Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106017677/sk3023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017677/sk3023Isup2.hkl |
CCDC reference: 616139
(+)-3,11-Dioxoandrost-4-ene-17β-carboxylic acid, prepared as described by Newman et al. (2002), was hydrogenated in ethanol solution over a 5% Pd/C catalyst to provide (I). Crystals suitable for X-ray were obtained from ethyl acetate (m.p. 559 K, with decomposition, requiring that the apparatus be preheated to near the melting point before sample introduction).
All H atoms for (I) were found in electron density difference maps but were placed in calculated positions and allowed to refine as riding on their respective C or O atoms. The O—H distance was fixed at 0.84 Å; methyl, methylene and methine C—H distances were fixed at 0.98, 0.99 and 1.00 Å, respectively. The sign of rotation for (I) is that assigned by Mason et al. (1937) and its absolute stereochemistry, confirmed by its Flack parameter (based on 1081 Friedel pairs, 91.4% coverage), conforms to that of other steroids (Fieser & Fieser, 1959; Klyne & Buckingham, 1978).
Data collection: SMART WNT/2000 (Bruker, 2000); cell refinement: SMART WNT/2000; data reduction: SAINT-Plus (Bruker,2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker,2000); software used to prepare material for publication: SHELXTL.
C20H28O4 | Dx = 1.313 Mg m−3 |
Mr = 332.42 | Melting point: 559 K |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8793 reflections |
a = 6.3684 (1) Å | θ = 3.9–65.0° |
b = 11.6102 (1) Å | µ = 0.72 mm−1 |
c = 22.7430 (2) Å | T = 100 K |
V = 1681.58 (3) Å3 | Block, colorless |
Z = 4 | 0.26 × 0.18 × 0.08 mm |
F(000) = 720 |
Bruker SMART CCD Apex-II area-detector diffractometer | 2741 independent reflections |
Radiation source: fine-focus sealed tube | 2503 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 65.0°, θmin = 3.9° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −7→7 |
Tmin = 0.833, Tmax = 0.947 | k = −13→13 |
8793 measured reflections | l = −25→26 |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0422P)2 + 0.4552P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2741 reflections | Δρmax = 0.22 e Å−3 |
220 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (2) |
C20H28O4 | V = 1681.58 (3) Å3 |
Mr = 332.42 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.3684 (1) Å | µ = 0.72 mm−1 |
b = 11.6102 (1) Å | T = 100 K |
c = 22.7430 (2) Å | 0.26 × 0.18 × 0.08 mm |
Bruker SMART CCD Apex-II area-detector diffractometer | 2741 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 2503 reflections with I > 2σ(I) |
Tmin = 0.833, Tmax = 0.947 | Rint = 0.021 |
8793 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.22 e Å−3 |
S = 1.04 | Δρmin = −0.17 e Å−3 |
2741 reflections | Absolute structure: Flack (1983) |
220 parameters | Absolute structure parameter: 0.1 (2) |
0 restraints |
