Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008777/na6083sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008777/na6083Isup2.hkl |
CCDC reference: 170757
The title compound, (I), was synthesized from 3-keto-bisnor-4-cholen-22-al by Horner–Wittig reaction, reesterification and DDQ-dehydration. The resulting ester was purified by column chromatographie (cyclohexane–ethyl acetate = 2:1, RF = 0,30) and then crystallized from cyclohexane with the addition of active charcoal. After filtration of the hot solution, crystals (m.p. 440.5–441.5 K) began to grow immediately by cooling to room temperature.
H atoms were placed in calculated positions with Uiso constrained to be 1.5 times Ueq of the carrier atom for the methyl-H and 1.2 times Ueq for the remaining H atoms.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELTXL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).
C25H34O3 | F(000) = 416 |
Mr = 382.52 | Dx = 1.177 Mg m−3 Dm = not determined Mg m−3 Dm measured by not measured |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4164 (2) Å | Cell parameters from 9365 reflections |
b = 7.5425 (2) Å | θ = 3.0–27.5° |
c = 14.4209 (3) Å | µ = 0.08 mm−1 |
β = 107.7621 (11)° | T = 293 K |
V = 1078.98 (4) Å3 | Block, colourless |
Z = 2 | 0.5 × 0.5 × 0.25 mm |
Nonius KappaCCD diffractometer | 1545 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
Detector resolution: 10 vertical, 18 horizontal pixels mm-1 | h = −13→13 |
316 frames via ω–rotation (Δω = 1°) with three sets at different κ–angles and two times 30 s per frame scans | k = −9→9 |
9365 measured reflections | l = −18→17 |
2593 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0619P)2] where P = (Fo2 + 2Fc2)/3 |
2593 reflections | (Δ/σ)max < 0.001 |
257 parameters | Δρmax = 0.13 e Å−3 |
1 restraint | Δρmin = −0.13 e Å−3 |
C25H34O3 | V = 1078.98 (4) Å3 |
Mr = 382.52 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.4164 (2) Å | µ = 0.08 mm−1 |
b = 7.5425 (2) Å | T = 293 K |
c = 14.4209 (3) Å | 0.5 × 0.5 × 0.25 mm |
β = 107.7621 (11)° |
Nonius KappaCCD diffractometer | 1545 reflections with I > 2σ(I) |
9365 measured reflections | Rint = 0.032 |
2593 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 1 restraint |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.13 e Å−3 |
2593 reflections | Δρmin = −0.13 e Å−3 |
257 parameters |
Experimental. The data collection covered the whole sphere of reciprocal space. The crystal-to-detector distance was 34 mm. Crystal decay was monitored by repeating the initial frames at the end of data collection and analysing the duplicate reflections. |
