3β,6α-Diacet-oxy-5,9α-dihy-droxy-5α-cholest-7-en-11-one.

The title compound, C31H48O7, a polyoxygenated steroid, was obtained by chemical oxidation of 7-de-hydro-cholesteryl acetate. The mol-ecular geometry features trans A/B and C/D junctions at the steroid core with the acetyl groups in the equatorial position and a fully extended conformation for the alkyl side chain. A chair conformation is observed for rings A and C while ring B adopts a half-chair conformation. The five-membered ring D has an envelope conformation, with the C atom bearing the methyl group at the flap. The terminal isopropyl group and one acetyl group are disordered over two sets of sites with 0.774 (8):0.226 (8) and 0.843 (7):0.157 (7) ratios, respectively. An intra-molecular S(6) O-H⋯O hydrogen-bonding motif involving a hy-droxy donor and acceptor is observed. In the crystal, chains of mol-ecules running along the b axis are formed via O-H⋯O hydrogen bonds between hy-droxy donors and carbonyl acceptors of the ordered acetyl group, giving rise to a C(14) motif. The chains are wrapped around the 21 screw axes.

Related literature

For general information on the isolation of polyoxygenated steroids from marine source, see: Notaro et al. (1991 ▶, 1992 ▶). For the synthesis of polyoxygenated steroids, see: Migliuolo et al. (1992 ▶). For new selective oxidation protocols, see: Piccialli et al. (1993 ▶); Notaro et al. (1994 ▶); Caserta et al. (2005 ▶); Piccialli, D’Errico et al. (2013 ▶). For recent examples of hydrogen bonding in crystals, see: Centore, Fusco, Jazbinsek et al. (2013 ▶); Centore et al. (2013a ▶,b ▶); Centore, Fusco, Capobianco et al. (2013 ▶). For the structure and packing of the 6β isomeric steroid see: Piccialli, Oliviero et al. (2013 ▶).

Experimental

Crystal data

C31H48O7

M = 532.69

Monoclinic,

a = 10.964 (2) Å

b = 9.155 (1) Å

c = 14.740 (2) Å

β = 92.98 (1)°

V = 1477.5 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 173 K

0.60 × 0.35 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.952, T max = 0.996

9976 measured reflections

3498 independent reflections

2502 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.107

S = 1.07

3498 reflections

414 parameters

43 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813016206/fj2632sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016206/fj2632Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C31H48O7	F(000) = 580
Mr = 532.69	Dx = 1.197 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 96 reflections
a = 10.964 (2) Å	θ = 3.7–18.4°
b = 9.155 (1) Å	µ = 0.08 mm−1
c = 14.740 (2) Å	T = 173 K
β = 92.98 (1)°	Block, colorless
V = 1477.5 (4) Å3	0.60 × 0.35 × 0.05 mm
Z = 2

Bruker–Nonius KappaCCD diffractometer	3498 independent reflections
Radiation source: normal-focus sealed tube	2502 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.2°
CCD rotation images, thick slices scans	h = −14→11
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −11→10
Tmin = 0.952, Tmax = 0.996	l = −19→17
9976 measured 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) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0293P)2 + 0.6674P] where P = (Fo2 + 2Fc2)/3
3498 reflections	(Δ/σ)max = 0.004
414 parameters	Δρmax = 0.24 e Å−3
43 restraints	Δρmin = −0.23 e Å−3

