17-Oxo-5[alpha]-androstane-3[alpha],4[beta]-diyl diacetate and 17-oxo-5[beta]-androstane-3[alpha],4[beta]-diyl diacetate

The title compounds, both C₂₃H₃₄O₅, are the 5[alpha] and 5[beta] configurations of two diacetate epimers. The 5[beta]-diacetate crystallizes in an hexagonal structure, unusual for steroid molecules. The unit cell has an accessible solvent volume of 358 Å³, responsible for clathrate behaviour. The 5[beta]-epimer also features some shorter than average bond lengths in the 3[alpha],4[beta]-acetoxy groups. The conformations of the molecules of both epimers are compared with those obtained through ab initio quantum chemistry calculations. Cohesion of the crystals can be attributed to van der Waals and weak molecular C-H...O interactions.

S1. Comment

The title compounds, (I) and (II), are the diacetate forms of 3α,4β-dihydroxy-5β-androstan-17-one (Andrade et al., 2003) and 3α,4β-dihydroxy-5α-androstan-17-one (Paixão, Andrade, de Almeida, Costa et al., 1998), respectively. These diols have been prepared as new key intermediates in recently developed strategies for the syntheses of formestane (Tavares da Silva et al., 1996, 2002), a potent aromatase inhibitor clinically used as an antitumor agent in the treatment of estrogen-dependent breast cancers, and of related ring-D lactone derivates (Andrade et al., 1999; Tavares da Silva et al., 1997; Paixão, Andrade, de Almeida, Tavares da Silva et al., 1998). Following our work on the determination of the molecular and crystal structures of potential aromatase inhibitors and intermediates of their syntheses, the present X-ray analysis aims to contribute to the elucidation of the different reactivities of the precursors of the above-mentioned intermediates (Tavares da Silva et al., 2002).

ORTEPII (Johnson, 1976) drawings of the molecules of 17-oxo-5α-androstane-3α,4β-diyl diacetate, (I), and 17-oxo-5β-androstane-3α,4β-diyl diacetate, (II), with the corresponding atomic numbering schemes and ring labels are shown in Figs. 1 and 2. The 5β diacetate (II) crystallizes in a hexagonal structure, space group P6₅. During structure analysis it became evident that the hexagonal symmetry, most unusual for this type of compound creates large accessible voids in the crystal structure that tend to host disordered solvent molecules. Crystals from two samples, A and B, prepared with different solvents were used to collect crystal data, but both evidenced the same chlatrate behavior. This affects the diffraction pattern mostly at low scattering angles; this diffuse scattering effect was corrected with the SQUEEZE program (Spek, 2003). The reported X-ray results for this compound were obtained with a crystal from sample A, grown from diethyl ether/diisopropyl ether solution.

For both molecules under study, most bond lengths and angles are within the expected ranges (Allen et al., 1987) [average values Csp³—Csp³ = 1.532 (11) and 1.530 (14) Å, Csp³—Csp² = 1.501 (15) and 1.502 (6) Å, C═O = 1.197 (6) and 1.195 (20) Å, Csp³—O = 1.457 (1) and 1.451 (3) Å, and Csp²—O = 1.349 (3) and 1.316 (2) Å, respectively, for the molecules of (I) and (II)]. The short C2—C3 bond lengths [1.511 (5) and 1.502 (5) Å, respectively, for the molecules of (I) and (II)] common to other related steroids were also found in this study. Compound (II) contains a very short C20═O20 bond, of 1.161 (5) Å, and a significantly shorter than average distance for both Csp²—O bonds. This short C20═O20 bond distance is probably an artifact of the relatively large anisotropic displacement tensor of atom O20. The distances between the terminal atoms are 11.040 (5) and 10.95 (5) Å (O20···O17), and 10.684 (5) and 8.501 (5) Å (O22···C17), for the two molecules. The C19—C10—C13—C18 pseudo-torsion angles are 0.6 (3) and 0.6 (4)° for molecules (I) and (II), showing that the steroid nuclei are essentially untwisted. Rings A, B and C have slightly flattened chair conformations, with average torsion angles of 52 (2), 56 (3) and 56 (2)°, respectively, for molecule (I), and 56 (2), 54.5 (2) and 55 (2)° for molecule (II); the presence of the acetoxy groups bonded to atoms C3 and C4 does not disturb the usual chair conformation of ring A of the steroid nucleus. The A/B ring junction is −5α,10β-quasi-trans [C1—C10—C5—C4 = −50.9 (4)° and C9—C10—C5—C6 = 59.4 (4)°] for molecule (I) and 5β,10β-quasi-cis [C1—C10—C5—C4 = 49.6 (4)° and C9—C10—C5—C6 = 53.8 (3)°], with a bowing angle of 67.5 (1)°, for molecule (II). Both five-membered rings D assume a conformation intermediate between a 14α-envelope and a 13β,14α-half-chair, being closer to the second in molecule (I) and to the first in molecule (II) [puckering parameters (Cremer & Pople, 1975; Boeyens, 1978), calculated using the atom sequence C13–C17: q₂ = 0.434 (4) and 0.421 (5) Å, ϕ₂ = 205.2 (5) and 208.0 (7)°; pseudo-rotation (Altona et al., 1968) and asymmetry parameters: Δ = −13.8 (7) and −18.8 (7)°, ϕ_m = 44.5 (4) and 43.4 (3)°, ΔC_s(13) = 23.4 (4) and 24.5 (4)°, ΔC_s(14) = 10.4 (4) and 7.8 (4)° and ΔC₂(13,14) = 8.3 (4) and 11.1 (4)°, respectively, for molecules (I) and (II)]. The environment around atom C17 is planar [the sum of the valence angles is 360.0 (6)° in (I) and 360.0 (7) in (II)]. For the 5α molecule (I), the two 3α,4β ring substituents are axial (Luger & Bulow, 1983), with angles of 4.9 (2) and 8.3 (2)°, respectively, being equatorial, with angles of 68.4 (2) and 62.4 (2)°, respectively, for the 5β-one epimer (II). The acetoxy groups attached to ring A are planar [the sums of the valence angles around atoms C20 and C22 are all equal to 360.0 within the s.u. values]. For molecule (I), the angles subtended by the C3/O3/C20/O20/C21 and C4/O4/C22/O22/C23 least-square planes to the C1–C17 reference plane are 89.44 (13) and 72.17 (12)°, respectively, and the angle between these two planes is 67.84 (12)°, showing a twist of the two groups; for molecule (II), the angles between the acetoxy least-square planes and the plane of ring A are 82.1 (17) and 88.27 (13)°, respectively, and the angle between those two planes is 51.17 (18)°.