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 | ||
O1 | 0.3896 (2) | 0.7502 (5) | −0.16936 (15) | 0.1220 (11) | |
O2 | −0.4991 (2) | 0.7506 (5) | 0.44296 (16) | 0.1251 (12) | |
O3 | −0.3843 (2) | 0.7433 (3) | 0.59963 (13) | 0.0844 (7) | |
C1 | 0.3370 (3) | 0.5868 (4) | 0.0457 (2) | 0.0755 (9) | |
H1 | 0.3376 | 0.4781 | 0.0763 | 0.091* | |
C2 | 0.3573 (3) | 0.5857 (6) | −0.0407 (3) | 0.0878 (11) | |
H2 | 0.3721 | 0.4783 | −0.0674 | 0.105* | |
C3 | 0.3568 (3) | 0.7469 (6) | −0.0941 (2) | 0.0843 (11) | |
C4 | 0.3169 (3) | 0.9056 (5) | −0.0536 (2) | 0.0768 (9) | |
H4 | 0.3056 | 1.0094 | −0.0900 | 0.092* | |
C5 | 0.2953 (3) | 0.9114 (4) | 0.0334 (2) | 0.0610 (7) | |
C6 | 0.2536 (4) | 1.0763 (4) | 0.0723 (3) | 0.0851 (10) | |
H6A | 0.2324 | 1.1658 | 0.0216 | 0.102* | |
H6B | 0.3286 | 1.1197 | 0.1256 | 0.102* | |
C7 | 0.1342 (3) | 1.0506 (4) | 0.1078 (2) | 0.0761 (9) | |
H7A | 0.0549 | 1.0306 | 0.0524 | 0.091* | |
H7B | 0.1194 | 1.1581 | 0.1400 | 0.091* | |
C8 | 0.1511 (3) | 0.8954 (3) | 0.17819 (18) | 0.0510 (6) | |
H8 | 0.2269 | 0.9212 | 0.2364 | 0.061* | |
C9 | 0.1836 (2) | 0.7268 (4) | 0.13078 (17) | 0.0490 (6) | |
H9 | 0.1085 | 0.7094 | 0.0711 | 0.059* | |
C10 | 0.3133 (3) | 0.7489 (4) | 0.09779 (17) | 0.0580 (7) | |
C11 | 0.1874 (3) | 0.5613 (3) | 0.1934 (2) | 0.0656 (8) | |
H11A | 0.1943 | 0.4570 | 0.1558 | 0.079* | |
H11B | 0.2674 | 0.5659 | 0.2496 | 0.079* | |
C12 | 0.0630 (3) | 0.5430 (4) | 0.2283 (2) | 0.0600 (7) | |
H12A | −0.0156 | 0.5198 | 0.1729 | 0.072* | |
H12B | 0.0752 | 0.4427 | 0.2723 | 0.072* | |
C13 | 0.0387 (2) | 0.7088 (3) | 0.28014 (16) | 0.0463 (6) | |
C14 | 0.0257 (3) | 0.8639 (3) | 0.20939 (17) | 0.0494 (7) | |
H14 | −0.0471 | 0.8332 | 0.1503 | 0.059* | |
C15 | −0.0261 (3) | 1.0183 (4) | 0.2574 (2) | 0.0648 (8) | |
H15A | −0.0786 | 1.1005 | 0.2088 | 0.078* | |
H15B | 0.0481 | 1.0819 | 0.3023 | 0.078* | |
C16 | −0.1146 (3) | 0.9276 (4) | 0.3117 (2) | 0.0666 (8) | |
H16A | −0.2081 | 0.9620 | 0.2833 | 0.080* | |
H16B | −0.0856 | 0.9621 | 0.3798 | 0.080* | |
C17 | −0.0986 (2) | 0.7243 (4) | 0.30202 (16) | 0.0493 (6) | |
H17 | −0.1689 | 0.6868 | 0.2430 | 0.059* | |
C18 | 0.1545 (2) | 0.7350 (4) | 0.37529 (17) | 0.0639 (7) | |
H18A | 0.2372 | 0.7540 | 0.3605 | 0.096* | |
H18B | 0.1627 | 0.6313 | 0.4153 | 0.096* | |
H18C | 0.1357 | 0.8361 | 0.4095 | 0.096* | |
C19 | 0.4414 (3) | 0.7732 (5) | 0.18624 (19) | 0.0834 (10) | |