Experimental. 'crystal mounted on cryoloop using Paratone-N' |
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 | 1.1200 (2) | 0.61313 (11) | 0.19770 (6) | 0.0309 (3) | |
O2 | 0.4872 (2) | 0.16426 (11) | 0.19024 (6) | 0.0300 (3) | |
O3 | 0.5549 (2) | −0.35589 (12) | 0.09136 (6) | 0.0367 (4) | |
O4 | 0.4724 (2) | −0.25845 (12) | 0.17271 (6) | 0.0351 (4) | |
C1 | 0.8089 (3) | 0.35923 (16) | 0.20835 (8) | 0.0251 (4) | |
C2 | 0.8218 (3) | 0.49173 (17) | 0.20910 (9) | 0.0271 (5) | |
C3 | 1.0114 (3) | 0.53648 (16) | 0.17732 (9) | 0.0268 (4) | |
C4 | 1.0544 (3) | 0.48312 (17) | 0.11828 (9) | 0.0299 (5) | |
C5 | 1.0369 (3) | 0.35187 (16) | 0.12008 (8) | 0.0252 (4) | |
C6 | 1.0876 (3) | 0.29936 (17) | 0.06036 (8) | 0.0267 (5) | |
C7 | 1.1005 (3) | 0.16881 (17) | 0.06601 (9) | 0.0259 (4) | |
C8 | 0.8982 (3) | 0.11726 (16) | 0.09008 (8) | 0.0219 (4) | |
C9 | 0.8390 (3) | 0.17514 (16) | 0.14962 (8) | 0.0224 (4) | |
C10 | 0.8251 (3) | 0.30905 (16) | 0.14571 (8) | 0.0234 (4) | |
C11 | 0.6477 (3) | 0.11519 (16) | 0.17612 (8) | 0.0225 (4) | |
C12 | 0.6658 (3) | −0.01498 (16) | 0.18246 (8) | 0.0258 (5) | |
C13 | 0.7120 (3) | −0.06801 (16) | 0.12211 (8) | 0.0226 (4) | |
C14 | 0.9142 (3) | −0.01284 (17) | 0.09808 (8) | 0.0235 (4) | |
C15 | 0.9660 (3) | −0.08786 (16) | 0.04466 (9) | 0.0271 (5) | |
C16 | 0.9092 (3) | −0.21043 (17) | 0.06534 (9) | 0.0303 (5) | |
C17 | 0.7743 (3) | −0.19684 (16) | 0.12155 (9) | 0.0264 (5) | |
C18 | 0.5233 (3) | −0.05009 (16) | 0.08124 (9) | 0.0270 (4) | |
C19 | 0.6374 (3) | 0.34631 (17) | 0.10812 (9) | 0.0275 (5) | |
C20 | 0.5912 (3) | −0.27927 (16) | 0.12537 (8) | 0.0268 (5) | |
H1A | 0.6740 | 0.3349 | 0.2261 | 0.030* | |
H1B | 0.9238 | 0.3274 | 0.2327 | 0.030* | |
H2A | 0.6939 | 0.5238 | 0.1906 | 0.032* | |
H2B | 0.8259 | 0.5186 | 0.2504 | 0.032* | |
H4 | 0.3755 | −0.3074 | 0.1745 | 0.053* | |
H4A | 1.1974 | 0.5049 | 0.1053 | 0.036* | |
H4B | 0.9532 | 0.5138 | 0.0892 | 0.036* | |
H5 | 1.1487 | 0.3245 | 0.1476 | 0.030* | |
H6A | 1.2231 | 0.3300 | 0.0458 | 0.032* | |
H6B | 0.9770 | 0.3203 | 0.0317 | 0.032* | |
H7A | 1.1302 | 0.1350 | 0.0269 | 0.031* | |
H7B | 1.2183 | 0.1485 | 0.0925 | 0.031* | |
H8 | 0.7832 | 0.1333 | 0.0613 | 0.026* | |
H9 | 0.9582 | 0.1584 | 0.1769 | 0.027* | |
H12A | 0.5330 | −0.0468 | 0.1983 | 0.031* | |
H12B | 0.7803 | −0.0342 | 0.2102 | 0.031* | |
H14 | 1.0267 | −0.0269 | 0.1279 | 0.028* | |
H15A | 1.1167 | −0.0823 | 0.0344 | 0.033* | |
H15B | 0.8808 | −0.0651 | 0.0101 | 0.033* | |
H16A | 1.0382 | −0.2549 | 0.0741 | 0.036* | |
H16B | 0.8291 | −0.2514 | 0.0345 | 0.036* | |
H17 | 0.8672 | −0.2112 | 0.1562 | 0.032* | |
H18A | 0.3966 | −0.0813 | 0.0998 | 0.040* | |
H18B | 0.5484 | −0.0899 | 0.0439 | 0.040* | |
H18C | 0.5042 | 0.0324 | 0.0739 | 0.040* | |
H19A | 0.6502 | 0.4283 | 0.0985 | 0.041* | |
H19B | 0.5071 | 0.3333 | 0.1300 | 0.041* | |
