Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013434/de1189sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013434/de1189Isup2.hkl |
CCDC reference: 197332
The title compound was prepared by dissolving 16-(2-pyridylmethylene)-3β-pyrrolidinoandrost-5-en-17β-ol (500 mg, 1.15 mmol) in dried dichloromethane (50 ml) and adding allylbromide (1 ml, 7.04 mol). The reaction mixture was stirred for a few minutes and kept at room temperature overnight. The solid residues were filtered and washed with dichloromethane to afford crystals of (I) (yield: 0.45 g, 68.36%; m.p. 517–521 K).
The structure was solved with DIRDIF99 (Beurskens et al., 1999) using the TRACOR option, with the Br atom at the origin. All H atoms, except the hydroxyl H atom and the water H atom, were treated as riding, with C—H distances in the range 0.93–0.98 Å and Uiso(H) = 1.5Ueq (C) for methyl H atoms and 1.2Ueq(C) for all others. The hydroxyl H atom was located from a difference Fourier map and refined using the DFIX option in SHELXL97 (Sheldrick, 1997), with H27—O27 0.81 (2) Å. It was included in the structure factor calculation with Uiso(H27) = 1.1Ueq(O27). At this stage, the maximum residual electron density of 2.87 e Å-3 indicated the presence of a possible atom site in a special position with half occupancy. This peak was found near Br, at a distance of 3.404 Å. It was assumed to be an O atom of the water molecule and was refined. One of the H atoms of the water molecule was located from a difference Fourier map and, using the DFIX option in SHELXL97, the coordinates of atom H1W were refined, with O1W—H1W restrained to 0.88 (2) Å, and H1W—H1W(symmetry equivalent) restrained to 1.44 (1) Å. It was included in the structure factor calculation with Uiso(H1W) = 1.1Ueq(O1W).
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: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.
C32H45BrN2O·0.5H2O | F(000) = 1196 |
Mr = 562.61 | Dx = 1.277 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 25 reflections |
a = 21.054 (4) Å | θ = 10–15° |
b = 9.3083 (18) Å | µ = 1.43 mm−1 |
c = 15.551 (4) Å | T = 293 K |
β = 106.15 (2)° | Plate, white |
V = 2927.4 (11) Å3 | 0.20 × 0.17 × 0.17 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | 2100 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω/2θ scans | h = 0→24 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.763, Tmax = 0.793 | l = −18→17 |
2835 measured reflections | 2 standard reflections every 120 min |
2751 independent reflections | intensity decay: none |
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)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0413P)2 + 2.1207P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2751 reflections | Δρmax = 0.29 e Å−3 |
336 parameters | Δρmin = −0.23 e Å−3 |
4 restraints | Absolute structure: Flack (1983) How many Friedels? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.002 (12) |