H19A | 0.5183 | 0.7894 | 0.1636 | 0.125* | |
H19B | 0.4545 | 0.6698 | 0.2269 | 0.125* | |
H19C | 0.4308 | 0.8753 | 0.2230 | 0.125* | |
C20 | −0.1203 (3) | 0.6199 (4) | 0.38660 (18) | 0.0546 (7) | |
H20 | −0.0456 | 0.6472 | 0.4452 | 0.066* | |
C21 | −0.1219 (3) | 0.4183 (4) | 0.3703 (2) | 0.0742 (8) | |
H21A | −0.1918 | 0.3889 | 0.3115 | 0.111* | |
H21B | −0.1387 | 0.3589 | 0.4243 | 0.111* | |
H21C | −0.0363 | 0.3812 | 0.3649 | 0.111* | |
C22 | −0.2483 (3) | 0.6706 (4) | 0.40544 (18) | 0.0615 (8) | |
H22 | −0.3252 | 0.6761 | 0.3517 | 0.074* | |
C23 | −0.2632 (3) | 0.7081 (4) | 0.49064 (18) | 0.0598 (7) | |
H23 | −0.1864 | 0.7165 | 0.5443 | 0.072* | |
C24 | −0.3948 (3) | 0.7375 (5) | 0.5052 (2) | 0.0702 (8) | |
C25 | −0.5086 (4) | 0.7595 (6) | 0.6239 (2) | 0.1080 (14) | |
H25A | −0.5674 | 0.6629 | 0.5953 | 0.162* | |
H25B | −0.5516 | 0.8697 | 0.5991 | 0.162* | |
H25C | −0.4894 | 0.7567 | 0.6933 | 0.162* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1118 (19) | 0.202 (3) | 0.0666 (13) | 0.012 (2) | 0.0492 (13) | 0.0094 (18) |
O2 | 0.0589 (14) | 0.245 (4) | 0.0766 (14) | 0.0354 (19) | 0.0276 (12) | 0.021 (2) |
O3 | 0.0788 (13) | 0.1183 (18) | 0.0682 (11) | 0.0187 (14) | 0.0403 (10) | −0.0027 (13) |
C1 | 0.079 (2) | 0.076 (2) | 0.089 (2) | 0.0116 (17) | 0.0514 (19) | 0.0064 (18) |
C2 | 0.082 (2) | 0.108 (3) | 0.091 (2) | 0.009 (2) | 0.052 (2) | −0.007 (2) |
C3 | 0.0577 (19) | 0.144 (3) | 0.0565 (16) | 0.008 (2) | 0.0244 (14) | 0.001 (2) |
C4 | 0.0623 (18) | 0.110 (3) | 0.0589 (18) | 0.0004 (18) | 0.0197 (15) | 0.0272 (19) |
C5 | 0.0528 (16) | 0.0737 (19) | 0.0576 (15) | −0.0052 (15) | 0.0184 (12) | 0.0139 (15) |
C6 | 0.116 (3) | 0.063 (2) | 0.092 (2) | −0.0027 (19) | 0.055 (2) | 0.0186 (17) |
C7 | 0.095 (2) | 0.0549 (17) | 0.089 (2) | 0.0045 (17) | 0.0432 (19) | 0.0127 (16) |
C8 | 0.0565 (16) | 0.0452 (14) | 0.0528 (13) | −0.0040 (12) | 0.0189 (12) | −0.0007 (12) |
C9 | 0.0511 (15) | 0.0519 (14) | 0.0471 (12) | −0.0022 (13) | 0.0196 (11) | −0.0007 (13) |
C10 | 0.0529 (16) | 0.0721 (18) | 0.0539 (14) | 0.0014 (14) | 0.0233 (13) | 0.0070 (15) |
C11 | 0.079 (2) | 0.0489 (16) | 0.087 (2) | 0.0081 (15) | 0.0525 (17) | 0.0013 (15) |
C12 | 0.0701 (19) | 0.0488 (14) | 0.0759 (18) | −0.0019 (14) | 0.0445 (16) | 0.0013 (13) |
C13 | 0.0447 (14) | 0.0481 (14) | 0.0498 (12) | −0.0003 (11) | 0.0200 (11) | −0.0023 (13) |
C14 | 0.0492 (15) | 0.0487 (15) | 0.0508 (14) | 0.0042 (12) | 0.0159 (12) | −0.0003 (12) |
C15 | 0.0763 (19) | 0.0520 (15) | 0.0728 (18) | 0.0089 (14) | 0.0327 (16) | −0.0003 (14) |