In order to infer whether the peculiarities of the 3α,4β-substituent bond lengths of (II) are intrinsic to the molecular configuration or solid state effects, a quantum chemistry calculation of the optimized geometry of the isolated molecules of (I) and (II) was performed using the computer program GAMESS (Schmidt et al., 1993). The Roothaan Hartree–Fock molecular orbital (MO) method was used for the ab-initio calculations. An extended 6–31 G(d,p) basis set was used with tight conditions for convergence of both the self-consistent field (SCF) cycles and the maximum energy and density gradients at the final optimized geometry (10⁻⁵ atomic units). The code was run in parallel on cluster of 12 Compac XP1000 workstations (Alpha EV67 processors, 667 MHz) running Linux.

The conformations of the steroid nuclei determined from the X-ray diffraction are well reproduced by the ab-initio MO calculations [(II): C4—C5—C6—C7: calculated 72.06, observed 73.1 (4)°; O3—C3—C4—O4: calculated −65.1, observed −66.9°]. The bond angles and lengths are also well reproduced by the calculations; however they predict for both epimers Csp²—O bond lengths that are closer to the values observed for the 5β epimer [O3—C20 calculated (I) 1.329, (II) 1.329 Å; O4—C22 (I) 1.331; (II) 1.328 Å]. The calculated values of the carbonyl C17═O17, C20═ O20 and C22═O22 bonds are 1.19 Å for both epimers.

Owing to the absence of any strong donor group, cohesion of these structures is mainly achieved by van der Waals interactions and weak hydrogen bonds involving C–H groups. Indeed, in both compounds, a few short contacts with suitable geometry to be classified as potential weak hydrogen bonds can be identified between the methylene H atoms of the acetoxy groups and the carbonyl O atoms attached to either ring D or the acetoxy group of a neighbouring molecule.

S2. Experimental

To prepare the title compound, 3α,4β-dihydroxy-5β-androstan-17-one (33.5 mg, 0.11 mmol) was dissolved in dry pyridine (1.5 ml), and acetic anhydride (0.3 ml) was added. After 120 h of stirring at room temperature, the solution was diluted with dichloromethane (100 ml), and the organic phase was washed with 10% aqueous hydrochloric acid (3 × 100 ml), 10% sodium hydrogen carbonate (2 × 100 ml) and water (2 × 100 ml), dried, and evaporated to dryness to give 5β-androstan-17-one-3α,4β-diyl diacetate (36.5 mg, 86%). ¹H NMR (300 MHz, CDCl₃, Me₄Si): δ_H 0.85 (3H, s, 19-H₃), 1.02 (3H, s, 18-H₃), 2.01 (3H, s, COCH₃), 2.04 (3H, s, COCH₃), 2.44 (1H, dd, J16β,16α = 19.0 Hz, J16β,15β = 8.0 Hz, 16β-H), 4.79 (1H, ddd, J3β,2α = 12.5 Hz, J3β,4α = 9.5 Hz, J3β,2α = 5.0 Hz, 3β-H), 5.38 (1H, dd, J4α,5β = 11.0 Hz, J4α,3β = 9.5 Hz, 4α-H); ¹³C NMR (75.6 MHz, CDCl₃, Me₄Si): δ_C 13.8, 20.1, 20.9, 21.1, 21.2, 21.7, 23.3, 24.8, 25.0, 31.0, 31.6, 34.1, 35.0, 35.9, 37.0, 42.2, 46.9, 51.2, 71.4, 75.8, 170.6, 170.8, 221.1. Crystals of samples A and B suitable for X-ray analysis were obtained by slow evaporation of solutions of the steroid in diethyl ether/diisopropyl ether and in acetone/n-hexane, respectively. The treatment of 3α,4β-dihydroxy-5α-androstan-17-one with the same conditions as described above gives an identical yield of the 3α,4β-diacetate derivative 5α-androstan-17-one-3α,4β-diyl diacetate. ¹H NMR (300 MHz, CDCl₃, Me₄Si): δ_H 0.86 (3H, s, 19-H₃), 1.02 (3H, s, 18-H₃), 2.07 (3H, s, COCH₃), 2.08 (3H, s, COCH₃), 2.45 (1H, dd, J16β,16α = 19.0 Hz, J16β,15β = 9.0 Hz, 16β-H), 4.84 (2H, m, 3-H, 4-H); ¹³C NMR (75.6 MHz, CDCl₃, Me₄Si): δ_C 13.6, 13.8, 19.6, 21.1, 21.3, 21.7, 22.2, 24.4, 31.0, 31.4, 32.0, 34.8, 35.7, 35.8, 44.0, 47.7, 51.5, 55.0, 69.4, 73.2, 169.8, 169.9, 221.3. Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the steroid in diethyl ether/diisopropyl ether.

S3. Refinement

All H atoms were refined as riding on their parent atoms using SHELXL97 defaults [C—H = 0.96–0.98 Å, and U_iso = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) for the other H atoms]. Owing to the absence of any significant anomalous scatterers, the absolute configuration of the molecules was not determined from the X-ray data but was known from the synthesis route. Therefore, Friedel pairs were merged before the refinement and the absolute configuration was assigned to correspond with that of the known chiral centers in the precursor molecule, which remained unchanged during the synthesis of compounds (I) and (II). A correction for diffuse effects due to the inclusion of disordered solvent molecules in the crystal structure was made for (I) using the SQUEEZE option of PLATON (van der Sluis & Spek, 1990; Spek, 2003). The total potential solvent volume per unit cell was calculated to be 358 ų (9.9% of the cell volume). The main void is located around the origin (0.000, 0.000, −0.038) corresponding to a volume of 356.3 ų and a diffuse electron count of 8.9 electrons as determined by the SQUEEZE procedure.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: HELENA for (I); ORTEPII (Johnson, 1976) for (II). For both compounds, software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) 17-Oxo-5α-androstane-3α,4β-diyl diacetate