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	Occ. (<1)
C1	1.2313 (3)	0.6868 (7)	0.3113 (2)	0.0272 (8)
H1A	1.2594	0.7237	0.3720	0.033*
H1B	1.2185	0.5801	0.3166	0.033*
C2	1.3314 (3)	0.7144 (7)	0.2447 (2)	0.0346 (9)
H2A	1.3508	0.8200	0.2433	0.042*
H2B	1.4065	0.6610	0.2650	0.042*
C3	1.2894 (3)	0.6642 (7)	0.1518 (2)	0.0292 (8)
H3	1.2725	0.5570	0.1533	0.035*
C4	1.1750 (3)	0.7445 (7)	0.1178 (2)	0.0255 (7)
H4A	1.1492	0.7092	0.0563	0.031*
H4B	1.1923	0.8504	0.1139	0.031*
C5	1.0716 (3)	0.7187 (6)	0.18291 (19)	0.0195 (7)
C6	0.9551 (3)	0.8041 (6)	0.15326 (19)	0.0224 (7)
H6	0.9748	0.9097	0.1444	0.027*
C7	0.8587 (3)	0.7886 (6)	0.2195 (2)	0.0230 (7)
H7	0.7773	0.8119	0.1994	0.028*
C8	0.8780 (2)	0.7447 (6)	0.30446 (19)	0.0187 (6)
C9	1.0055 (3)	0.7047 (6)	0.34476 (19)	0.0207 (7)
C10	1.1079 (3)	0.7597 (6)	0.2832 (2)	0.0216 (7)
C11	1.0205 (3)	0.7551 (6)	0.44532 (19)	0.0226 (7)
C12	0.9153 (3)	0.7191 (6)	0.50437 (19)	0.0245 (7)
H12A	0.9314	0.7613	0.5657	0.029*
H12B	0.9085	0.6118	0.5108	0.029*
C13	0.7943 (3)	0.7805 (6)	0.46246 (19)	0.0212 (7)
C14	0.7768 (3)	0.7126 (6)	0.36678 (19)	0.0222 (7)
H14	0.7775	0.6043	0.3760	0.027*
C15	0.6462 (3)	0.7519 (7)	0.3353 (2)	0.0293 (8)
H15A	0.6130	0.6816	0.2894	0.035*
H15B	0.6419	0.8517	0.3095	0.035*
C16	0.5767 (3)	0.7423 (7)	0.4239 (2)	0.0314 (8)
H16A	0.5215	0.6567	0.4220	0.038*
H16B	0.5272	0.8315	0.4316	0.038*
C17	0.6749 (3)	0.7270 (7)	0.50405 (19)	0.0244 (7)
H17A	0.6849	0.6204	0.5171	0.029*
C18	0.8001 (3)	0.9459 (6)	0.4582 (2)	0.0256 (7)
H18A	0.8630	0.9754	0.4171	0.038*
H18B	0.8202	0.9849	0.5191	0.038*
H18C	0.7207	0.9843	0.4357	0.038*
C19	1.1215 (3)	0.9269 (6)	0.2916 (2)	0.0281 (8)
H19A	1.1683	0.9507	0.3482	0.042*
H19B	1.0404	0.9718	0.2923	0.042*
H19C	1.1644	0.9644	0.2398	0.042*
C20	0.6328 (3)	0.7998 (6)	0.5910 (2)	0.0246 (7)
H20	0.6188	0.9058	0.5778	0.030*
C21	0.7275 (3)	0.7879 (6)	0.6704 (2)	0.0294 (8)
H21A	0.7452	0.6848	0.6830	0.044*
H21B	0.6954	0.8336	0.7244	0.044*
H21C	0.8026	0.8379	0.6548	0.044*
C22	0.5109 (3)	0.7333 (7)	0.6181 (2)	0.0347 (8)
H22A	0.4555	0.7270	0.5630	0.042*
H22B	0.5266	0.6323	0.6397	0.042*
C23	0.4456 (3)	0.8149 (7)	0.6905 (3)	0.0387 (9)
H23A	0.5002	0.8212	0.7460	0.046*
H23B	0.4287	0.9158	0.6691	0.046*
C24A	0.3273 (3)	0.7443 (7)	0.7141 (3)	0.0438 (10)	0.774 (8)
H24A	0.2838	0.7146	0.6566	0.053*	0.774 (8)
H24B	0.3477	0.6538	0.7484	0.053*	0.774 (8)
C25A	0.2395 (4)	0.8302 (7)	0.7680 (3)	0.0349 (13)	0.774 (8)
H25B	0.2118	0.9134	0.7281	0.042*	0.774 (8)
C26A	0.1269 (6)	0.7425 (12)	0.7838 (8)	0.072 (3)	0.774 (8)
H26D	0.1489	0.6570	0.8211	0.108*	0.774 (8)
H26E	0.0895	0.7104	0.7253	0.108*	0.774 (8)
H26F	0.0686	0.8030	0.8153	0.108*	0.774 (8)