C32H45BrN2O·0.5H2O | V = 2927.4 (11) Å3 |
Mr = 562.61 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 21.054 (4) Å | µ = 1.43 mm−1 |
b = 9.3083 (18) Å | T = 293 K |
c = 15.551 (4) Å | 0.20 × 0.17 × 0.17 mm |
β = 106.15 (2)° |
Enraf-Nonius CAD-4 diffractometer | 2100 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.763, Tmax = 0.793 | 2 standard reflections every 120 min |
2835 measured reflections | intensity decay: none |
2751 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.089 | Δρmax = 0.29 e Å−3 |
S = 1.08 | Δρmin = −0.23 e Å−3 |
2751 reflections | Absolute structure: Flack (1983) How many Friedels? |
336 parameters | Absolute structure parameter: −0.002 (12) |
4 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 | 0.0921 (2) | 0.2900 (6) | 0.6058 (3) | 0.0429 (11) | |
H1A | 0.0506 | 0.2931 | 0.5590 | 0.051* | |
H1B | 0.1090 | 0.1926 | 0.6084 | 0.051* | |
C2 | 0.0791 (2) | 0.3259 (6) | 0.6955 (3) | 0.0473 (12) | |
H2A | 0.0616 | 0.4227 | 0.6939 | 0.057* | |
H2B | 0.0468 | 0.2598 | 0.7070 | 0.057* | |
C3 | 0.1437 (2) | 0.3138 (5) | 0.7689 (3) | 0.0396 (11) | |
H3 | 0.1620 | 0.2182 | 0.7643 | 0.048* | |
C4 | 0.1926 (2) | 0.4242 (5) | 0.7512 (3) | 0.0428 (11) | |
H4A | 0.1755 | 0.5202 | 0.7542 | 0.051* | |
H4B | 0.2344 | 0.4160 | 0.7971 | 0.051* | |
C5 | 0.2036 (2) | 0.4006 (5) | 0.6603 (3) | 0.0364 (10) | |
C6 | 0.2648 (2) | 0.3911 (5) | 0.6524 (3) | 0.0402 (11) | |
H6 | 0.2996 | 0.3947 | 0.7045 | 0.048* | |
C7 | 0.2816 (2) | 0.3752 (6) | 0.5656 (3) | 0.0430 (12) | |
H7A | 0.2990 | 0.2794 | 0.5625 | 0.052* | |
H7B | 0.3161 | 0.4433 | 0.5641 | 0.052* | |
C8 | 0.22291 (19) | 0.3993 (5) | 0.4840 (3) | 0.0351 (10) | |
H8 | 0.2149 | 0.5027 | 0.4755 | 0.042* | |
C9 | 0.16032 (19) | 0.3267 (5) | 0.4986 (2) | 0.0371 (10) | |
H9 | 0.1725 | 0.2265 | 0.5143 | 0.045* | |
C10 | 0.1417 (2) | 0.3925 (5) | 0.5803 (3) | 0.0374 (11) | |
C11 | 0.1027 (2) | 0.3219 (7) | 0.4127 (3) | 0.0494 (12) | |
H11A | 0.0682 | 0.2607 | 0.4227 | 0.059* | |
H11B | 0.0846 | 0.4179 | 0.4000 | 0.059* | |
C12 | 0.1221 (2) | 0.2667 (6) | 0.3309 (3) | 0.0474 (12) | |
H12A | 0.1343 | 0.1661 | 0.3395 | 0.057* | |
H12B | 0.0844 | 0.2741 | 0.2784 | 0.057* | |
C13 | 0.1795 (2) | 0.3512 (5) | 0.3154 (3) | 0.0382 (10) | |
C14 | 0.23666 (19) | 0.3374 (5) | 0.4013 (3) | 0.0356 (10) | |
H14 | 0.2432 | 0.2341 | 0.4124 | 0.043* | |
C15 | 0.2974 (2) | 0.3899 (6) | 0.3737 (3) | 0.0439 (11) | |
H15A | 0.3012 | 0.4937 | 0.3778 | 0.053* | |
H15B | 0.3377 | 0.3471 | 0.4110 | 0.053* | |
C16 | 0.2833 (2) | 0.3397 (5) | 0.2775 (3) | 0.0442 (11) | |
C17 | 0.2121 (2) | 0.2845 (5) | 0.2485 (3) | 0.0449 (11) | |
H17 | 0.2135 | 0.1803 | 0.2578 | 0.054* | |
C18 | 0.1600 (2) | 0.5075 (8) | 0.2884 (3) | 0.0514 (11) | |
H18A | 0.1975 | 0.5576 | 0.2793 | 0.077* | |
H18B | 0.1459 | 0.5538 | 0.3350 | 0.077* | |
H18C | 0.1246 | 0.5086 | 0.2339 | 0.077* | |
C19 | 0.1117 (2) | 0.5415 (6) | 0.5600 (3) | 0.0529 (15) | |