Crystal data

C23H34O5	F(000) = 848
Mr = 390.50	Dx = 1.220 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 6.742 (7) Å	θ = 4.8–9.3°
b = 12.174 (4) Å	µ = 0.08 mm^−1
c = 25.893 (6) Å	T = 293 K
V = 2125 (2) Å^3	Plate, colourless
Z = 4	0.50 × 0.45 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.035
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 3.1°
Graphite monochromator	h = −8→8
ω–2θ scans	k = −15→15
5566 measured reflections	l = −33→33
2812 independent reflections	3 standard reflections every 200 min
1613 reflections with I > 2σ(I)	intensity decay: 5.4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.8677P] where P = (Fo^2 + 2Fc^2)/3
2812 reflections	(Δ/σ)max = 0.047
257 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O3	0.3026 (4)	0.4847 (2)	0.95223 (9)	0.0557 (6)
O4	−0.1361 (3)	0.63468 (19)	0.91701 (10)	0.0555 (6)
O17	0.5712 (5)	0.4909 (2)	0.60155 (13)	0.0941 (11)
O20	0.2409 (5)	0.3618 (3)	1.01471 (11)	0.0841 (10)
O22	−0.0785 (5)	0.8036 (2)	0.94799 (13)	0.0818 (9)
C1	0.1129 (6)	0.4077 (3)	0.85417 (13)	0.0529 (9)
H1A	0.0577	0.3487	0.8335	0.064*
H1B	0.2539	0.3942	0.8578	0.064*
C2	0.0173 (6)	0.4050 (3)	0.90745 (14)	0.0564 (10)
H2A	−0.1254	0.4114	0.9037	0.068*
H2B	0.0455	0.3349	0.9236	0.068*
C3	0.0913 (5)	0.4964 (3)	0.94194 (14)	0.0527 (9)
H3	0.0174	0.4962	0.9745	0.063*
C4	0.0749 (5)	0.6084 (3)	0.91636 (14)	0.0502 (9)
H4	0.1466	0.6626	0.9372	0.060*
C5	0.1574 (5)	0.6096 (2)	0.86162 (12)	0.0452 (8)
H5	0.2995	0.5953	0.8658	0.054*
C6	0.1475 (6)	0.7228 (2)	0.83641 (13)	0.0495 (9)
H6A	0.0109	0.7405	0.8282	0.059*
H6B	0.1969	0.7779	0.8602	0.059*
C7	0.2719 (6)	0.7238 (2)	0.78729 (13)	0.0513 (9)
H7A	0.2546	0.7940	0.7701	0.062*
H7B	0.4107	0.7170	0.7966	0.062*
C8	0.2188 (5)	0.6325 (2)	0.74979 (12)	0.0429 (8)
H8	0.0857	0.6465	0.7361	0.051*
C9	0.2194 (5)	0.5195 (2)	0.77653 (12)	0.0434 (8)
H9	0.3549	0.5089	0.7893	0.052*
C10	0.0834 (5)	0.5167 (3)	0.82541 (13)	0.0434 (8)
C11	0.1820 (6)	0.4252 (3)	0.73848 (13)	0.0549 (10)
H11A	0.0469	0.4301	0.7258	0.066*
H11B	0.1956	0.3558	0.7565	0.066*
C12	0.3257 (6)	0.4268 (3)	0.69220 (14)	0.0562 (10)
H12A	0.4596	0.4124	0.7041	0.067*
H12B	0.2894	0.3695	0.6680	0.067*
C13	0.3187 (5)	0.5370 (3)	0.66553 (13)	0.0490 (8)
C14	0.3651 (5)	0.6281 (2)	0.70455 (13)	0.0464 (8)
H14	0.4933	0.6083	0.7198	0.056*
C15	0.4054 (6)	0.7289 (3)	0.67123 (15)	0.0594 (10)
H15A	0.4829	0.7830	0.6899	0.071*
H15B	0.2828	0.7624	0.6596	0.071*
C16	0.5235 (6)	0.6808 (3)	0.62555 (16)	0.0663 (11)
H16A	0.4796	0.7128	0.5932	0.080*
H16B	0.6642	0.6950	0.6297	0.080*
C17	0.4818 (6)	0.5582 (3)	0.62657 (17)	0.0618 (11)
C18	0.1199 (6)	0.5530 (3)	0.63688 (15)	0.0632 (11)
H18A	0.1224	0.6214	0.6184	0.076*
H18B	0.0133	0.5540	0.6614	0.076*
H18C	0.1004	0.4937	0.6130	0.076*
C19	−0.1371 (5)	0.5297 (3)	0.80993 (14)	0.0564 (10)
H19A	−0.1751	0.4699	0.7878	0.068*
H19B	−0.1548	0.5979	0.7920	0.068*
H19C	−0.2182	0.5292	0.8404	0.068*
C20	0.3551 (6)	0.4167 (3)	0.99094 (14)	0.0576 (10)
C21	0.5746 (6)	0.4199 (4)	0.99988 (17)	0.0746 (13)
H21A	0.6019	0.4586	1.0314	0.090*
H21B	0.6379	0.4570	0.9716	0.090*
H21C	0.6247	0.3463	1.0023	0.090*
C22	−0.1933 (6)	0.7342 (3)	0.93472 (14)	0.0562 (10)
C23	−0.4110 (6)	0.7443 (3)	0.93425 (17)	0.0694 (12)
H23A	−0.4476	0.8188	0.9418	0.083*
H23B	−0.4667	0.6964	0.9599	0.083*
H23C	−0.4606	0.7243	0.9008	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0490 (14)	0.0636 (15)	0.0544 (14)	−0.0013 (13)	0.0008 (12)	0.0122 (13)
O4	0.0437 (14)	0.0567 (14)	0.0660 (15)	0.0011 (12)	0.0019 (13)	−0.0121 (13)
O17	0.093 (2)	0.0694 (18)	0.119 (3)	−0.0044 (19)	0.049 (2)	−0.0211 (19)
O20	0.090 (2)	0.096 (2)	0.0665 (18)	−0.0169 (19)	0.0015 (18)	0.0296 (17)
O22	0.079 (2)	0.0588 (16)	0.107 (2)	0.0063 (17)	−0.020 (2)	−0.0233 (17)
C1	0.056 (2)	0.0397 (17)	0.063 (2)	−0.0078 (18)	−0.0006 (19)	0.0020 (16)
C2	0.060 (2)	0.0452 (18)	0.064 (2)	−0.0079 (18)	0.006 (2)	0.0056 (17)
C3	0.049 (2)	0.058 (2)	0.051 (2)	−0.0039 (18)	0.0015 (17)	0.0038 (17)
C4	0.044 (2)	0.0499 (19)	0.056 (2)	−0.0016 (16)	−0.0038 (18)	−0.0048 (17)
C5	0.041 (2)	0.0394 (17)	0.0548 (19)	−0.0006 (15)	−0.0039 (17)	−0.0026 (14)
C6	0.052 (2)	0.0388 (16)	0.058 (2)	−0.0011 (16)	−0.0033 (18)	−0.0042 (16)
C7	0.054 (2)	0.0330 (16)	0.067 (2)	−0.0024 (17)	−0.002 (2)	0.0020 (16)
C8	0.0410 (18)	0.0370 (16)	0.0507 (18)	−0.0011 (16)	−0.0065 (17)	0.0023 (15)
C9	0.0438 (17)	0.0335 (15)	0.0530 (19)	0.0006 (15)	−0.0070 (16)	−0.0006 (15)
C10	0.0423 (18)	0.0373 (16)	0.0507 (19)	−0.0037 (16)	−0.0037 (17)	−0.0011 (15)
C11	0.067 (3)	0.0377 (17)	0.060 (2)	−0.0085 (19)	0.001 (2)	−0.0006 (16)
C12	0.064 (3)	0.0379 (18)	0.067 (2)	−0.0005 (19)	0.003 (2)	−0.0095 (17)
C13	0.047 (2)	0.0444 (18)	0.056 (2)	−0.0027 (16)	0.0024 (18)	−0.0037 (16)
C14	0.0391 (19)	0.0367 (16)	0.063 (2)	0.0005 (16)	−0.0019 (17)	0.0014 (16)
C15	0.061 (2)	0.0462 (19)	0.071 (3)	−0.0030 (19)	0.004 (2)	0.0021 (18)
C16	0.066 (3)	0.055 (2)	0.078 (3)	−0.008 (2)	0.016 (2)	0.001 (2)
C17	0.057 (2)	0.056 (2)	0.072 (3)	−0.001 (2)	0.008 (2)	−0.008 (2)
C18	0.061 (2)	0.072 (3)	0.057 (2)	−0.008 (2)	−0.006 (2)	−0.005 (2)
C19	0.047 (2)	0.056 (2)	0.066 (2)	−0.0066 (19)	−0.0040 (18)	−0.0080 (18)
C20	0.068 (3)	0.061 (2)	0.044 (2)	0.001 (2)	0.002 (2)	0.0078 (18)
C21	0.061 (3)	0.094 (3)	0.069 (3)	0.011 (3)	−0.002 (2)	0.018 (3)
C22	0.067 (3)	0.054 (2)	0.047 (2)	0.005 (2)	−0.002 (2)	−0.0026 (18)
C23	0.061 (3)	0.075 (3)	0.073 (3)	0.015 (2)	0.011 (2)	0.007 (2)