H19C | 0.6349 | 0.3011 | 0.0717 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0297 (8) | 0.0270 (7) | 0.0333 (7) | −0.0018 (6) | 0.0090 (7) | −0.0038 (6) |
O3 | 0.0467 (10) | 0.0313 (8) | 0.0323 (8) | −0.0074 (7) | 0.0035 (7) | −0.0086 (7) |
O4 | 0.0421 (9) | 0.0305 (8) | 0.0325 (8) | −0.0126 (7) | 0.0103 (7) | −0.0076 (6) |
O1 | 0.0352 (8) | 0.0258 (7) | 0.0315 (7) | −0.0067 (6) | −0.0001 (7) | −0.0010 (6) |
C8 | 0.0211 (10) | 0.0266 (10) | 0.0178 (9) | 0.0010 (8) | −0.0002 (8) | −0.0003 (8) |
C11 | 0.0259 (11) | 0.0245 (10) | 0.0170 (9) | −0.0007 (9) | 0.0034 (8) | −0.0037 (8) |
C3 | 0.0313 (11) | 0.0209 (9) | 0.0280 (10) | 0.0025 (9) | −0.0022 (10) | 0.0028 (8) |
C12 | 0.0297 (11) | 0.0250 (10) | 0.0227 (10) | −0.0024 (9) | 0.0035 (9) | 0.0000 (8) |
C5 | 0.0248 (11) | 0.0269 (10) | 0.0238 (10) | −0.0028 (9) | 0.0003 (9) | −0.0009 (9) |
C4 | 0.0298 (11) | 0.0290 (11) | 0.0309 (11) | −0.0042 (9) | 0.0033 (10) | 0.0020 (9) |
C9 | 0.0231 (10) | 0.0246 (10) | 0.0194 (9) | −0.0011 (8) | 0.0003 (8) | 0.0003 (8) |
C14 | 0.0226 (10) | 0.0273 (10) | 0.0207 (9) | 0.0022 (8) | −0.0004 (8) | −0.0020 (8) |
C1 | 0.0266 (11) | 0.0248 (10) | 0.0237 (10) | −0.0017 (8) | 0.0027 (9) | 0.0013 (8) |
C6 | 0.0244 (10) | 0.0312 (11) | 0.0246 (10) | −0.0042 (8) | 0.0056 (9) | 0.0005 (8) |
C13 | 0.0241 (10) | 0.0238 (10) | 0.0200 (10) | −0.0021 (8) | 0.0003 (9) | −0.0012 (8) |
C20 | 0.0352 (11) | 0.0212 (10) | 0.0241 (10) | 0.0037 (9) | −0.0042 (10) | 0.0004 (9) |
C10 | 0.0239 (10) | 0.0245 (10) | 0.0216 (10) | −0.0008 (8) | 0.0003 (9) | 0.0003 (8) |
C16 | 0.0317 (11) | 0.0263 (10) | 0.0328 (11) | 0.0045 (9) | 0.0001 (10) | −0.0064 (9) |
C17 | 0.0313 (11) | 0.0238 (10) | 0.0240 (10) | 0.0039 (9) | −0.0027 (9) | −0.0022 (8) |
C7 | 0.0244 (10) | 0.0310 (10) | 0.0222 (9) | 0.0016 (9) | 0.0031 (9) | −0.0018 (8) |
C2 | 0.0317 (11) | 0.0249 (10) | 0.0245 (11) | −0.0006 (9) | 0.0010 (10) | −0.0007 (8) |
C19 | 0.0287 (11) | 0.0247 (10) | 0.0292 (11) | −0.0011 (9) | 0.0012 (9) | 0.0014 (9) |
C18 | 0.0256 (10) | 0.0247 (9) | 0.0306 (11) | 0.0005 (9) | 0.0004 (9) | −0.0010 (8) |
C15 | 0.0258 (11) | 0.0288 (10) | 0.0268 (10) | 0.0016 (9) | 0.0005 (9) | −0.0047 (8) |
O2—C11 | 1.213 (2) | C1—C10 | 1.543 (3) |
O3—C20 | 1.201 (2) | C1—H1A | 0.99 |
O4—C20 | 1.338 (2) | C1—H1B | 0.99 |
O4—H4 | 0.84 | C6—C7 | 1.523 (3) |
O1—C3 | 1.219 (2) | C6—H6A | 0.99 |
C8—C7 | 1.523 (3) | C6—H6B | 0.9900 |
C8—C14 | 1.525 (2) | C13—C18 | 1.533 (3) |
C8—C9 | 1.558 (3) | C13—C17 | 1.548 (3) |
C8—H8 | 1.0000 | C20—C17 | 1.511 (3) |
C11—C12 | 1.523 (2) | C10—C19 | 1.532 (3) |
C11—C9 | 1.527 (3) | C16—C15 | 1.542 (3) |
C3—C2 | 1.500 (3) | C16—C17 | 1.548 (3) |
C3—C4 | 1.504 (3) | C16—H16A | 0.9900 |
C12—C13 | 1.533 (2) | C16—H16B | 0.9900 |
C12—H12A | 0.9900 | C17—H17 | 1.0000 |
C12—H12B | 0.9900 | C7—H7A | 0.9900 |
C5—C6 | 1.523 (3) | C7—H7B | 0.9900 |
C5—C4 | 1.528 (3) | C2—H2A | 0.9900 |
C5—C10 | 1.551 (3) | C2—H2B | 0.9900 |
C5—H5 | 1.0000 | C19—H19A | 0.9800 |