C27A	0.2935 (11)	0.8984 (13)	0.8535 (6)	0.068 (2)	0.774 (8)
H27D	0.2329	0.9626	0.8795	0.101*	0.774 (8)
H27E	0.3656	0.9557	0.8395	0.101*	0.774 (8)
H27F	0.3171	0.8216	0.8972	0.101*	0.774 (8)
C24B	0.3273 (3)	0.7443 (7)	0.7141 (3)	0.0438 (10)	0.226 (8)
H24C	0.3371	0.6379	0.7052	0.053*	0.226 (8)
H24D	0.2641	0.7775	0.6683	0.053*	0.226 (8)
C25B	0.2751 (15)	0.7655 (18)	0.8072 (12)	0.0349 (14)	0.226 (8)
H25A	0.3302	0.7091	0.8505	0.042*	0.226 (8)
C26B	0.281 (4)	0.921 (2)	0.840 (3)	0.068 (2)	0.226 (8)
H26A	0.3668	0.9473	0.8546	0.101*	0.226 (8)
H26B	0.2347	0.9304	0.8947	0.101*	0.226 (8)
H26C	0.2470	0.9856	0.7925	0.101*	0.226 (8)
C27B	0.1508 (17)	0.700 (4)	0.815 (3)	0.063 (10)	0.226 (8)
H27A	0.1318	0.6366	0.7623	0.095*	0.226 (8)
H27B	0.0897	0.7775	0.8167	0.095*	0.226 (8)
H27C	0.1496	0.6415	0.8707	0.095*	0.226 (8)
C30	0.9133 (3)	0.8178 (6)	−0.0083 (2)	0.0255 (7)
C31	0.8490 (3)	0.7403 (7)	−0.0855 (2)	0.0333 (8)
H31A	0.8661	0.7894	−0.1426	0.050*
H31B	0.7608	0.7415	−0.0774	0.050*
H31C	0.8776	0.6390	−0.0874	0.050*
O1	1.0437 (2)	0.5655 (6)	0.18240 (15)	0.0226 (5)
H1C	1.031 (3)	0.538 (4)	0.134 (2)	0.027*
O2	1.0090 (2)	0.5488 (6)	0.35657 (15)	0.0234 (5)
H1D	1.007 (3)	0.519 (4)	0.303 (3)	0.028*
O3	1.1125 (2)	0.8138 (6)	0.47619 (15)	0.0310 (6)
O4	1.3878 (2)	0.6926 (6)	0.09140 (16)	0.0394 (7)
O5A	1.3419 (4)	0.4895 (7)	0.0110 (3)	0.0720 (16)	0.843 (7)
C28A	1.4072 (5)	0.5927 (7)	0.0263 (3)	0.0461 (18)	0.843 (7)
C29A	1.5189 (6)	0.6266 (12)	−0.0245 (5)	0.058 (2)	0.843 (7)
H29D	1.5884	0.5706	0.0017	0.086*	0.843 (7)
H29E	1.5369	0.7312	−0.0198	0.086*	0.843 (7)
H29F	1.5044	0.5999	−0.0885	0.086*	0.843 (7)
O5B	1.407 (2)	0.466 (2)	0.0706 (19)	0.0720 (17)	0.157 (7)
C28B	1.431 (3)	0.590 (2)	0.053 (3)	0.0461 (19)	0.157 (7)
C29B	1.538 (4)	0.636 (5)	−0.001 (4)	0.058 (3)	0.157 (7)
H29A	1.5166	0.7253	−0.0346	0.086*	0.157 (7)
H29B	1.5566	0.5579	−0.0433	0.086*	0.157 (7)
H29C	1.6088	0.6541	0.0407	0.086*	0.157 (7)
O6	0.90421 (18)	0.7413 (6)	0.06841 (13)	0.0239 (5)
O7	0.9678 (2)	0.9317 (6)	−0.01271 (15)	0.0352 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0224 (17)	0.038 (2)	0.0204 (15)	0.0016 (15)	−0.0016 (12)	0.0000 (15)
C2	0.0206 (17)	0.050 (2)	0.0335 (18)	−0.0059 (17)	0.0037 (14)	0.0041 (18)
C3	0.0181 (17)	0.044 (2)	0.0266 (17)	−0.0020 (15)	0.0118 (13)	0.0021 (16)
C4	0.0217 (16)	0.0338 (19)	0.0217 (15)	−0.0037 (15)	0.0080 (12)	0.0013 (16)
C5	0.0209 (16)	0.0218 (17)	0.0163 (14)	−0.0022 (13)	0.0044 (11)	−0.0005 (13)
C6	0.0252 (17)	0.0259 (18)	0.0161 (14)	−0.0028 (14)	0.0006 (12)	−0.0009 (14)
C7	0.0193 (16)	0.0287 (19)	0.0210 (15)	0.0019 (13)	0.0012 (12)	−0.0027 (14)
C8	0.0165 (15)	0.0199 (16)	0.0197 (15)	−0.0018 (13)	0.0027 (11)	−0.0002 (14)