Geometric parameters (Å, º)

O3—C20	1.347 (4)	C10—C19	1.548 (5)
O3—C3	1.456 (4)	C11—C12	1.541 (5)
O4—C22	1.352 (4)	C11—H11A	0.9700
O4—C4	1.458 (4)	C11—H11B	0.9700
O17—C17	1.206 (4)	C12—C13	1.509 (5)
O20—C20	1.191 (5)	C12—H12A	0.9700
O22—C22	1.196 (4)	C12—H12B	0.9700
C1—C2	1.523 (5)	C13—C17	1.515 (5)
C1—C10	1.534 (4)	C13—C14	1.532 (4)
C1—H1A	0.9700	C13—C18	1.544 (5)
C1—H1B	0.9700	C14—C15	1.524 (5)
C2—C3	1.511 (5)	C14—H14	0.9800
C2—H2A	0.9700	C15—C16	1.541 (5)
C2—H2B	0.9700	C15—H15A	0.9700
C3—C4	1.520 (5)	C15—H15B	0.9700
C3—H3	0.9800	C16—C17	1.519 (5)
C4—C5	1.523 (5)	C16—H16A	0.9700
C4—H4	0.9800	C16—H16B	0.9700
C5—C6	1.526 (4)	C18—H18A	0.9600
C5—C10	1.552 (4)	C18—H18B	0.9600
C5—H5	0.9800	C18—H18C	0.9600
C6—C7	1.523 (5)	C19—H19A	0.9600
C6—H6A	0.9700	C19—H19B	0.9600
C6—H6B	0.9700	C19—H19C	0.9600
C7—C8	1.519 (4)	C20—C21	1.499 (6)
C7—H7A	0.9700	C21—H21A	0.9600
C7—H7B	0.9700	C21—H21B	0.9600
C8—C14	1.532 (5)	C21—H21C	0.9600
C8—C9	1.541 (4)	C22—C23	1.473 (6)
C8—H8	0.9800	C23—H23A	0.9600
C9—C11	1.533 (4)	C23—H23B	0.9600
C9—C10	1.563 (5)	C23—H23C	0.9600
C9—H9	0.9800
C20—O3—C3	116.9 (3)	C12—C11—H11B	109.0
C22—O4—C4	118.6 (3)	H11A—C11—H11B	107.8
C2—C1—C10	113.8 (3)	C13—C12—C11	110.3 (3)
C2—C1—H1A	108.8	C13—C12—H12A	109.6
C10—C1—H1A	108.8	C11—C12—H12A	109.6
C2—C1—H1B	108.8	C13—C12—H12B	109.6
C10—C1—H1B	108.8	C11—C12—H12B	109.6
H1A—C1—H1B	107.7	H12A—C12—H12B	108.1
C3—C2—C1	112.3 (3)	C12—C13—C17	115.7 (3)
C3—C2—H2A	109.1	C12—C13—C14	109.6 (3)
C1—C2—H2A	109.1	C17—C13—C14	99.6 (3)
C3—C2—H2B	109.1	C12—C13—C18	111.0 (3)
C1—C2—H2B	109.1	C17—C13—C18	106.8 (3)
H2A—C2—H2B	107.9	C14—C13—C18	113.7 (3)
O3—C3—C2	111.1 (3)	C15—C14—C8	121.3 (3)
O3—C3—C4	103.8 (3)	C15—C14—C13	104.2 (3)
C2—C3—C4	112.3 (3)	C8—C14—C13	113.5 (3)
O3—C3—H3	109.9	C15—C14—H14	105.5
C2—C3—H3	109.9	C8—C14—H14	105.5
C4—C3—H3	109.9	C13—C14—H14	105.5
O4—C4—C3	105.2 (3)	C14—C15—C16	102.8 (3)
O4—C4—C5	111.4 (3)	C14—C15—H15A	111.2
C3—C4—C5	112.8 (3)	C16—C15—H15A	111.2
O4—C4—H4	109.1	C14—C15—H15B	111.2
C3—C4—H4	109.1	C16—C15—H15B	111.2
C5—C4—H4	109.1	H15A—C15—H15B	109.1
C4—C5—C6	113.0 (3)	C17—C16—C15	105.3 (3)
C4—C5—C10	116.0 (3)	C17—C16—H16A	110.7
C6—C5—C10	112.7 (3)	C15—C16—H16A	110.7
C4—C5—H5	104.6	C17—C16—H16B	110.7
C6—C5—H5	104.6	C15—C16—H16B	110.7
C10—C5—H5	104.6	H16A—C16—H16B	108.8
C7—C6—C5	109.9 (3)	O17—C17—C13	127.2 (4)
C7—C6—H6A	109.7	O17—C17—C16	124.5 (4)
C5—C6—H6A	109.7	C13—C17—C16	108.3 (3)
C7—C6—H6B	109.7	C13—C18—H18A	109.5
C5—C6—H6B	109.7	C13—C18—H18B	109.5
H6A—C6—H6B	108.2	H18A—C18—H18B	109.5
C8—C7—C6	113.5 (3)	C13—C18—H18C	109.5
C8—C7—H7A	108.9	H18A—C18—H18C	109.5
C6—C7—H7A	108.9	H18B—C18—H18C	109.5
C8—C7—H7B	108.9	C10—C19—H19A	109.5
C6—C7—H7B	108.9	C10—C19—H19B	109.5
H7A—C7—H7B	107.7	H19A—C19—H19B	109.5
C7—C8—C14	111.3 (3)	C10—C19—H19C	109.5
C7—C8—C9	111.5 (3)	H19A—C19—H19C	109.5