C16 | 0.0693 (19) | 0.0665 (17) | 0.0714 (17) | 0.0117 (15) | 0.0326 (15) | −0.0037 (16) |
C17 | 0.0427 (13) | 0.0604 (14) | 0.0456 (12) | 0.0021 (12) | 0.0145 (10) | −0.0039 (13) |
C18 | 0.0484 (15) | 0.0849 (19) | 0.0585 (14) | −0.0033 (15) | 0.0166 (12) | 0.0056 (17) |
C19 | 0.0545 (18) | 0.130 (3) | 0.0646 (16) | −0.0087 (18) | 0.0167 (14) | 0.0202 (19) |
C20 | 0.0438 (15) | 0.0727 (17) | 0.0501 (14) | 0.0023 (13) | 0.0184 (12) | −0.0017 (13) |
C21 | 0.089 (2) | 0.0677 (19) | 0.0803 (19) | −0.0058 (17) | 0.0472 (17) | 0.0067 (17) |
C22 | 0.0466 (16) | 0.089 (2) | 0.0490 (14) | 0.0019 (14) | 0.0142 (12) | 0.0036 (14) |
C23 | 0.0486 (16) | 0.0791 (18) | 0.0538 (14) | 0.0060 (14) | 0.0187 (12) | −0.0006 (15) |
C24 | 0.064 (2) | 0.095 (2) | 0.0588 (16) | 0.0129 (18) | 0.0279 (16) | 0.0018 (18) |
C25 | 0.102 (3) | 0.144 (4) | 0.109 (3) | 0.021 (3) | 0.077 (2) | 0.007 (3) |
O1—C3 | 1.234 (3) | C13—C14 | 1.531 (3) |
O2—C24 | 1.184 (3) | C13—C18 | 1.539 (3) |
O3—C24 | 1.333 (3) | C13—C17 | 1.560 (3) |
O3—C25 | 1.445 (3) | C14—C15 | 1.534 (3) |
C1—C2 | 1.326 (4) | C14—H14 | 0.9800 |
C1—C10 | 1.495 (4) | C15—C16 | 1.541 (4) |
C1—H1 | 0.9300 | C15—H15A | 0.9700 |
C2—C3 | 1.439 (5) | C15—H15B | 0.9700 |
C2—H2 | 0.9300 | C16—C17 | 1.553 (4) |
C3—C4 | 1.447 (5) | C16—H16A | 0.9700 |
C4—C5 | 1.341 (4) | C16—H16B | 0.9700 |
C4—H4 | 0.9300 | C17—C20 | 1.525 (4) |
C5—C6 | 1.482 (4) | C17—H17 | 0.9800 |
C5—C10 | 1.515 (4) | C18—H18A | 0.9600 |
C6—C7 | 1.496 (4) | C18—H18B | 0.9600 |
C6—H6A | 0.9700 | C18—H18C | 0.9600 |
C6—H6B | 0.9700 | C19—H19A | 0.9600 |
C7—C8 | 1.524 (4) | C19—H19B | 0.9600 |
C7—H7A | 0.9700 | C19—H19C | 0.9600 |
C7—H7B | 0.9700 | C20—C22 | 1.490 (3) |
C8—C14 | 1.524 (3) | C20—C21 | 1.539 (4) |
C8—C9 | 1.530 (3) | C20—H20 | 0.9800 |
C8—H8 | 0.9800 | C21—H21A | 0.9600 |
C9—C11 | 1.534 (4) | C21—H21B | 0.9600 |
C9—C10 | 1.572 (3) | C21—H21C | 0.9600 |
C9—H9 | 0.9800 | C22—C23 | 1.315 (3) |
C10—C19 | 1.550 (4) | C22—H22 | 0.9300 |
C11—C12 | 1.534 (3) | C23—C24 | 1.465 (4) |
C11—H11A | 0.9700 | C23—H23 | 0.9300 |
C11—H11B | 0.9700 | C25—H25A | 0.9600 |
C12—C13 | 1.517 (3) | C25—H25B | 0.9600 |
C12—H12A | 0.9700 | C25—H25C | 0.9600 |
C12—H12B | 0.9700 | ||
C24—O3—C25 | 116.7 (2) | C8—C14—C13 | 114.02 (19) |
C2—C1—C10 | 125.1 (3) | C8—C14—C15 | 117.7 (2) |
C2—C1—H1 | 117.4 | C13—C14—C15 | 104.54 (18) |
C10—C1—H1 | 117.4 | C8—C14—H14 | 106.6 |
C1—C2—C3 | 121.5 (3) | C13—C14—H14 | 106.6 |
C1—C2—H2 | 119.3 | C15—C14—H14 | 106.6 |