C9	0.0232 (16)	0.0204 (18)	0.0181 (15)	0.0008 (13)	−0.0016 (12)	0.0006 (13)
C10	0.0187 (16)	0.0259 (18)	0.0202 (15)	−0.0029 (13)	0.0002 (12)	0.0024 (14)
C11	0.0214 (17)	0.0271 (18)	0.0187 (15)	0.0071 (14)	−0.0036 (12)	0.0014 (14)
C12	0.0254 (17)	0.033 (2)	0.0149 (14)	0.0031 (15)	0.0026 (12)	0.0014 (15)
C13	0.0207 (16)	0.0267 (19)	0.0164 (14)	−0.0005 (13)	0.0021 (11)	−0.0009 (13)
C14	0.0211 (16)	0.0301 (19)	0.0155 (14)	−0.0012 (14)	0.0020 (11)	−0.0008 (14)
C15	0.0198 (17)	0.049 (2)	0.0187 (15)	−0.0014 (16)	0.0012 (12)	−0.0057 (17)
C16	0.0223 (17)	0.051 (2)	0.0216 (16)	−0.0022 (17)	0.0040 (12)	−0.0052 (17)
C17	0.0240 (16)	0.0291 (19)	0.0205 (15)	−0.0021 (15)	0.0048 (12)	−0.0031 (15)
C18	0.0266 (18)	0.0278 (19)	0.0227 (16)	−0.0016 (14)	0.0051 (13)	0.0015 (15)
C19	0.0308 (19)	0.030 (2)	0.0242 (17)	−0.0075 (15)	0.0021 (14)	0.0003 (16)
C20	0.0274 (17)	0.0272 (18)	0.0196 (15)	0.0011 (14)	0.0046 (12)	−0.0008 (14)
C21	0.0363 (19)	0.031 (2)	0.0214 (16)	0.0057 (15)	0.0043 (13)	−0.0021 (15)
C22	0.0323 (19)	0.042 (2)	0.0313 (18)	−0.0052 (18)	0.0156 (14)	−0.0043 (18)
C23	0.035 (2)	0.040 (2)	0.043 (2)	−0.0067 (18)	0.0176 (16)	−0.0121 (19)
C24A	0.039 (2)	0.048 (2)	0.047 (2)	−0.009 (2)	0.0235 (17)	−0.010 (2)
C25A	0.033 (3)	0.036 (3)	0.037 (3)	−0.001 (2)	0.014 (2)	0.000 (2)
C26A	0.056 (5)	0.049 (6)	0.115 (10)	−0.007 (4)	0.058 (5)	−0.013 (6)
C27A	0.061 (4)	0.094 (5)	0.050 (4)	0.011 (4)	0.020 (3)	−0.023 (4)
C24B	0.039 (2)	0.048 (2)	0.047 (2)	−0.009 (2)	0.0235 (17)	−0.010 (2)
C25B	0.033 (3)	0.036 (3)	0.038 (3)	−0.001 (2)	0.014 (2)	0.000 (3)
C26B	0.061 (4)	0.094 (5)	0.050 (4)	0.011 (4)	0.020 (3)	−0.023 (4)
C27B	0.049 (15)	0.06 (2)	0.09 (2)	0.008 (13)	0.038 (13)	0.033 (15)
C30	0.0236 (17)	0.034 (2)	0.0197 (16)	0.0052 (16)	0.0040 (12)	0.0057 (15)
C31	0.0327 (19)	0.047 (2)	0.0201 (16)	−0.0001 (18)	0.0025 (13)	0.0009 (17)
O1	0.0261 (13)	0.0218 (12)	0.0201 (11)	−0.0021 (10)	0.0031 (9)	−0.0031 (10)
O2	0.0288 (13)	0.0225 (13)	0.0192 (11)	0.0017 (10)	0.0031 (9)	0.0009 (10)
O3	0.0267 (13)	0.0419 (15)	0.0239 (12)	−0.0032 (11)	−0.0029 (9)	−0.0074 (11)
O4	0.0250 (13)	0.0554 (18)	0.0391 (14)	−0.0021 (12)	0.0145 (10)	0.0044 (13)
O5A	0.084 (3)	0.067 (3)	0.069 (3)	−0.013 (2)	0.049 (3)	−0.022 (2)
C28A	0.038 (3)	0.059 (3)	0.044 (4)	0.010 (2)	0.021 (3)	0.006 (3)
C29A	0.045 (4)	0.079 (4)	0.052 (5)	0.019 (3)	0.031 (4)	0.023 (4)
O5B	0.084 (4)	0.067 (3)	0.069 (3)	−0.013 (3)	0.049 (3)	−0.022 (3)
C28B	0.038 (3)	0.059 (3)	0.044 (4)	0.010 (3)	0.021 (3)	0.006 (3)
C29B	0.045 (4)	0.079 (4)	0.052 (5)	0.019 (3)	0.031 (4)	0.023 (4)
O6	0.0253 (12)	0.0297 (13)	0.0167 (10)	−0.0024 (10)	0.0011 (8)	0.0017 (10)
O7	0.0441 (16)	0.0382 (16)	0.0232 (12)	−0.0102 (12)	0.0005 (10)	0.0098 (12)