C14—C8—C9	108.1 (3)	H19B—C19—H19C	109.5
C7—C8—H8	108.6	O20—C20—O3	124.1 (4)
C14—C8—H8	108.6	O20—C20—C21	125.0 (4)
C9—C8—H8	108.6	O3—C20—C21	111.0 (3)
C11—C9—C8	112.3 (3)	C20—C21—H21A	109.5
C11—C9—C10	114.0 (3)	C20—C21—H21B	109.5
C8—C9—C10	112.4 (3)	H21A—C21—H21B	109.5
C11—C9—H9	105.7	C20—C21—H21C	109.5
C8—C9—H9	105.7	H21A—C21—H21C	109.5
C10—C9—H9	105.7	H21B—C21—H21C	109.5
C1—C10—C19	109.8 (3)	O22—C22—O4	123.1 (4)
C1—C10—C5	107.2 (3)	O22—C22—C23	126.1 (4)
C19—C10—C5	113.0 (3)	O4—C22—C23	110.9 (4)
C1—C10—C9	109.6 (3)	C22—C23—H23A	109.5
C19—C10—C9	110.6 (3)	C22—C23—H23B	109.5
C5—C10—C9	106.5 (3)	H23A—C23—H23B	109.5
C9—C11—C12	112.7 (3)	C22—C23—H23C	109.5
C9—C11—H11A	109.0	H23A—C23—H23C	109.5
C12—C11—H11A	109.0	H23B—C23—H23C	109.5
C9—C11—H11B	109.0
C10—C1—C2—C3	−57.1 (4)	C8—C9—C10—C19	66.5 (4)
C20—O3—C3—C2	−83.9 (4)	C11—C9—C10—C5	174.1 (3)
C20—O3—C3—C4	155.3 (3)	C8—C9—C10—C5	−56.6 (3)
C1—C2—C3—O3	−63.7 (4)	C8—C9—C11—C12	53.6 (4)
C1—C2—C3—C4	52.0 (4)	C10—C9—C11—C12	−177.0 (3)
C22—O4—C4—C3	130.6 (3)	C9—C11—C12—C13	−54.7 (4)
C22—O4—C4—C5	−106.8 (4)	C11—C12—C13—C17	167.8 (3)
O3—C3—C4—O4	−166.5 (3)	C11—C12—C13—C14	56.2 (4)
C2—C3—C4—O4	73.5 (4)	C11—C12—C13—C18	−70.3 (4)
O3—C3—C4—C5	71.9 (4)	C7—C8—C14—C15	−54.9 (4)
C2—C3—C4—C5	−48.2 (4)	C9—C8—C14—C15	−177.6 (3)
O4—C4—C5—C6	63.8 (4)	C7—C8—C14—C13	179.8 (3)
C3—C4—C5—C6	−178.1 (3)	C9—C8—C14—C13	57.1 (4)
O4—C4—C5—C10	−68.5 (4)	C12—C13—C14—C15	166.0 (3)
C3—C4—C5—C10	49.6 (4)	C17—C13—C14—C15	44.2 (4)
C4—C5—C6—C7	167.6 (3)	C18—C13—C14—C15	−69.0 (4)
C10—C5—C6—C7	−58.5 (4)	C12—C13—C14—C8	−60.0 (4)
C5—C6—C7—C8	53.5 (4)	C17—C13—C14—C8	178.2 (3)
C6—C7—C8—C14	−172.6 (3)	C18—C13—C14—C8	64.9 (4)
C6—C7—C8—C9	−51.9 (4)	C8—C14—C15—C16	−168.9 (3)
C7—C8—C9—C11	−175.6 (3)	C13—C14—C15—C16	−39.5 (4)
C14—C8—C9—C11	−53.0 (4)	C14—C15—C16—C17	18.5 (4)
C7—C8—C9—C10	54.2 (4)	C12—C13—C17—O17	27.6 (6)
C14—C8—C9—C10	176.8 (3)	C14—C13—C17—O17	144.9 (5)
C2—C1—C10—C19	−69.2 (4)	C18—C13—C17—O17	−96.5 (5)
C2—C1—C10—C5	53.9 (4)	C12—C13—C17—C16	−149.8 (3)
C2—C1—C10—C9	169.2 (3)	C14—C13—C17—C16	−32.5 (4)
C4—C5—C10—C1	−50.9 (4)	C18—C13—C17—C16	86.1 (4)
C6—C5—C10—C1	176.7 (3)	C15—C16—C17—O17	−168.4 (4)
C4—C5—C10—C19	70.2 (4)	C15—C16—C17—C13	9.1 (4)
C6—C5—C10—C19	−62.2 (4)	C3—O3—C20—O20	4.6 (5)
C4—C5—C10—C9	−168.1 (3)	C3—O3—C20—C21	−175.4 (3)
C6—C5—C10—C9	59.4 (4)	C4—O4—C22—O22	3.1 (6)
C11—C9—C10—C1	58.4 (4)	C4—O4—C22—C23	−177.9 (3)
C8—C9—C10—C1	−172.3 (3)	C19—C10—C13—C18	0.6 (3)
C11—C9—C10—C19	−62.8 (4)

(II) 17-Oxo-5β-androstane-3α,4β-diyl diacetate

Crystal data

C23H34O5	Dx = 1.078 Mg m^−3
Mr = 390.50	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P65	Cell parameters from 25 reflections
Hall symbol: P 65	θ = 8.8–18.5°
a = 22.885 (3) Å	µ = 0.08 mm^−1
c = 7.9582 (12) Å	T = 293 K
V = 3609.4 (9) Å^3	Prism, colourless
Z = 6	0.37 × 0.24 × 0.24 mm
F(000) = 1272