C3—C2—H2 | 119.3 | C14—C15—C16 | 103.9 (2) |
O1—C3—C2 | 122.1 (4) | C14—C15—H15A | 111.0 |
O1—C3—C4 | 122.0 (4) | C16—C15—H15A | 111.0 |
C2—C3—C4 | 116.0 (2) | C14—C15—H15B | 111.0 |
C5—C4—C3 | 123.8 (3) | C16—C15—H15B | 111.0 |
C5—C4—H4 | 118.1 | H15A—C15—H15B | 109.0 |
C3—C4—H4 | 118.1 | C15—C16—C17 | 107.2 (2) |
C4—C5—C6 | 122.3 (3) | C15—C16—H16A | 110.3 |
C4—C5—C10 | 121.5 (3) | C17—C16—H16A | 110.3 |
C6—C5—C10 | 116.3 (2) | C15—C16—H16B | 110.3 |
C5—C6—C7 | 113.1 (2) | C17—C16—H16B | 110.3 |
C5—C6—H6A | 109.0 | H16A—C16—H16B | 108.5 |
C7—C6—H6A | 109.0 | C20—C17—C16 | 113.0 (2) |
C5—C6—H6B | 109.0 | C20—C17—C13 | 119.4 (2) |
C7—C6—H6B | 109.0 | C16—C17—C13 | 102.9 (2) |
H6A—C6—H6B | 107.8 | C20—C17—H17 | 106.9 |
C6—C7—C8 | 112.8 (3) | C16—C17—H17 | 106.9 |
C6—C7—H7A | 109.0 | C13—C17—H17 | 106.9 |
C8—C7—H7A | 109.0 | C13—C18—H18A | 109.5 |
C6—C7—H7B | 109.0 | C13—C18—H18B | 109.5 |
C8—C7—H7B | 109.0 | H18A—C18—H18B | 109.5 |
H7A—C7—H7B | 107.8 | C13—C18—H18C | 109.5 |
C14—C8—C7 | 112.4 (2) | H18A—C18—H18C | 109.5 |
C14—C8—C9 | 109.19 (19) | H18B—C18—H18C | 109.5 |
C7—C8—C9 | 109.71 (19) | C10—C19—H19A | 109.5 |
C14—C8—H8 | 108.5 | C10—C19—H19B | 109.5 |
C7—C8—H8 | 108.5 | H19A—C19—H19B | 109.5 |
C9—C8—H8 | 108.5 | C10—C19—H19C | 109.5 |
C8—C9—C11 | 112.51 (17) | H19A—C19—H19C | 109.5 |
C8—C9—C10 | 112.04 (19) | H19B—C19—H19C | 109.5 |
C11—C9—C10 | 113.2 (2) | C22—C20—C17 | 111.9 (2) |
C8—C9—H9 | 106.1 | C22—C20—C21 | 108.2 (2) |
C11—C9—H9 | 106.1 | C17—C20—C21 | 112.7 (2) |
C10—C9—H9 | 106.1 | C22—C20—H20 | 108.0 |
C1—C10—C5 | 111.3 (2) | C17—C20—H20 | 108.0 |
C1—C10—C19 | 106.1 (2) | C21—C20—H20 | 108.0 |
C5—C10—C19 | 108.9 (3) | C20—C21—H21A | 109.5 |
C1—C10—C9 | 110.8 (2) | C20—C21—H21B | 109.5 |
C5—C10—C9 | 108.3 (2) | H21A—C21—H21B | 109.5 |
C19—C10—C9 | 111.53 (18) | C20—C21—H21C | 109.5 |
C12—C11—C9 | 113.2 (2) | H21A—C21—H21C | 109.5 |
C12—C11—H11A | 108.9 | H21B—C21—H21C | 109.5 |
C9—C11—H11A | 108.9 | C23—C22—C20 | 126.3 (2) |
C12—C11—H11B | 108.9 | C23—C22—H22 | 116.8 |
C9—C11—H11B | 108.9 | C20—C22—H22 | 116.8 |
H11A—C11—H11B | 107.7 | C22—C23—C24 | 123.3 (3) |
C13—C12—C11 | 111.9 (2) | C22—C23—H23 | 118.4 |
C13—C12—H12A | 109.2 | C24—C23—H23 | 118.4 |
C11—C12—H12A | 109.2 | O2—C24—O3 | 122.8 (2) |
C13—C12—H12B | 109.2 | O2—C24—C23 | 125.9 (2) |
C11—C12—H12B | 109.2 | O3—C24—C23 | 111.3 (3) |
H12A—C12—H12B | 107.9 | O3—C25—H25A | 109.5 |
C12—C13—C14 | 107.20 (17) | O3—C25—H25B | 109.5 |
C12—C13—C18 | 110.0 (2) | H25A—C25—H25B | 109.5 |