C1—C2	1.532 (4)	C20—C22	1.539 (4)
C1—C10	1.546 (4)	C20—H20	1.0000
C1—H1A	0.9900	C21—H21A	0.9800
C1—H1B	0.9900	C21—H21B	0.9800
C2—C3	1.494 (5)	C21—H21C	0.9800
C2—H2A	0.9900	C22—C23	1.514 (5)
C2—H2B	0.9900	C22—H22A	0.9900
C3—O4	1.458 (4)	C22—H22B	0.9900
C3—C4	1.516 (5)	C23—C24A	1.506 (5)
C3—H3	1.0000	C23—H23A	0.9900
C4—C5	1.540 (4)	C23—H23B	0.9900
C4—H4A	0.9900	C24A—C25A	1.501 (2)
C4—H4B	0.9900	C24A—H24A	0.9900
C5—O1	1.435 (4)	C24A—H24B	0.9900
C5—C6	1.542 (4)	C25A—C27A	1.500 (2)
C5—C10	1.557 (4)	C25A—C26A	1.501 (2)
C6—O6	1.461 (4)	C25A—H25B	1.0000
C6—C7	1.482 (4)	C26A—H26D	0.9800
C6—H6	1.0000	C26A—H26E	0.9800
C7—C8	1.322 (4)	C26A—H26F	0.9800
C7—H7	0.9500	C27A—H27D	0.9800
C8—C14	1.506 (4)	C27A—H27E	0.9800
C8—C9	1.534 (4)	C27A—H27F	0.9800
C9—O2	1.438 (4)	C25B—C27B	1.500 (2)
C9—C11	1.553 (4)	C25B—C26B	1.501 (2)
C9—C10	1.563 (4)	C25B—H25A	1.0000
C10—C19	1.542 (5)	C26B—H26A	0.9800
C11—O3	1.210 (4)	C26B—H26B	0.9800
C11—C12	1.517 (4)	C26B—H26C	0.9800
C12—C13	1.540 (4)	C27B—H27A	0.9800
C12—H12A	0.9900	C27B—H27B	0.9800
C12—H12B	0.9900	C27B—H27C	0.9800
C13—C18	1.517 (5)	C30—O7	1.205 (4)
C13—C14	1.544 (4)	C30—O6	1.339 (4)
C13—C17	1.553 (4)	C30—C31	1.487 (5)
C14—C15	1.525 (4)	C31—H31A	0.9800
C14—H14	1.0000	C31—H31B	0.9800
C15—C16	1.548 (4)	C31—H31C	0.9800
C15—H15A	0.9900	O1—H1C	0.76 (4)
C15—H15B	0.9900	O2—H1D	0.84 (4)
C16—C17	1.562 (4)	O4—C28B	1.20 (3)
C16—H16A	0.9900	O4—C28A	1.3500 (11)
C16—H16B	0.9900	O5A—C28A	1.2000 (10)
C17—C20	1.536 (4)	C28A—C29A	1.5003 (11)
C17—H17A	1.0000	C29A—H29D	0.9800
C18—H18A	0.9800	C29A—H29E	0.9800
C18—H18B	0.9800	C29A—H29F	0.9800
C18—H18C	0.9800	O5B—C28B	1.2000 (15)
C19—H19A	0.9800	C28B—C29B	1.5003 (15)
C19—H19B	0.9800	C29B—H29A	0.9800
C19—H19C	0.9800	C29B—H29B	0.9800
C20—C21	1.528 (4)	C29B—H29C	0.9800
C2—C1—C10	113.8 (3)	C16—C17—H17A	107.3
C2—C1—H1A	108.8	C13—C18—H18A	109.5
C10—C1—H1A	108.8	C13—C18—H18B	109.5
C2—C1—H1B	108.8	H18A—C18—H18B	109.5