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.033
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.1°
Graphite monochromator	h = −18→25
ω–2θ scans	k = −16→25
7826 measured reflections	l = −10→10
2953 independent reflections	3 standard reflections every 150 min
1369 reflections with I > 2σ(I)	intensity decay: 6.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0825P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max < 0.001
2953 reflections	Δρmax = 0.19 e Å^−3
258 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0041 (12)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O3	0.08172 (11)	0.25266 (11)	0.2307 (4)	0.0668 (8)
O4	0.12401 (11)	0.35112 (11)	−0.0174 (4)	0.0627 (7)
O17	−0.31483 (14)	0.23121 (19)	0.1126 (5)	0.1158 (12)
O20	0.18538 (16)	0.29103 (17)	0.3172 (7)	0.1378 (18)
O22	0.05760 (16)	0.26578 (17)	−0.1883 (4)	0.0990 (10)
C1	0.0375 (2)	0.3760 (2)	0.4114 (6)	0.0788 (12)
H1A	0.0828	0.4100	0.4443	0.095*
H1B	0.0072	0.3725	0.5010	0.095*
C2	0.0351 (2)	0.3081 (2)	0.3946 (5)	0.0717 (11)
H2A	0.0471	0.2958	0.5003	0.086*
H2B	−0.0100	0.2730	0.3634	0.086*
C3	0.08484 (17)	0.31670 (16)	0.2603 (5)	0.0573 (10)
H3	0.1305	0.3504	0.2961	0.069*
C4	0.06884 (16)	0.33755 (16)	0.0952 (5)	0.0504 (9)
H4	0.0264	0.3010	0.0502	0.061*
C5	0.06531 (16)	0.40238 (15)	0.1082 (5)	0.0542 (9)
H5	0.1108	0.4387	0.1364	0.065*
C6	0.04707 (17)	0.42064 (18)	−0.0605 (5)	0.0662 (11)
H6A	0.0563	0.4669	−0.0563	0.079*
H6B	0.0753	0.4179	−0.1475	0.079*
C7	−0.02616 (17)	0.37473 (18)	−0.1059 (5)	0.0580 (9)
H7A	−0.0338	0.3296	−0.1255	0.070*
H7B	−0.0359	0.3904	−0.2097	0.070*
C8	−0.07444 (15)	0.37179 (15)	0.0302 (4)	0.0471 (8)
H8	−0.0691	0.4168	0.0416	0.057*
C9	−0.05700 (15)	0.35191 (15)	0.2007 (4)	0.0486 (8)
H9	−0.0615	0.3075	0.1834	0.058*
C10	0.01821 (18)	0.39998 (16)	0.2502 (5)	0.0577 (10)
C11	−0.10806 (19)	0.3422 (2)	0.3384 (5)	0.0671 (11)
H11A	−0.0984	0.3239	0.4376	0.081*
H11B	−0.1023	0.3858	0.3680	0.081*
C12	−0.18131 (18)	0.2955 (2)	0.2876 (6)	0.0703 (11)
H12A	−0.1894	0.2499	0.2742	0.084*
H12B	−0.2109	0.2950	0.3755	0.084*
C13	−0.19691 (17)	0.31856 (18)	0.1262 (5)	0.0594 (9)
C14	−0.14760 (16)	0.32248 (16)	−0.0104 (4)	0.0505 (8)
H14	−0.1515	0.2778	−0.0129	0.061*
C15	−0.17840 (19)	0.3285 (2)	−0.1740 (5)	0.0661 (11)
H15A	−0.1620	0.3143	−0.2691	0.079*
H15B	−0.1689	0.3743	−0.1924	0.079*
C16	−0.2551 (2)	0.2795 (2)	−0.1439 (7)	0.0861 (14)
H16A	−0.2816	0.2985	−0.1877	0.103*
H16B	−0.2697	0.2364	−0.1983	0.103*
C17	−0.2630 (2)	0.2710 (2)	0.0429 (6)	0.0732 (12)
C18	−0.1973 (2)	0.3857 (2)	0.1485 (7)	0.0837 (13)
H18A	−0.1537	0.4203	0.1859	0.126*
H18B	−0.2307	0.3796	0.2303	0.126*
H18C	−0.2078	0.3987	0.0430	0.126*
C19	0.0318 (2)	0.47211 (18)	0.2829 (8)	0.0966 (17)
H19A	0.0180	0.4876	0.1868	0.145*
H19B	0.0791	0.5016	0.3025	0.145*
H19C	0.0067	0.4721	0.3797	0.145*
C20	0.13576 (19)	0.2479 (2)	0.2602 (7)	0.0809 (14)
C21	0.1253 (2)	0.1802 (2)	0.2039 (9)	0.111 (2)
H21A	0.0842	0.1448	0.2512	0.167*
H21B	0.1625	0.1753	0.2413	0.167*
H21C	0.1227	0.1775	0.0835	0.167*
C22	0.1128 (2)	0.3105 (2)	−0.1460 (6)	0.0728 (11)
C23	0.1771 (3)	0.3281 (3)	−0.2352 (8)	0.126 (2)
H23A	0.2064	0.3762	−0.2342	0.189*
H23B	0.1673	0.3125	−0.3493	0.189*
H23C	0.1989	0.3070	−0.1794	0.189*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0515 (13)	0.0587 (13)	0.096 (2)	0.0322 (11)	−0.0187 (13)	−0.0035 (14)
O4	0.0515 (13)	0.0682 (15)	0.0676 (17)	0.0294 (12)	0.0071 (13)	−0.0090 (15)
O17	0.0577 (16)	0.127 (3)	0.128 (3)	0.0207 (18)	0.025 (2)	0.014 (3)
O20	0.074 (2)	0.098 (2)	0.245 (5)	0.0457 (19)	−0.073 (3)	−0.032 (3)
O22	0.090 (2)	0.112 (2)	0.071 (2)	0.0321 (19)	−0.0024 (19)	−0.029 (2)
C1	0.076 (2)	0.111 (3)	0.061 (3)	0.056 (2)	−0.010 (2)	−0.031 (3)
C2	0.074 (2)	0.098 (3)	0.051 (3)	0.049 (2)	−0.007 (2)	0.008 (2)
C3	0.0490 (19)	0.0510 (19)	0.068 (3)	0.0221 (15)	−0.009 (2)	−0.0051 (19)
C4	0.0466 (17)	0.0491 (17)	0.059 (2)	0.0263 (15)	−0.0023 (17)	−0.0062 (18)
C5	0.0487 (17)	0.0406 (17)	0.071 (3)	0.0205 (15)	−0.0036 (19)	−0.0078 (18)
C6	0.063 (2)	0.059 (2)	0.081 (3)	0.0346 (18)	0.018 (2)	0.023 (2)
C7	0.064 (2)	0.073 (2)	0.050 (2)	0.0430 (19)	0.0133 (19)	0.0141 (19)
C8	0.062 (2)	0.0435 (17)	0.046 (2)	0.0337 (16)	0.0073 (17)	0.0064 (16)
C9	0.0545 (19)	0.0466 (17)	0.050 (2)	0.0292 (15)	0.0043 (17)	−0.0010 (17)
C10	0.064 (2)	0.0545 (19)	0.058 (2)	0.0324 (17)	−0.009 (2)	−0.0180 (19)
C11	0.082 (3)	0.083 (3)	0.050 (3)	0.052 (2)	0.011 (2)	0.001 (2)
C12	0.065 (2)	0.081 (3)	0.064 (3)	0.035 (2)	0.019 (2)	0.012 (2)
C13	0.057 (2)	0.068 (2)	0.063 (3)	0.0381 (18)	0.009 (2)	0.007 (2)
C14	0.0545 (18)	0.0503 (18)	0.052 (2)	0.0304 (15)	0.0071 (17)	0.0080 (17)
C15	0.070 (2)	0.083 (3)	0.059 (3)	0.048 (2)	−0.002 (2)	0.003 (2)
C16	0.068 (3)	0.092 (3)	0.097 (4)	0.039 (2)	−0.013 (3)	−0.005 (3)
C17	0.060 (2)	0.086 (3)	0.078 (3)	0.040 (2)	0.010 (2)	0.008 (2)
C18	0.094 (3)	0.093 (3)	0.092 (3)	0.068 (3)	0.006 (3)	−0.003 (3)
C19	0.089 (3)	0.059 (2)	0.143 (5)	0.038 (2)	−0.002 (3)	−0.038 (3)
C20	0.049 (2)	0.066 (2)	0.124 (4)	0.027 (2)	−0.013 (3)	0.009 (3)
C21	0.093 (3)	0.082 (3)	0.181 (6)	0.060 (3)	−0.021 (4)	−0.001 (4)
C22	0.077 (3)	0.089 (3)	0.058 (3)	0.046 (2)	0.010 (2)	0.000 (3)
C23	0.103 (4)	0.183 (5)	0.093 (4)	0.073 (4)	0.034 (4)	−0.022 (4)