C14—C13—C18 | 112.4 (2) | O3—C25—H25C | 109.5 |
C12—C13—C17 | 117.6 (2) | H25A—C25—H25C | 109.5 |
C14—C13—C17 | 100.23 (18) | H25B—C25—H25C | 109.5 |
C18—C13—C17 | 109.13 (17) | ||
C10—C1—C2—C3 | −0.6 (5) | C11—C12—C13—C18 | −65.8 (3) |
C1—C2—C3—O1 | 172.1 (3) | C11—C12—C13—C17 | 168.5 (2) |
C1—C2—C3—C4 | −7.3 (5) | C7—C8—C14—C13 | 179.9 (2) |
O1—C3—C4—C5 | −172.2 (3) | C9—C8—C14—C13 | 58.0 (2) |
C2—C3—C4—C5 | 7.2 (5) | C7—C8—C14—C15 | −57.0 (3) |
C3—C4—C5—C6 | −179.6 (3) | C9—C8—C14—C15 | −179.0 (2) |
C3—C4—C5—C10 | 0.8 (5) | C12—C13—C14—C8 | −60.9 (2) |
C4—C5—C6—C7 | 130.1 (3) | C18—C13—C14—C8 | 60.1 (2) |
C10—C5—C6—C7 | −50.2 (4) | C17—C13—C14—C8 | 175.82 (19) |
C5—C6—C7—C8 | 51.2 (4) | C12—C13—C14—C15 | 169.1 (2) |
C6—C7—C8—C14 | −176.7 (2) | C18—C13—C14—C15 | −69.9 (3) |
C6—C7—C8—C9 | −55.0 (3) | C17—C13—C14—C15 | 45.9 (2) |
C14—C8—C9—C11 | −50.4 (3) | C8—C14—C15—C16 | −160.0 (2) |
C7—C8—C9—C11 | −174.0 (3) | C13—C14—C15—C16 | −32.3 (3) |
C14—C8—C9—C10 | −179.3 (2) | C14—C15—C16—C17 | 5.7 (3) |
C7—C8—C9—C10 | 57.1 (3) | C15—C16—C17—C20 | 152.3 (2) |
C2—C1—C10—C5 | 8.1 (4) | C15—C16—C17—C13 | 22.1 (3) |
C2—C1—C10—C19 | −110.2 (3) | C12—C13—C17—C20 | 77.2 (3) |
C2—C1—C10—C9 | 128.6 (3) | C14—C13—C17—C20 | −167.2 (2) |
C4—C5—C10—C1 | −8.0 (4) | C18—C13—C17—C20 | −48.9 (3) |
C6—C5—C10—C1 | 172.4 (2) | C12—C13—C17—C16 | −156.7 (2) |
C4—C5—C10—C19 | 108.6 (3) | C14—C13—C17—C16 | −41.0 (2) |
C6—C5—C10—C19 | −71.1 (3) | C18—C13—C17—C16 | 77.2 (2) |
C4—C5—C10—C9 | −130.0 (3) | C16—C17—C20—C22 | 50.6 (3) |
C6—C5—C10—C9 | 50.4 (3) | C13—C17—C20—C22 | 171.8 (2) |
C8—C9—C10—C1 | −176.1 (2) | C16—C17—C20—C21 | 172.8 (2) |
C11—C9—C10—C1 | 55.4 (3) | C13—C17—C20—C21 | −66.0 (3) |
C8—C9—C10—C5 | −53.8 (3) | C17—C20—C22—C23 | −132.3 (3) |
C11—C9—C10—C5 | 177.7 (2) | C21—C20—C22—C23 | 103.0 (3) |
C8—C9—C10—C19 | 66.0 (3) | C20—C22—C23—C24 | −172.9 (3) |
C11—C9—C10—C19 | −62.6 (3) | C25—O3—C24—O2 | 2.4 (5) |
C8—C9—C11—C12 | 49.8 (3) | C25—O3—C24—C23 | −175.9 (3) |
C10—C9—C11—C12 | 178.1 (2) | C22—C23—C24—O2 | −8.9 (5) |
C9—C11—C12—C13 | −53.6 (3) | C22—C23—C24—O3 | 169.4 (3) |
C11—C12—C13—C14 | 56.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O2i | 0.96 | 2.64 | 3.441 (3) | 141 |
C21—H21A···O1ii | 0.96 | 2.64 | 3.585 (3) | 168 |
C25—H25C···O1iii | 0.96 | 2.65 | 3.456 (5) | 142 |
Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z; (iii) x−1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H34O3 |
Mr | 382.52 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 10.4164 (2), 7.5425 (2), 14.4209 (3) |