H19A | 0.0728 | 0.5362 | 0.5101 | 0.079* | |
H19B | 0.1432 | 0.6048 | 0.5456 | 0.079* | |
H19C | 0.1001 | 0.5776 | 0.6114 | 0.079* | |
C20 | 0.3233 (2) | 0.3344 (6) | 0.2254 (3) | 0.0478 (12) | |
H20 | 0.3038 | 0.3063 | 0.1666 | 0.057* | |
C21 | 0.3940 (3) | 0.3666 (5) | 0.2477 (3) | 0.0523 (13) | |
C22 | 0.4291 (3) | 0.3459 (7) | 0.1857 (4) | 0.0692 (16) | |
H22 | 0.4070 | 0.3171 | 0.1279 | 0.083* | |
C23 | 0.4967 (3) | 0.3676 (8) | 0.2089 (6) | 0.091 (2) | |
H23 | 0.5207 | 0.3524 | 0.1677 | 0.109* | |
C24 | 0.5270 (3) | 0.4116 (9) | 0.2930 (6) | 0.095 (2) | |
H24 | 0.5725 | 0.4262 | 0.3111 | 0.114* | |
C25 | 0.4900 (3) | 0.4344 (9) | 0.3514 (5) | 0.095 (2) | |
H25 | 0.5116 | 0.4650 | 0.4090 | 0.114* | |
N26 | 0.4249 (2) | 0.4155 (6) | 0.3305 (3) | 0.0713 (14) | |
O27 | 0.17983 (18) | 0.3102 (4) | 0.1567 (2) | 0.0548 (9) | |
H27 | 0.167 (3) | 0.231 (3) | 0.138 (3) | 0.060* | |
N28 | 0.13579 (18) | 0.3287 (5) | 0.8641 (2) | 0.0409 (9) | |
C29 | 0.0840 (3) | 0.2230 (7) | 0.8782 (3) | 0.0566 (14) | |
H29A | 0.0678 | 0.1623 | 0.8260 | 0.068* | |
H29B | 0.1025 | 0.1625 | 0.9299 | 0.068* | |
C30 | 0.0292 (3) | 0.3158 (9) | 0.8929 (4) | 0.082 (2) | |
H30A | −0.0030 | 0.3379 | 0.8365 | 0.098* | |
H30B | 0.0070 | 0.2683 | 0.9320 | 0.098* | |
C31 | 0.0632 (3) | 0.4480 (8) | 0.9354 (4) | 0.084 (2) | |
H31A | 0.0858 | 0.4320 | 0.9981 | 0.101* | |
H31B | 0.0322 | 0.5268 | 0.9304 | 0.101* | |
C32 | 0.1118 (2) | 0.4776 (7) | 0.8822 (3) | 0.0526 (14) | |
H32A | 0.1483 | 0.5360 | 0.9164 | 0.063* | |
H32B | 0.0905 | 0.5266 | 0.8266 | 0.063* | |
C33 | 0.2020 (2) | 0.3001 (6) | 0.9335 (3) | 0.0471 (12) | |
H33A | 0.2333 | 0.3736 | 0.9281 | 0.057* | |
H33B | 0.1960 | 0.3073 | 0.9929 | 0.057* | |
C34 | 0.2299 (3) | 0.1567 (6) | 0.9232 (3) | 0.0553 (13) | |
H34 | 0.2053 | 0.0755 | 0.9278 | 0.066* | |
C35 | 0.2872 (3) | 0.1390 (7) | 0.9080 (3) | 0.0629 (15) | |
H35A | 0.3127 | 0.2185 | 0.9031 | 0.076* | |
H35B | 0.3025 | 0.0469 | 0.9020 | 0.076* | |
Br | 0.12664 (3) | −0.00156 (7) | 0.08584 (3) | 0.0677 (2) | |
O1W | 0.5000 | 0.2660 (8) | 0.0000 | 0.104 (2) | |
H1W | 0.5354 (9) | 0.319 (4) | 0.021 (5) | 0.115* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.032 (2) | 0.063 (3) | 0.033 (2) | −0.009 (2) | 0.0085 (18) | 0.003 (2) |
C2 | 0.041 (3) | 0.064 (3) | 0.038 (2) | −0.007 (3) | 0.014 (2) | 0.005 (2) |
C3 | 0.046 (2) | 0.046 (3) | 0.029 (2) | −0.001 (2) | 0.0134 (19) | −0.001 (2) |
C4 | 0.042 (3) | 0.052 (3) | 0.032 (2) | −0.010 (2) | 0.008 (2) | −0.006 (2) |
C5 | 0.039 (2) | 0.043 (3) | 0.025 (2) | −0.003 (2) | 0.0048 (18) | 0.000 (2) |
C6 | 0.035 (2) | 0.054 (3) | 0.030 (2) | −0.003 (2) | 0.0057 (18) | −0.004 (2) |
C7 | 0.034 (2) | 0.057 (3) | 0.037 (2) | −0.003 (2) | 0.0087 (19) | −0.002 (2) |
C8 | 0.033 (2) | 0.039 (2) | 0.035 (2) | −0.006 (2) | 0.0118 (19) | 0.000 (2) |
C9 | 0.033 (2) | 0.046 (3) | 0.029 (2) | −0.003 (2) | 0.0040 (17) | 0.005 (2) |
C10 | 0.036 (2) | 0.045 (3) | 0.032 (2) | −0.002 (2) | 0.0106 (19) | 0.000 (2) |