Geometric parameters (Å, º)

O3—C20	1.315 (4)	C10—C19	1.541 (5)
O3—C3	1.451 (4)	C11—C12	1.524 (5)
O4—C22	1.319 (5)	C11—H11A	0.9700
O4—C4	1.449 (4)	C11—H11B	0.9700
O17—C17	1.210 (5)	C12—C13	1.498 (6)
O20—C20	1.161 (5)	C12—H12A	0.9700
O22—C22	1.211 (5)	C12—H12B	0.9700
C1—C2	1.532 (5)	C13—C17	1.505 (5)
C1—C10	1.544 (6)	C13—C14	1.537 (5)
C1—H1A	0.9700	C13—C18	1.551 (5)
C1—H1B	0.9700	C14—C15	1.519 (5)
C2—C3	1.502 (5)	C14—H14	0.9800
C2—H2A	0.9700	C15—C16	1.558 (6)
C2—H2B	0.9700	C15—H15A	0.9700
C3—C4	1.505 (5)	C15—H15B	0.9700
C3—H3	0.9800	C16—C17	1.499 (7)
C4—C5	1.529 (4)	C16—H16A	0.9700
C4—H4	0.9800	C16—H16B	0.9700
C5—C6	1.526 (5)	C18—H18A	0.9600
C5—C10	1.544 (5)	C18—H18B	0.9600
C5—H5	0.9800	C18—H18C	0.9600
C6—C7	1.511 (5)	C19—H19A	0.9600
C6—H6A	0.9700	C19—H19B	0.9600
C6—H6B	0.9700	C19—H19C	0.9600
C7—C8	1.525 (5)	C20—C21	1.513 (6)
C7—H7A	0.9700	C21—H21A	0.9600
C7—H7B	0.9700	C21—H21B	0.9600
C8—C14	1.514 (4)	C21—H21C	0.9600
C8—C9	1.546 (5)	C22—C23	1.496 (6)
C8—H8	0.9800	C23—H23A	0.9600
C9—C11	1.534 (5)	C23—H23B	0.9600
C9—C10	1.560 (5)	C23—H23C	0.9600
C9—H9	0.9800
C20—O3—C3	118.8 (3)	C9—C11—H11B	108.8
C22—O4—C4	119.2 (3)	H11A—C11—H11B	107.7
C2—C1—C10	114.6 (3)	C13—C12—C11	110.7 (3)
C2—C1—H1A	108.6	C13—C12—H12A	109.5
C10—C1—H1A	108.6	C11—C12—H12A	109.5
C2—C1—H1B	108.6	C13—C12—H12B	109.5
C10—C1—H1B	108.6	C11—C12—H12B	109.5
H1A—C1—H1B	107.6	H12A—C12—H12B	108.1
C3—C2—C1	106.8 (3)	C12—C13—C17	116.9 (3)
C3—C2—H2A	110.4	C12—C13—C14	109.2 (3)
C1—C2—H2A	110.4	C17—C13—C14	100.0 (3)
C3—C2—H2B	110.4	C12—C13—C18	111.8 (4)
C1—C2—H2B	110.4	C17—C13—C18	105.4 (3)
H2A—C2—H2B	108.6	C14—C13—C18	113.0 (3)
O3—C3—C2	109.4 (3)	C8—C14—C15	120.4 (3)
O3—C3—C4	106.4 (3)	C8—C14—C13	113.5 (3)
C2—C3—C4	112.0 (3)	C15—C14—C13	104.5 (3)
O3—C3—H3	109.7	C8—C14—H14	105.8
C2—C3—H3	109.7	C15—C14—H14	105.8
C4—C3—H3	109.7	C13—C14—H14	105.8
O4—C4—C3	106.5 (3)	C14—C15—C16	102.1 (3)
O4—C4—C5	107.3 (3)	C14—C15—H15A	111.3
C3—C4—C5	112.8 (3)	C16—C15—H15A	111.3
O4—C4—H4	110.1	C14—C15—H15B	111.3
C3—C4—H4	110.1	C16—C15—H15B	111.3
C5—C4—H4	110.1	H15A—C15—H15B	109.2
C6—C5—C4	111.1 (3)	C17—C16—C15	105.3 (4)
C6—C5—C10	111.9 (3)	C17—C16—H16A	110.7
C4—C5—C10	112.9 (3)	C15—C16—H16A	110.7
C6—C5—H5	106.8	C17—C16—H16B	110.7
C4—C5—H5	106.8	C15—C16—H16B	110.7
C10—C5—H5	106.8	H16A—C16—H16B	108.8
C7—C6—C5	112.4 (3)	O17—C17—C16	124.1 (4)
C7—C6—H6A	109.1	O17—C17—C13	126.5 (4)
C5—C6—H6A	109.1	C16—C17—C13	109.3 (4)
C7—C6—H6B	109.1	C13—C18—H18A	109.5
C5—C6—H6B	109.1	C13—C18—H18B	109.5
H6A—C6—H6B	107.9	H18A—C18—H18B	109.5
C6—C7—C8	112.8 (3)	C13—C18—H18C	109.5
C6—C7—H7A	109.0	H18A—C18—H18C	109.5
C8—C7—H7A	109.0	H18B—C18—H18C	109.5