β (°) | 107.7621 (11) |
V (Å3) | 1078.98 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.5 × 0.5 × 0.25 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9365, 2593, 1545 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.114, 1.01 |
No. of reflections | 2593 |
No. of parameters | 257 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.13 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELTXL-Plus (Sheldrick, 1991), SHELXL97 and PARST95 (Nardelli, 1995).
C17—C13—C14—C15 | 45.9 (2) | C16—C17—C20—C21 | 172.8 (2) |
C13—C14—C15—C16 | −32.3 (3) | C13—C17—C20—C21 | −66.0 (3) |
C14—C15—C16—C17 | 5.7 (3) | C17—C20—C22—C23 | −132.3 (3) |
C15—C16—C17—C13 | 22.1 (3) | C21—C20—C22—C23 | 103.0 (3) |
C14—C13—C17—C16 | −41.0 (2) |
Tomono et al. (1999) isolated an unknown steroid from an octocoral Dendronephthya sp. of the order Alcyonacea and they characterized it as methyl-3-oxochola-1,4,22-trien-24-oate without specifying the configuration at C20. In order to determine its structure unequivocally, an X-ray analysis has been undertaken. Starting from 3-keto-bisnor-4-cholen-22-al, the title compound, (I), has been synthesized in a three-step procedure and crystals were grown from cyclohexane.
The structure shown in Fig. 1 discloses the expected all-trans stereochemistry at the ring junctures. All bond lenghts and angles of the steroidal skeleton are within normal ranges (Duax & Norton, 1975). Selected torsion angles of the side chain and ring D are given in Table 1. The calculated values of Δ = 20.15° and ψm = 45.2° indicate a D ring conformation midway between a 13β-envelope and a 13β,14α-half-chair (Altona et al., 1968). To us, the most valuable piece of information that can be deduced from Fig. 1 is the relative configuration at C20. Since the stereochemistry in the cholan-type ring system is undoubted, one can easily determine the C20 configuration to be R. The substituents at C20 are staggered with respect to those at C17, with the methyl C21 anti to C16. The remainder of the side chain extends away from the steroid rings. The shortest intermolecular H···O contact is 2.641 (3) Å. A comparison of the title compound with the natural product shows great differences mainly in the 1H NMR chemical shifts of the side chain. This observation indicates a different configuration at C20. To get a reliable proof, the corresponding (20S)-methyl ester has been synthesized. Its crystal structure is described in Linker et al. (2001).