 (2) | C21—N26—C25—C24 | 1.7 (5) |
C11—C12—C13—C14 | 58.5 (3) | C23—C24—C25—N26 | 1.0 (6) |
C11—C12—C13—C18 | −68.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N26i | 0.82 | 2.04 | 2.833 (3) | 162 |
O27—H27A···O3 | 1.01 | 2.05 | 2.886 (3) | 139 |
O27—H27B···O17i | 1.01 | 1.90 | 2.907 (3) | 176 |
Symmetry code: (i) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C25H31NO2·H2O |
Mr | 395.52 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.5376 (3), 11.8766 (10), 13.5312 (15) |
β (°) | 91.197 (12) |
V (Å3) | 1050.39 (15) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.3 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.800, 0.988 |
No. of measured, independent and observed [I > 2s(I)] reflections | 2187, 2003, 1888 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.117, 1.14 |
No. of reflections | 2003 |
No. of parameters | 267 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.
O17—C17 | 1.206 (3) | C10—C19 | 1.549 (4) |
C1—C2 | 1.523 (3) | C13—C18 | 1.547 (4) |
C2—C1—C10 | 114.2 (2) | C17—C13—C18 | 104.7 (2) |
O3—C3—C2 | 108.1 (2) | O17—C17—C13 | 126.8 (3) |
C5—C10—C19 | 108.5 (2) | ||
C10—C1—C2—C3 | −57.1 (3) | C7—C8—C9—C10 | 60.6 (3) |
C10—C5—C6—C7 | 0.1 (4) | C6—C5—C10—C9 | 15.4 (3) |
C5—C6—C7—C8 | 14.8 (4) | C8—C9—C10—C5 | −45.5 (3) |
C6—C7—C8—C9 | −43.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N26i | 0.82 | 2.04 | 2.833 (3) | 162 |
O27—H27A···O3 | 1.01 | 2.05 | 2.886 (3) | 139 |
O27—H27B···O17i | 1.01 | 1.90 | 2.907 (3) | 176 |
Symmetry code: (i) x−1, y, z−1. |
The structure determination of the title compound, (I), was undertaken to investigate the conformation of the fused-ring system and the configuration of the 16-(2-pyridylmethylene) functionaly with respect to the carbonyl group at position 17.
Compound (I), an epiandrostene derivative, is a steroid in which rings A, B and C are essentially rigid, whereas ring D has a flexible conformation with respect to the side chain. The absolute configuration of (I) is based on the known configuration of the starting material, namely epiandrosterone (Weeks et al., 1971). The torsion angles show that rings A and C adopt chair conformations. The short C2—C3 bond distance of 1.507 (4) Å in (I) is in agreement with other related steroids (Paixao et al., 1998). Ring B has an 8β,9α-half-chair conformation. The C5—C6 distance of 1.338 (4) Å confirms the localization of a double bond at this position. Atoms C8 and C9 are displaced to opposite sides by 0.359 (5) and 0.389 (5) Å, respectively, from the mean C10/C5/C6/C7 plane (Cox et al., 1981). Ring D has a 13,14-half-chair conformation. The five torsion angles of ring D [C13–C14–C15–C16 - 32.4 (3), C14–C15–C16–C17 12.0 (3), C15–C16–C17–C13 12.8 (3), C16–C17–C13–C14 - 32.3 (3) and C17–C13–C14–C15 40.1 (3)°] are comparable with the reported values of -37.6 (2), 16.3 (2), 11.3 (2), -33.7 (2) and 43.7 (2)°, respectively (Paixao et al., 1998). The C17–C16–C20–C21 torsion angle of 173.2 (3)° indicates that the 2-pyridyl ring has an E configuration with respect to the carbonyl group at position 17; the C20 H atom is Z with respect to this carbonyl group. The O17 atom is equatorially substituted at C17, and O3 is equatorially substituted at C3. The dihedral angle between the pyridine ring and the androstene moiety is 8.71 (12)°. The geometry of the rings is trans at the B/C and C/D ring junctions.
The structure of (I) is stabilized by a network of hydrogen bonds involving the hydroxyl O, carbonyl O and pyridyl N atoms of the steroid moiety, and the O atom of the water molecule (Table 2). The hydroxyl O3 atom at C3 takes part in two intermolecular hydrogen bonds, one as a donor towards the pyridyl nitrogen (N26) and the other as an acceptor from the water molecule (O27). In addition to this, the water molecule also has another intermolecular hydrogen bond involving the carbonyl oxygen (O17). In this way an infinite one-dimensional chain of molecules is assembled (Fig. 2).