C6—C7—H7B	109.0	C10—C19—H19A	109.5
C8—C7—H7B	109.0	C10—C19—H19B	109.5
H7A—C7—H7B	107.8	H19A—C19—H19B	109.5
C14—C8—C7	112.9 (3)	C10—C19—H19C	109.5
C14—C8—C9	108.7 (3)	H19A—C19—H19C	109.5
C7—C8—C9	110.4 (2)	H19B—C19—H19C	109.5
C14—C8—H8	108.3	O20—C20—O3	124.0 (4)
C7—C8—H8	108.3	O20—C20—C21	124.9 (4)
C9—C8—H8	108.3	O3—C20—C21	111.0 (4)
C11—C9—C8	112.3 (2)	C20—C21—H21A	109.5
C11—C9—C10	114.5 (3)	C20—C21—H21B	109.5
C8—C9—C10	111.7 (3)	H21A—C21—H21B	109.5
C11—C9—H9	105.9	C20—C21—H21C	109.5
C8—C9—H9	105.9	H21A—C21—H21C	109.5
C10—C9—H9	105.9	H21B—C21—H21C	109.5
C5—C10—C19	108.8 (3)	O22—C22—O4	124.3 (4)
C5—C10—C1	107.6 (3)	O22—C22—C23	124.5 (4)
C19—C10—C1	107.5 (3)	O4—C22—C23	111.1 (4)
C5—C10—C9	110.2 (3)	C22—C23—H23A	109.5
C19—C10—C9	111.0 (3)	C22—C23—H23B	109.5
C1—C10—C9	111.7 (3)	H23A—C23—H23B	109.5
C12—C11—C9	113.8 (3)	C22—C23—H23C	109.5
C12—C11—H11A	108.8	H23A—C23—H23C	109.5
C9—C11—H11A	108.8	H23B—C23—H23C	109.5
C12—C11—H11B	108.8
C10—C1—C2—C3	60.8 (4)	C8—C9—C10—C19	65.8 (4)
C20—O3—C3—C2	−117.8 (4)	C11—C9—C10—C1	56.6 (4)
C20—O3—C3—C4	121.1 (4)	C8—C9—C10—C1	−174.3 (3)
C1—C2—C3—O3	−176.3 (3)	C8—C9—C11—C12	50.8 (4)
C1—C2—C3—C4	−58.6 (4)	C10—C9—C11—C12	179.6 (3)
C22—O4—C4—C3	111.6 (4)	C9—C11—C12—C13	−53.7 (4)
C22—O4—C4—C5	−127.4 (3)	C11—C12—C13—C17	169.0 (3)
O3—C3—C4—O4	−66.5 (3)	C11—C12—C13—C14	56.5 (4)
C2—C3—C4—O4	174.0 (3)	C11—C12—C13—C18	−69.4 (4)
O3—C3—C4—C5	176.0 (2)	C7—C8—C14—C15	−55.5 (4)
C2—C3—C4—C5	56.6 (4)	C9—C8—C14—C15	−178.3 (3)
O4—C4—C5—C6	64.6 (3)	C7—C8—C14—C13	179.6 (3)
C3—C4—C5—C6	−178.4 (3)	C9—C8—C14—C13	56.8 (3)
O4—C4—C5—C10	−168.7 (3)	C12—C13—C14—C8	−60.9 (4)
C3—C4—C5—C10	−51.8 (4)	C17—C13—C14—C8	175.9 (3)
C4—C5—C6—C7	73.2 (4)	C18—C13—C14—C8	64.3 (4)
C10—C5—C6—C7	−54.1 (4)	C12—C13—C14—C15	166.1 (3)
C5—C6—C7—C8	54.6 (4)	C17—C13—C14—C15	42.8 (3)
C6—C7—C8—C14	−176.4 (3)	C18—C13—C14—C15	−68.8 (4)
C6—C7—C8—C9	−54.6 (4)	C8—C14—C15—C16	−168.2 (3)
C14—C8—C9—C11	−50.6 (3)	C13—C14—C15—C16	−39.2 (4)
C7—C8—C9—C11	−174.9 (3)	C14—C15—C16—C17	19.9 (4)
C14—C8—C9—C10	179.2 (3)	C15—C16—C17—O17	−172.6 (4)
C7—C8—C9—C10	54.9 (3)	C15—C16—C17—C13	6.8 (5)
C6—C5—C10—C19	−68.1 (4)	C12—C13—C17—O17	31.6 (6)
C4—C5—C10—C19	165.7 (3)	C14—C13—C17—O17	149.3 (4)
C6—C5—C10—C1	175.8 (3)	C18—C13—C17—O17	−93.3 (5)
C4—C5—C10—C1	49.6 (4)	C12—C13—C17—C16	−147.8 (4)
C6—C5—C10—C9	53.8 (3)	C14—C13—C17—C16	−30.1 (4)
C4—C5—C10—C9	−72.4 (4)	C18—C13—C17—C16	87.3 (4)
C2—C1—C10—C5	−56.2 (4)	C3—O3—C20—O20	4.2 (8)
C2—C1—C10—C19	−173.2 (4)	C3—O3—C20—C21	−173.6 (4)
C2—C1—C10—C9	64.9 (4)	C4—O4—C22—O22	7.9 (6)
C11—C9—C10—C5	176.1 (3)	C4—O4—C22—C23	−173.5 (4)
C8—C9—C10—C5	−54.8 (3)	C19—C10—C13—C18	0.7 (4)
C11—C9—C10—C19	−63.3 (4)