C11 | 0.036 (2) | 0.077 (4) | 0.035 (2) | −0.009 (3) | 0.0093 (19) | 0.001 (3) |
C12 | 0.037 (2) | 0.071 (3) | 0.030 (2) | −0.011 (2) | 0.0022 (18) | 0.000 (2) |
C13 | 0.037 (2) | 0.045 (3) | 0.033 (2) | −0.007 (2) | 0.0103 (19) | −0.002 (2) |
C14 | 0.034 (2) | 0.041 (2) | 0.030 (2) | −0.008 (2) | 0.0068 (18) | 0.001 (2) |
C15 | 0.044 (3) | 0.052 (3) | 0.039 (2) | −0.009 (2) | 0.017 (2) | −0.005 (2) |
C16 | 0.052 (3) | 0.039 (3) | 0.046 (3) | −0.006 (2) | 0.020 (2) | 0.006 (2) |
C17 | 0.058 (3) | 0.044 (3) | 0.033 (2) | −0.007 (2) | 0.011 (2) | 0.002 (2) |
C18 | 0.061 (3) | 0.055 (3) | 0.039 (2) | 0.003 (4) | 0.0148 (19) | 0.007 (3) |
C19 | 0.051 (3) | 0.063 (5) | 0.046 (2) | 0.007 (3) | 0.014 (2) | 0.009 (2) |
C20 | 0.063 (3) | 0.044 (3) | 0.042 (3) | −0.005 (3) | 0.023 (2) | −0.002 (2) |
C21 | 0.065 (3) | 0.041 (3) | 0.060 (3) | −0.009 (3) | 0.034 (3) | −0.003 (2) |
C22 | 0.089 (4) | 0.062 (4) | 0.072 (4) | −0.010 (3) | 0.050 (3) | −0.010 (3) |
C23 | 0.078 (4) | 0.090 (5) | 0.132 (6) | −0.018 (4) | 0.074 (5) | −0.018 (5) |
C24 | 0.060 (4) | 0.100 (6) | 0.137 (6) | −0.022 (4) | 0.045 (4) | −0.029 (5) |
C25 | 0.059 (4) | 0.126 (7) | 0.112 (5) | −0.030 (4) | 0.042 (4) | −0.027 (5) |
N26 | 0.058 (3) | 0.087 (4) | 0.076 (3) | −0.017 (3) | 0.031 (3) | −0.018 (3) |
O27 | 0.074 (2) | 0.059 (2) | 0.0288 (16) | −0.015 (2) | 0.0103 (16) | 0.0005 (16) |
N28 | 0.048 (2) | 0.046 (2) | 0.0326 (18) | 0.0011 (19) | 0.0171 (16) | −0.0004 (18) |
C29 | 0.072 (4) | 0.069 (4) | 0.034 (2) | −0.017 (3) | 0.024 (2) | 0.006 (3) |
C30 | 0.050 (3) | 0.130 (6) | 0.074 (4) | −0.010 (4) | 0.033 (3) | −0.022 (4) |
C31 | 0.074 (4) | 0.111 (6) | 0.080 (4) | 0.006 (4) | 0.040 (3) | −0.019 (4) |
C32 | 0.059 (3) | 0.053 (4) | 0.049 (2) | 0.009 (3) | 0.020 (2) | −0.006 (3) |
C33 | 0.056 (3) | 0.056 (3) | 0.030 (2) | 0.000 (3) | 0.012 (2) | 0.002 (2) |
C34 | 0.066 (3) | 0.051 (3) | 0.043 (3) | 0.003 (3) | 0.008 (2) | 0.009 (2) |
C35 | 0.080 (4) | 0.057 (4) | 0.054 (3) | 0.014 (3) | 0.022 (3) | 0.005 (3) |
Br | 0.0699 (3) | 0.0681 (3) | 0.0571 (3) | −0.0114 (4) | 0.0044 (2) | 0.0042 (4) |
O1W | 0.108 (5) | 0.079 (5) | 0.118 (6) | 0.000 | 0.020 (5) | 0.000 |
C1—C2 | 1.532 (6) | C17—O27 | 1.420 (5) |
C1—C10 | 1.544 (6) | C17—H17 | 0.9800 |
C1—H1A | 0.9700 | C18—H18A | 0.9600 |
C1—H1B | 0.9700 | C18—H18B | 0.9600 |
C2—C3 | 1.518 (6) | C18—H18C | 0.9600 |
C2—H2A | 0.9700 | C19—H19A | 0.9600 |
C2—H2B | 0.9700 | C19—H19B | 0.9600 |
C3—C4 | 1.531 (6) | C19—H19C | 0.9600 |
C3—N28 | 1.543 (5) | C20—C21 | 1.463 (7) |
C3—H3 | 0.9800 | C20—H20 | 0.9300 |
C4—C5 | 1.511 (6) | C21—N26 | 1.351 (7) |
C4—H4A | 0.9700 | C21—C22 | 1.381 (7) |
C4—H4B | 0.9700 | C22—C23 | 1.384 (8) |
C5—C6 | 1.331 (6) | C22—H22 | 0.9300 |
C5—C10 | 1.533 (6) | C23—C24 | 1.349 (10) |
C6—C7 | 1.494 (6) | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—C25 | 1.367 (9) |
C7—C8 | 1.522 (6) | C24—H24 | 0.9300 |