C4—H4A | 0.99 | C19—H19B | 0.9800 |
C4—H4B | 0.99 | C19—H19C | 0.9800 |
C9—C10 | 1.560 (2) | C18—H18A | 0.9800 |
C9—H9 | 1.0000 | C18—H18B | 0.9800 |
C14—C15 | 1.531 (3) | C18—H18C | 0.9800 |
C14—C13 | 1.539 (3) | C15—H15A | 0.9900 |
C14—H14 | 1.00 | C15—H15B | 0.9900 |
C1—C2 | 1.541 (2) | ||
C20—O4—H4 | 109.5 | C12—C13—C14 | 108.15 (16) |
C7—C8—C14 | 112.07 (16) | C18—C13—C14 | 112.58 (15) |
C7—C8—C9 | 110.35 (15) | C12—C13—C17 | 116.41 (16) |
C14—C8—C9 | 109.87 (15) | C18—C13—C17 | 109.10 (15) |
C7—C8—H8 | 108.1 | C14—C13—C17 | 100.64 (16) |
C14—C8—H8 | 108.1 | O3—C20—O4 | 122.88 (19) |
C9—C8—H8 | 108.1 | O3—C20—C17 | 125.50 (19) |
O2—C11—C12 | 120.33 (17) | O4—C20—C17 | 111.61 (16) |
O2—C11—C9 | 124.22 (17) | C19—C10—C1 | 110.89 (16) |
C12—C11—C9 | 115.42 (16) | C19—C10—C5 | 112.23 (15) |
O1—C3—C2 | 121.75 (18) | C1—C10—C5 | 106.51 (15) |
O1—C3—C4 | 122.49 (19) | C19—C10—C9 | 110.94 (16) |
C2—C3—C4 | 115.73 (17) | C1—C10—C9 | 109.12 (15) |
C11—C12—C13 | 109.17 (15) | C5—C10—C9 | 106.95 (16) |
C11—C12—H12A | 109.8 | C15—C16—C17 | 106.73 (15) |
C13—C12—H12A | 109.8 | C15—C16—H16A | 110.4 |
C11—C12—H12B | 109.8 | C17—C16—H16A | 110.4 |
C13—C12—H12B | 109.8 | C15—C16—H16B | 110.4 |
H12A—C12—H12B | 108.3 | C17—C16—H16B | 110.4 |
C6—C5—C4 | 111.08 (15) | H16A—C16—H16B | 108.6 |
C6—C5—C10 | 113.01 (15) | C20—C17—C13 | 114.44 (17) |
C4—C5—C10 | 113.14 (16) | C20—C17—C16 | 114.28 (16) |
C6—C5—H5 | 106.3 | C13—C17—C16 | 104.34 (16) |
C4—C5—H5 | 106.3 | C20—C17—H17 | 107.8 |
C10—C5—H5 | 106.3 | C13—C17—H17 | 107.8 |
C3—C4—C5 | 111.93 (16) | C16—C17—H17 | 107.8 |
C3—C4—H4A | 109.2 | C8—C7—C6 | 112.06 (16) |
C5—C4—H4A | 109.2 | C8—C7—H7A | 109.2 |
C3—C4—H4B | 109.2 | C6—C7—H7A | 109.2 |
C5—C4—H4B | 109.2 | C8—C7—H7B | 109.2 |
H4A—C4—H4B | 107.9 | C6—C7—H7B | 109.2 |
C11—C9—C8 | 109.85 (15) | H7A—C7—H7B | 107.9 |
C11—C9—C10 | 115.57 (16) | C3—C2—C1 | 112.57 (16) |
C8—C9—C10 | 113.22 (15) | C3—C2—H2A | 109.1 |
C11—C9—H9 | 105.8 | C1—C2—H2A | 109.1 |
C8—C9—H9 | 105.8 | C3—C2—H2B | 109.1 |
C10—C9—H9 | 105.8 | C1—C2—H2B | 109.1 |
C8—C14—C15 | 118.91 (16) | H2A—C2—H2B | 107.8 |
C8—C14—C13 | 113.51 (16) | C10—C19—H19A | 109.5 |
C15—C14—C13 | 103.02 (16) | C10—C19—H19B | 109.5 |
C8—C14—H14 | 106.9 | H19A—C19—H19B | 109.5 |
C15—C14—H14 | 106.9 | C10—C19—H19C | 109.5 |
C13—C14—H14 | 106.9 | H19A—C19—H19C | 109.5 |
C2—C1—C10 | 112.55 (15) | H19B—C19—H19C | 109.5 |
C2—C1—H1A | 109.1 | C13—C18—H18A | 109.5 |
C10—C1—H1A | 109.1 | C13—C18—H18B | 109.5 |
C2—C1—H1B | 109.1 | H18A—C18—H18B | 109.5 |
C10—C1—H1B | 109.1 | C13—C18—H18C | 109.5 |
H1A—C1—H1B | 107.8 | H18A—C18—H18C | 109.5 |
C5—C6—C7 | 109.54 (16) | H18B—C18—H18C | 109.5 |
C5—C6—H6A | 109.8 | C14—C15—C16 | 103.45 (16) |
C7—C6—H6A | 109.8 | C14—C15—H15A | 111.1 |
C5—C6—H6B | 109.8 | C16—C15—H15A | 111.1 |
C7—C6—H6B | 109.8 | C14—C15—H15B | 111.1 |
H6A—C6—H6B | 108.2 | C16—C15—H15B | 111.1 |