C10—C1—H1B	108.8	C13—C18—H18C	109.5
H1A—C1—H1B	107.7	H18A—C18—H18C	109.5
C3—C2—C1	109.8 (3)	H18B—C18—H18C	109.5
C3—C2—H2A	109.7	C10—C19—H19A	109.5
C1—C2—H2A	109.7	C10—C19—H19B	109.5
C3—C2—H2B	109.7	H19A—C19—H19B	109.5
C1—C2—H2B	109.7	C10—C19—H19C	109.5
H2A—C2—H2B	108.2	H19A—C19—H19C	109.5
O4—C3—C2	107.6 (3)	H19B—C19—H19C	109.5
O4—C3—C4	109.7 (3)	C21—C20—C17	112.7 (3)
C2—C3—C4	111.4 (3)	C21—C20—C22	109.7 (3)
O4—C3—H3	109.4	C17—C20—C22	110.3 (3)
C2—C3—H3	109.4	C21—C20—H20	108.0
C4—C3—H3	109.4	C17—C20—H20	108.0
C3—C4—C5	110.0 (3)	C22—C20—H20	108.0
C3—C4—H4A	109.7	C20—C21—H21A	109.5
C5—C4—H4A	109.7	C20—C21—H21B	109.5
C3—C4—H4B	109.7	H21A—C21—H21B	109.5
C5—C4—H4B	109.7	C20—C21—H21C	109.5
H4A—C4—H4B	108.2	H21A—C21—H21C	109.5
O1—C5—C4	108.0 (2)	H21B—C21—H21C	109.5
O1—C5—C6	108.7 (2)	C23—C22—C20	115.9 (3)
C4—C5—C6	111.8 (3)	C23—C22—H22A	108.3
O1—C5—C10	106.5 (2)	C20—C22—H22A	108.3
C4—C5—C10	113.2 (2)	C23—C22—H22B	108.3
C6—C5—C10	108.3 (2)	C20—C22—H22B	108.3
O6—C6—C7	105.8 (2)	H22A—C22—H22B	107.4
O6—C6—C5	108.5 (2)	C24A—C23—C22	113.3 (3)
C7—C6—C5	111.9 (3)	C24A—C23—H23A	108.9
O6—C6—H6	110.2	C22—C23—H23A	108.9
C7—C6—H6	110.2	C24A—C23—H23B	108.9
C5—C6—H6	110.2	C22—C23—H23B	108.9
C8—C7—C6	124.6 (3)	H23A—C23—H23B	107.7
C8—C7—H7	117.7	C25A—C24A—C23	118.8 (3)
C6—C7—H7	117.7	C25A—C24A—H24A	107.6
C7—C8—C14	123.4 (3)	C23—C24A—H24A	107.6
C7—C8—C9	122.5 (3)	C25A—C24A—H24B	107.6
C14—C8—C9	113.7 (2)	C23—C24A—H24B	107.6
O2—C9—C8	107.6 (2)	H24A—C24A—H24B	107.1
O2—C9—C11	100.3 (2)	C27A—C25A—C26A	112.6 (4)
C8—C9—C11	110.4 (2)	C27A—C25A—C24A	115.2 (6)
O2—C9—C10	112.0 (2)	C26A—C25A—C24A	111.0 (5)
C8—C9—C10	111.4 (2)	C27A—C25A—H25B	105.7
C11—C9—C10	114.5 (2)	C26A—C25A—H25B	105.7
C19—C10—C1	109.1 (3)	C24A—C25A—H25B	105.7
C19—C10—C5	109.5 (3)	C27B—C25B—C26B	112.6 (5)
C1—C10—C5	109.1 (2)	C27B—C25B—H25A	105.4
C19—C10—C9	110.0 (3)	C26B—C25B—H25A	105.4
C1—C10—C9	110.5 (2)	C25B—C26B—H26A	109.5