C7—H7A | 0.9700 | C25—N26 | 1.329 (7) |
C7—H7B | 0.9700 | C25—H25 | 0.9300 |
C8—C14 | 1.510 (6) | O27—H27 | 0.81 (2) |
C8—C9 | 1.553 (6) | N28—C32 | 1.528 (7) |
C8—H8 | 0.9800 | N28—C29 | 1.529 (7) |
C9—C11 | 1.535 (5) | N28—C33 | 1.530 (6) |
C9—C10 | 1.557 (6) | C29—C30 | 1.510 (8) |
C9—H9 | 0.9800 | C29—H29A | 0.9700 |
C10—C19 | 1.520 (7) | C29—H29B | 0.9700 |
C11—C12 | 1.528 (6) | C30—C31 | 1.483 (10) |
C11—H11A | 0.9700 | C30—H30A | 0.9700 |
C11—H11B | 0.9700 | C30—H30B | 0.9700 |
C12—C13 | 1.516 (6) | C31—C32 | 1.510 (8) |
C12—H12A | 0.9700 | C31—H31A | 0.9700 |
C12—H12B | 0.9700 | C31—H31B | 0.9700 |
C13—C17 | 1.530 (6) | C32—H32A | 0.9700 |
C13—C14 | 1.534 (5) | C32—H32B | 0.9700 |
C13—C18 | 1.537 (9) | C33—C34 | 1.486 (8) |
C14—C15 | 1.537 (6) | C33—H33A | 0.9700 |
C14—H14 | 0.9800 | C33—H33B | 0.9700 |
C15—C16 | 1.516 (6) | C34—C35 | 1.301 (7) |
C15—H15A | 0.9700 | C34—H34 | 0.9300 |
C15—H15B | 0.9700 | C35—H35A | 0.9300 |
C16—C20 | 1.321 (6) | C35—H35B | 0.9300 |
C16—C17 | 1.529 (6) | O1W—H1W | 0.88 (2) |
C2—C1—C10 | 113.8 (4) | C20—C16—C15 | 129.3 (4) |
C2—C1—H1A | 108.8 | C20—C16—C17 | 123.1 (4) |
C10—C1—H1A | 108.8 | C15—C16—C17 | 107.6 (4) |
C2—C1—H1B | 108.8 | O27—C17—C16 | 113.3 (4) |
C10—C1—H1B | 108.8 | O27—C17—C13 | 115.8 (4) |
H1A—C1—H1B | 107.7 | C16—C17—C13 | 104.6 (4) |
C3—C2—C1 | 108.5 (4) | O27—C17—H17 | 107.6 |
C3—C2—H2A | 110.0 | C16—C17—H17 | 107.6 |
C1—C2—H2A | 110.0 | C13—C17—H17 | 107.6 |
C3—C2—H2B | 110.0 | C13—C18—H18A | 109.5 |
C1—C2—H2B | 110.0 | C13—C18—H18B | 109.5 |
H2A—C2—H2B | 108.4 | H18A—C18—H18B | 109.5 |
C2—C3—C4 | 108.8 (4) | C13—C18—H18C | 109.5 |
C2—C3—N28 | 113.6 (3) | H18A—C18—H18C | 109.5 |
C4—C3—N28 | 111.7 (4) | H18B—C18—H18C | 109.5 |
C2—C3—H3 | 107.5 | C10—C19—H19A | 109.5 |
C4—C3—H3 | 107.5 | C10—C19—H19B | 109.5 |
N28—C3—H3 | 107.5 | H19A—C19—H19B | 109.5 |
C5—C4—C3 | 110.8 (4) | C10—C19—H19C | 109.5 |
C5—C4—H4A | 109.5 | H19A—C19—H19C | 109.5 |
C3—C4—H4A | 109.5 | H19B—C19—H19C | 109.5 |
C5—C4—H4B | 109.5 | C16—C20—C21 | 128.8 (5) |
C3—C4—H4B | 109.5 | C16—C20—H20 | 115.6 |
H4A—C4—H4B | 108.1 | C21—C20—H20 | 115.6 |
C6—C5—C4 | 120.1 (4) | N26—C21—C22 | 120.2 (5) |
C6—C5—C10 | 123.3 (4) | N26—C21—C20 | 118.9 (4) |
C4—C5—C10 | 116.7 (4) | C22—C21—C20 | 120.8 (5) |
C5—C6—C7 | 124.7 (4) | C21—C22—C23 | 120.6 (6) |
C5—C6—H6 | 117.7 | C21—C22—H22 | 119.7 |
C7—C6—H6 | 117.7 | C23—C22—H22 | 119.7 |
C6—C7—C8 | 113.4 (3) | C24—C23—C22 | 118.0 (6) |
C6—C7—H7A | 108.9 | C24—C23—H23 | 121.0 |
C8—C7—H7A | 108.9 | C22—C23—H23 | 121.0 |
C6—C7—H7B | 108.9 | C23—C24—C25 | 119.3 (6) |
C8—C7—H7B | 108.9 | C23—C24—H24 | 120.4 |
H7A—C7—H7B | 107.7 | C25—C24—H24 | 120.4 |
C14—C8—C7 | 110.5 (3) | N26—C25—C24 | 123.8 (7) |
C14—C8—C9 | 109.3 (3) | N26—C25—H25 | 118.1 |
C7—C8—C9 | 109.8 (3) | C24—C25—H25 | 118.1 |
C14—C8—H8 | 109.1 | C25—N26—C21 | 117.9 (5) |
C7—C8—H8 | 109.1 | C17—O27—H27 | 104 (4) |
C9—C8—H8 | 109.1 | C32—N28—C29 | 105.8 (4) |