C12—C13—C18 | 109.75 (16) | H15A—C15—H15B | 109.0 |
O2—C11—C12—C13 | 121.12 (19) | C4—C5—C10—C19 | 62.9 (2) |
C9—C11—C12—C13 | −57.0 (2) | C6—C5—C10—C1 | 174.01 (16) |
O1—C3—C4—C5 | 135.6 (2) | C4—C5—C10—C1 | −58.7 (2) |
C2—C3—C4—C5 | −46.1 (2) | C6—C5—C10—C9 | 57.4 (2) |
C6—C5—C4—C3 | −178.26 (17) | C4—C5—C10—C9 | −175.25 (16) |
C10—C5—C4—C3 | 53.4 (2) | C11—C9—C10—C19 | −59.5 (2) |
O2—C11—C9—C8 | −124.94 (19) | C8—C9—C10—C19 | 68.4 (2) |
C12—C11—C9—C8 | 53.1 (2) | C11—C9—C10—C1 | 63.0 (2) |
O2—C11—C9—C10 | 4.6 (3) | C8—C9—C10—C1 | −169.09 (16) |
C12—C11—C9—C10 | −177.30 (16) | C11—C9—C10—C5 | 177.82 (15) |
C7—C8—C9—C11 | −174.74 (15) | C8—C9—C10—C5 | −54.2 (2) |
C14—C8—C9—C11 | −50.7 (2) | O3—C20—C17—C13 | 125.6 (2) |
C7—C8—C9—C10 | 54.4 (2) | O4—C20—C17—C13 | −55.6 (2) |
C14—C8—C9—C10 | 178.48 (16) | O3—C20—C17—C16 | 5.3 (3) |
C7—C8—C14—C15 | −58.4 (2) | O4—C20—C17—C16 | −175.78 (16) |
C9—C8—C14—C15 | 178.58 (16) | C12—C13—C17—C20 | 80.9 (2) |
C7—C8—C14—C13 | −179.75 (15) | C18—C13—C17—C20 | −44.0 (2) |
C9—C8—C14—C13 | 57.2 (2) | C14—C13—C17—C20 | −162.55 (16) |
C4—C5—C6—C7 | 171.63 (16) | C12—C13—C17—C16 | −153.51 (17) |
C10—C5—C6—C7 | −60.0 (2) | C18—C13—C17—C16 | 81.65 (19) |
C11—C12—C13—C18 | −65.9 (2) | C14—C13—C17—C16 | −36.94 (19) |
C11—C12—C13—C14 | 57.2 (2) | C15—C16—C17—C20 | 139.58 (17) |
C11—C12—C13—C17 | 169.56 (17) | C15—C16—C17—C13 | 13.9 (2) |
C8—C14—C13—C12 | −60.6 (2) | C14—C8—C7—C6 | −177.68 (16) |
C15—C14—C13—C12 | 169.52 (15) | C9—C8—C7—C6 | −54.9 (2) |
C8—C14—C13—C18 | 60.9 (2) | C5—C6—C7—C8 | 57.6 (2) |
C15—C14—C13—C18 | −69.05 (19) | O1—C3—C2—C1 | −135.7 (2) |
C8—C14—C13—C17 | 176.89 (15) | C4—C3—C2—C1 | 46.0 (2) |
C15—C14—C13—C17 | 46.97 (18) | C10—C1—C2—C3 | −52.8 (2) |
C2—C1—C10—C19 | −64.6 (2) | C8—C14—C15—C16 | −165.08 (17) |
C2—C1—C10—C5 | 57.8 (2) | C13—C14—C15—C16 | −38.54 (19) |
C2—C1—C10—C9 | 172.95 (16) | C17—C16—C15—C14 | 15.0 (2) |
C6—C5—C10—C19 | −64.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.84 | 1.94 | 2.7537 (18) | 162 |
C19—H19A···O3ii | 0.98 | 2.58 | 3.518 (2) | 159 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C20H28O4 |
Mr | 332.42 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 6.3684 (1), 11.6102 (1), 22.7430 (2) |
V (Å3) | 1681.58 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.26 × 0.18 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD Apex-II area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.833, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8793, 2741, 2503 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.085, 1.04 |
No. of reflections | 2741 |
No. of parameters | 220 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.17 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.1 (2) |
Computer programs: SMART WNT/2000 (Bruker, 2000), SMART WNT/2000, SAINT-Plus (Bruker,2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker,2000), SHELXTL.