C5—C10—C9	108.5 (2)	C25B—C26B—H26B	109.5
O3—C11—C12	121.6 (3)	H26A—C26B—H26B	109.5
O3—C11—C9	122.4 (3)	C25B—C26B—H26C	109.5
C12—C11—C9	115.9 (3)	H26A—C26B—H26C	109.5
C11—C12—C13	110.8 (2)	H26B—C26B—H26C	109.5
C11—C12—H12A	109.5	C25B—C27B—H27A	109.5
C13—C12—H12A	109.5	C25B—C27B—H27B	109.5
C11—C12—H12B	109.5	H27A—C27B—H27B	109.5
C13—C12—H12B	109.5	C25B—C27B—H27C	109.5
H12A—C12—H12B	108.1	H27A—C27B—H27C	109.5
C18—C13—C12	110.1 (3)	H27B—C27B—H27C	109.5
C18—C13—C14	111.6 (3)	O7—C30—O6	123.8 (3)
C12—C13—C14	106.4 (2)	O7—C30—C31	126.1 (3)
C18—C13—C17	111.7 (3)	O6—C30—C31	110.1 (3)
C12—C13—C17	116.9 (3)	C30—C31—H31A	109.5
C14—C13—C17	99.6 (2)	C30—C31—H31B	109.5
C8—C14—C15	118.6 (3)	H31A—C31—H31B	109.5
C8—C14—C13	114.7 (3)	C30—C31—H31C	109.5
C15—C14—C13	104.6 (2)	H31A—C31—H31C	109.5
C8—C14—H14	106.0	H31B—C31—H31C	109.5
C15—C14—H14	106.0	C5—O1—H1C	111 (3)
C13—C14—H14	106.0	C9—O2—H1D	102 (3)
C14—C15—C16	103.1 (2)	C28B—O4—C28A	20 (2)
C14—C15—H15A	111.2	C28B—O4—C3	118.2 (12)
C16—C15—H15A	111.2	C28A—O4—C3	117.5 (3)
C14—C15—H15B	111.2	O5A—C28A—O4	123.5 (4)
C16—C15—H15B	111.2	O5A—C28A—C29A	124.3 (4)
H15A—C15—H15B	109.1	O4—C28A—C29A	112.2 (5)
C15—C16—C17	107.0 (2)	O5B—C28B—O4	123 (2)
C15—C16—H16A	110.3	O5B—C28B—C29B	124.3 (4)
C17—C16—H16A	110.3	O4—C28B—C29B	112 (2)
C15—C16—H16B	110.3	C28B—C29B—H29A	109.5
C17—C16—H16B	110.3	C28B—C29B—H29B	109.5
H16A—C16—H16B	108.6	H29A—C29B—H29B	109.5
C20—C17—C13	119.2 (3)	C28B—C29B—H29C	109.5
C20—C17—C16	111.5 (3)	H29A—C29B—H29C	109.5
C13—C17—C16	103.6 (2)	H29B—C29B—H29C	109.5
C20—C17—H17A	107.3	C30—O6—C6	118.4 (3)
C13—C17—H17A	107.3
C10—C1—C2—C3	−56.6 (4)	C9—C11—C12—C13	−55.5 (4)
C1—C2—C3—O4	−179.9 (3)	C11—C12—C13—C18	−63.1 (3)
C1—C2—C3—C4	59.8 (4)	C11—C12—C13—C14	58.0 (3)
O4—C3—C4—C5	−178.3 (3)	C11—C12—C13—C17	168.1 (3)
C2—C3—C4—C5	−59.3 (4)	C7—C8—C14—C15	−8.6 (5)
C3—C4—C5—O1	−63.0 (3)	C9—C8—C14—C15	178.2 (3)