C11—C9—C8 | 112.5 (3) | C32—N28—C33 | 108.1 (4) |
C11—C9—C10 | 113.9 (3) | C29—N28—C33 | 109.5 (4) |
C8—C9—C10 | 111.4 (4) | C32—N28—C3 | 112.8 (4) |
C11—C9—H9 | 106.1 | C29—N28—C3 | 110.6 (4) |
C8—C9—H9 | 106.1 | C33—N28—C3 | 109.9 (3) |
C10—C9—H9 | 106.1 | C30—C29—N28 | 105.0 (5) |
C19—C10—C5 | 109.6 (4) | C30—C29—H29A | 110.7 |
C19—C10—C1 | 110.2 (4) | N28—C29—H29A | 110.7 |
C5—C10—C1 | 107.8 (3) | C30—C29—H29B | 110.7 |
C19—C10—C9 | 111.9 (4) | N28—C29—H29B | 110.7 |
C5—C10—C9 | 109.3 (3) | H29A—C29—H29B | 108.8 |
C1—C10—C9 | 107.9 (4) | C31—C30—C29 | 104.4 (5) |
C12—C11—C9 | 113.9 (4) | C31—C30—H30A | 110.9 |
C12—C11—H11A | 108.8 | C29—C30—H30A | 110.9 |
C9—C11—H11A | 108.8 | C31—C30—H30B | 110.9 |
C12—C11—H11B | 108.8 | C29—C30—H30B | 110.9 |
C9—C11—H11B | 108.8 | H30A—C30—H30B | 108.9 |
H11A—C11—H11B | 107.7 | C30—C31—C32 | 103.0 (5) |
C13—C12—C11 | 111.5 (4) | C30—C31—H31A | 111.2 |
C13—C12—H12A | 109.3 | C32—C31—H31A | 111.2 |
C11—C12—H12A | 109.3 | C30—C31—H31B | 111.2 |
C13—C12—H12B | 109.3 | C32—C31—H31B | 111.2 |
C11—C12—H12B | 109.3 | H31A—C31—H31B | 109.1 |
H12A—C12—H12B | 108.0 | C31—C32—N28 | 104.2 (5) |
C12—C13—C17 | 115.2 (4) | C31—C32—H32A | 110.9 |
C12—C13—C14 | 106.6 (3) | N28—C32—H32A | 110.9 |
C17—C13—C14 | 99.5 (3) | C31—C32—H32B | 110.9 |
C12—C13—C18 | 111.8 (4) | N28—C32—H32B | 110.9 |
C17—C13—C18 | 109.5 (4) | H32A—C32—H32B | 108.9 |
C14—C13—C18 | 113.7 (4) | C34—C33—N28 | 113.0 (4) |
C8—C14—C13 | 114.8 (3) | C34—C33—H33A | 109.0 |
C8—C14—C15 | 119.2 (4) | N28—C33—H33A | 109.0 |
C13—C14—C15 | 104.1 (3) | C34—C33—H33B | 109.0 |
C8—C14—H14 | 105.9 | N28—C33—H33B | 109.0 |
C13—C14—H14 | 105.9 | H33A—C33—H33B | 107.8 |
C15—C14—H14 | 105.9 | C35—C34—C33 | 123.2 (5) |
C16—C15—C14 | 103.1 (3) | C35—C34—H34 | 118.4 |
C16—C15—H15A | 111.1 | C33—C34—H34 | 118.4 |
C14—C15—H15A | 111.1 | C34—C35—H35A | 120.0 |
C16—C15—H15B | 111.1 | C34—C35—H35B | 120.0 |
C14—C15—H15B | 111.1 | H35A—C35—H35B | 120.0 |
H15A—C15—H15B | 109.1 | ||
C10—C1—C2—C3 | −61.2 (6) | C15—C16—C17—O27 | 146.3 (4) |
C1—C2—C3—C4 | 62.2 (5) | C20—C16—C17—C13 | −163.7 (5) |
C1—C2—C3—N28 | −172.7 (4) | C15—C16—C17—C13 | 19.2 (5) |
C2—C3—C4—C5 | −58.0 (5) | C12—C13—C17—O27 | 81.6 (5) |
N28—C3—C4—C5 | 175.7 (4) | C14—C13—C17—O27 | −164.9 (4) |
C3—C4—C5—C6 | −129.1 (5) | C18—C13—C17—O27 | −45.4 (5) |
C3—C4—C5—C10 | 52.4 (6) | C12—C13—C17—C16 | −152.9 (4) |
C4—C5—C6—C7 | −176.9 (5) | C14—C13—C17—C16 | −39.3 (4) |
C10—C5—C6—C7 | 1.6 (8) | C18—C13—C17—C16 | 80.1 (4) |
C5—C6—C7—C8 | 11.1 (7) | C15—C16—C20—C21 | 4.5 (10) |
C6—C7—C8—C14 | −162.1 (4) | C17—C16—C20—C21 | −171.9 (5) |
C6—C7—C8—C9 | −41.5 (6) | C16—C20—C21—N26 | −3.6 (9) |
C14—C8—C9—C11 | −47.7 (5) | C16—C20—C21—C22 | 175.7 (6) |
C7—C8—C9—C11 | −169.1 (4) | N26—C21—C22—C23 | 3.5 (9) |
C14—C8—C9—C10 | −177.0 (4) | C20—C21—C22—C23 | −175.8 (6) |
C7—C8—C9—C10 | 61.6 (5) | C21—C22—C23—C24 | −1.0 (11) |
C6—C5—C10—C19 | −105.8 (5) | C22—C23—C24—C25 | −0.8 (12) |