O3—C20 | 1.201 (2) | O4—C20 | 1.338 (2) |
O3—C20—C17 | 125.50 (19) | O4—C20—C17 | 111.61 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.84 | 1.94 | 2.7537 (18) | 162 |
C19—H19A···O3ii | 0.98 | 2.58 | 3.518 (2) | 159 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
For our study of hydrogen-bonding modes in crystalline keto acids, steroid examples are of special value as molecularly rigid single enantiomers with the potential to bear multiple ketone receptors. The title compound, (I), supplements our previous reports on steroidal diketo acids (Thompson et al., 2001; Lalancette & Thompson, 2003; Kikolski et al., 2006). Compound (I) is distantly related to the surfactant steroidal acids isolatable from vertebrate bile, but is directly derived from (+)-3,11-dioxoandrost-4-ene-17β-carboxylic acid, whose structure we have also published (Newman et al., 2002) and which served as its synthetic source (Experimental).
Fig. 1 shows the asymmetric unit for (I), which is conformationally rigid, with significant rotational options only at the carboxyl group attached at atom C17. The O3—C20—C17—C16 torsion angle is 5.3 (3)°.
Full or partial averaging of C—O bond lengths and C—C—O angles by disorder is often seen in dimeric carboxylic acids, but not in other hydrogen-bonding modes, whose geometry cannot support the averaging mechanisms. Because (I) is found to aggregate catemerically (see below), the values in (I) are comparable to those typical of highly ordered dimeric carboxyls (Borthwick, 1980) (see Table 1).
Fig. 2 shows the packing of the cell and includes extra molecules to illustrate the translational acid-to-ketone hydrogen-bonding scheme. Each carboxylic acid group is linked to the 3-ketone in the A ring of a molecule translationally related in both the a and the b directions, with the C-ring ketone not involved in the hydrogen bonding. Four hydrogen-bonding chains pass through the cell, the order of their directional alignments along c being −a-b, +a-b, +a + b, −a + b. Within the 2.7 Å range we standardly survey for non-bonded C—H···O packing interactions (Steiner, 1997); a single 2.58 Å intermolecular close contact was found, connecting atom O3 with a C19 methyl H atom in a translationally related molecule (Table 2).
We characterize the geometry of hydrogen bonding to carbonyls using a combination of H···O=C angle and H···O=C—C torsion angle. These describe the approach of the acid H atom to the receptor O atom in terms of its deviation from, respectively, C=O axiality (ideal = 120°) and planarity with the carbonyl (ideal = 0°). In (I), these two angles are 136 and −2.3°.
There is a very strong similarity in both molecular shape and carboxyl conformation between (I) and the Δ4 enone from which it was derived (Newman et al., 2002). The only significant difference appears to be the flattening that occurs in the enone around C4 and C5 as a result of their sp2-hybridization. It is therefore not surprising that both molecules aggregate similarly, as translational catemers. Despite these similarities, the packing arrangements for the two compounds are quite different, with the enone crystallizing in a monoclinic cell (P21, Z = 2), while (I) crystallizes in an orthorhombic system (P212121, Z = 4).
The solid-state (KBr) IR spectrum of (I) has C═O absorptions at 1731 and 1704 cm−1, with a peak separation typical of the shifts seen in catemers, due, respectively, to removal of hydrogen bonding from the acid C═O group and addition of hydrogen bonding to the ketone. In CHCl3 solution, where dimers predominate, these coalesce to a single peak at 1705 cm−1.