C4—C5—C10—C19 | 72.7 (5) | C23—C24—C25—N26 | 0.2 (13) |
C6—C5—C10—C1 | 134.2 (5) | C24—C25—N26—C21 | 2.2 (11) |
C4—C5—C10—C1 | −47.3 (6) | C22—C21—N26—C25 | −3.9 (9) |
C6—C5—C10—C9 | 17.2 (6) | C20—C21—N26—C25 | 175.3 (6) |
C4—C5—C10—C9 | −164.3 (4) | C2—C3—N28—C32 | −64.9 (5) |
C2—C1—C10—C19 | −68.2 (5) | C4—C3—N28—C32 | 58.6 (5) |
C2—C1—C10—C5 | 51.3 (5) | C2—C3—N28—C29 | 53.4 (6) |
C2—C1—C10—C9 | 169.3 (4) | C4—C3—N28—C29 | 176.9 (4) |
C11—C9—C10—C19 | −54.8 (5) | C2—C3—N28—C33 | 174.3 (4) |
C8—C9—C10—C19 | 73.6 (4) | C4—C3—N28—C33 | −62.1 (5) |
C11—C9—C10—C5 | −176.4 (4) | C32—N28—C29—C30 | 6.4 (5) |
C8—C9—C10—C5 | −48.0 (5) | C33—N28—C29—C30 | 122.7 (4) |
C11—C9—C10—C1 | 66.6 (5) | C3—N28—C29—C30 | −116.1 (4) |
C8—C9—C10—C1 | −164.9 (4) | N28—C29—C30—C31 | −30.1 (6) |
C8—C9—C11—C12 | 48.2 (6) | C29—C30—C31—C32 | 42.3 (7) |
C10—C9—C11—C12 | 176.1 (4) | C30—C31—C32—N28 | −37.8 (6) |
C9—C11—C12—C13 | −54.3 (6) | C29—N28—C32—C31 | 19.1 (5) |
C11—C12—C13—C17 | 167.3 (4) | C33—N28—C32—C31 | −98.1 (5) |
C11—C12—C13—C14 | 57.9 (5) | C3—N28—C32—C31 | 140.1 (4) |
C11—C12—C13—C18 | −66.9 (5) | C32—N28—C33—C34 | 179.3 (4) |
C7—C8—C14—C13 | 177.9 (4) | C29—N28—C33—C34 | 64.5 (5) |
C9—C8—C14—C13 | 57.0 (5) | C3—N28—C33—C34 | −57.2 (5) |
C7—C8—C14—C15 | −57.7 (5) | N28—C33—C34—C35 | 120.3 (5) |
C9—C8—C14—C15 | −178.6 (4) | C13—C17—O27—H27 | −113 (4) |
C12—C13—C14—C8 | −62.1 (5) | C16—C17—O27—H27 | 126 (4) |
C17—C13—C14—C8 | 177.8 (4) | C15—C16—C17—H17 | −95.0 |
C18—C13—C14—C8 | 61.5 (5) | C20—C16—C17—H17 | 82.1 |
C12—C13—C14—C15 | 165.9 (4) | C17—C16—C20—H20 | 8.1 |
C17—C13—C14—C15 | 45.8 (4) | C22—C21—C20—H20 | −4.3 |
C18—C13—C14—C15 | −70.5 (5) | C15—C16—C20—H20 | −175.5 |
C8—C14—C15—C16 | −163.9 (4) | N26—C21—C20—H20 | 176.4 |
C13—C14—C15—C16 | −34.5 (5) | C18—C13—C14—H14 | 178.0 |
C14—C15—C16—C20 | −167.6 (5) | H9—C9—C8—H8 | −172.9 |
C14—C15—C16—C17 | 9.3 (5) | C19—C10—C13—C18 | 7.5 (4) |
C20—C16—C17—O27 | −36.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O27—H27···Br | 0.81 (3) | 2.38 (3) | 3.194 (4) | 178 (6) |
O1W—H1W···Bri | 0.88 (4) | 2.53 (4) | 3.405 (5) | 172 (3) |
Symmetry code: (i) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C32H45BrN2O·0.5H2O |
Mr | 562.61 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 21.054 (4), 9.3083 (18), 15.551 (4) |
β (°) | 106.15 (2) |
V (Å3) | 2927.4 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.43 |
Crystal size (mm) | 0.20 × 0.17 × 0.17 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.763, 0.793 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2835, 2751, 2100 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.089, 1.08 |
No. of reflections | 2751 |
No. of parameters | 336 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.23 |
Absolute structure | Flack (1983) How many Friedels? |
Absolute structure parameter | −0.002 (12) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), DIRDIF99 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O27—H27···Br | 0.81 (3) | 2.38 (3) | 3.194 (4) | 178 (6) |
O1W—H1W···Bri | 0.88 (4) | 2.53 (4) | 3.405 (5) | 172 (3) |
Symmetry code: (i) x+1/2, y+1/2, z. |
The present 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 (Vasuki et al., 2001; Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002; Vasuki, Thamotharan et al., 2002). It is well known that minor changes in the basic composition of steroids significantly alters their biological activities (Duax & Norton, 1975). We are particularly interested in studying the conformational flexibilities of steroids due to various possible substitutions at the C3, C16 and C17 positions. \sch
The puckering parameters in (I) [Ring A: Q = 0.576 (5) Å, θ = 10.1 (5)° and ϕ = 84 (3)°; Ring C: Q = 0.562 (5) Å, θ = 8.9 (5)° and ϕ = 251 (3)° (Cremer & Pople, 1975)] show that rings A and C adopt chair conformations. The presence of the pyrrolidine moiety bonded to C3 does not disturb the usual chair conformation of ring A of the steroid nucleus. The C5—C6 [Csp2—Csp2] distance of 1.331 (6) Å confirms the localization of a double bond at this position. Due to this double bond, the environment of atom C5 is planar, and hence ring B adopts the 8β,9α half-chair conformation [Q = 0.498 (5) Å, θ = 50.9 (6)° and ϕ = 217.5 (7)°]. Similar observations have been reported by Caira et al. (1995), Andrade et al. (2001) and Hema et al. (2002).
Ring D adopts a slightly deformed 14α envelope conformation, with pseudorotation parameters Δ = 12.6° and ϕm = 46.0° (Altona et al., 1968). The pyrrolidine ring at C3 exhibits a slightly distorted β envelope conformation, with Δ = 18° and ϕm = 42.6 (3)°. The C17—C16—C20—C21 torsion angle of -171.9 (5)° indicates that the 2-pyridyl ring has an E configuration with respect to the hydroxyl group at position 17. The larger exocyclic angle at C15—C16—C20 [129.3 (4)°] compared with C17—C16—C20 [123.1 (4)°] might be a consequence of repulsion between the lone pair of electrons on atom N26 of the pyridine ring and atom H15B on C15 (N26···H15B 2.573 Å).
The C19—C10···C13—C18 pseudo torsion angle is 7.5 (4)°. The equatorially substituted pyrrolidine moiety is oriented at an angle of 78.5 (3)° with respect to the central steroid nucleus. The dihedral angle between the plane of the pyridine ring and the average molecular plane comprising rings A, B, C and D is 11.4 (2)°. The dihedral angle between the pyridine and pyrrolidine rings is 59.6 (3)°. The valency angles C8—C14—C15 [119.2 (4)°] and C14—C13—C17 [99.5 (3)°] are close to the expected values of 121.2° and 101.4°, respectively (Duax & Norton, 1975). The geometry of the rings is trans at the B/C and C/D ring junctions.
The structure of (I) is stabilized by an O—H···Br network which involves both the hydroxyl group of the steroid and the water molecules included in the lattice, and a projection down the b axis is shown in Fig. 2.