C3—C4—C5—C6	177.4 (3)	C7—C8—C14—C13	−133.2 (3)
C3—C4—C5—C10	54.7 (4)	C9—C8—C14—C13	53.6 (4)
O1—C5—C6—O6	−51.2 (3)	C18—C13—C14—C8	61.1 (4)
C4—C5—C6—O6	68.0 (3)	C12—C13—C14—C8	−59.0 (4)
C10—C5—C6—O6	−166.6 (2)	C17—C13—C14—C8	179.1 (3)
O1—C5—C6—C7	65.2 (3)	C18—C13—C14—C15	−70.5 (3)
C4—C5—C6—C7	−175.6 (3)	C12—C13—C14—C15	169.4 (3)
C10—C5—C6—C7	−50.2 (3)	C17—C13—C14—C15	47.5 (3)
O6—C6—C7—C8	136.2 (3)	C8—C14—C15—C16	−165.5 (3)
C5—C6—C7—C8	18.2 (5)	C13—C14—C15—C16	−36.1 (4)
C6—C7—C8—C14	−172.3 (3)	C14—C15—C16—C17	10.4 (4)
C6—C7—C8—C9	0.3 (5)	C18—C13—C17—C20	−46.0 (4)
C7—C8—C9—O2	−108.6 (3)	C12—C13—C17—C20	82.1 (4)
C14—C8—C9—O2	64.7 (3)	C14—C13—C17—C20	−163.9 (3)
C7—C8—C9—C11	142.9 (3)	C18—C13—C17—C16	78.6 (3)
C14—C8—C9—C11	−43.8 (4)	C12—C13—C17—C16	−153.4 (3)
C7—C8—C9—C10	14.6 (4)	C14—C13—C17—C16	−39.3 (3)
C14—C8—C9—C10	−172.2 (3)	C15—C16—C17—C20	148.0 (3)
C2—C1—C10—C19	−68.7 (4)	C15—C16—C17—C13	18.5 (4)
C2—C1—C10—C5	50.9 (4)	C13—C17—C20—C21	−58.8 (4)
C2—C1—C10—C9	170.2 (3)	C16—C17—C20—C21	−179.4 (3)
O1—C5—C10—C19	−172.0 (2)	C13—C17—C20—C22	178.2 (3)
C4—C5—C10—C19	69.4 (3)	C16—C17—C20—C22	57.5 (4)
C6—C5—C10—C19	−55.2 (3)	C21—C20—C22—C23	67.4 (4)
O1—C5—C10—C1	68.6 (3)	C17—C20—C22—C23	−167.8 (3)
C4—C5—C10—C1	−50.0 (4)	C20—C22—C23—C24A	−179.9 (3)
C6—C5—C10—C1	−174.6 (3)	C22—C23—C24A—C25A	−165.9 (4)
O1—C5—C10—C9	−51.8 (3)	C23—C24A—C25A—C27A	−51.2 (7)
C4—C5—C10—C9	−170.5 (3)	C23—C24A—C25A—C26A	179.3 (6)
C6—C5—C10—C9	64.9 (3)	C2—C3—O4—C28B	120 (2)
O2—C9—C10—C19	−166.0 (3)	C4—C3—O4—C28B	−119 (2)
C8—C9—C10—C19	73.5 (3)	C2—C3—O4—C28A	142.1 (4)
C11—C9—C10—C19	−52.6 (3)	C4—C3—O4—C28A	−96.6 (4)
O2—C9—C10—C1	−45.4 (3)	C28B—O4—C28A—O5A	104 (4)
C8—C9—C10—C1	−166.0 (3)	C3—O4—C28A—O5A	6.5 (7)
C11—C9—C10—C1	67.9 (3)	C28B—O4—C28A—C29A	−77 (4)
O2—C9—C10—C5	74.2 (3)	C3—O4—C28A—C29A	−173.9 (4)
C8—C9—C10—C5	−46.4 (3)	C28A—O4—C28B—O5B	−102 (6)
C11—C9—C10—C5	−172.5 (3)	C3—O4—C28B—O5B	−9 (5)
O2—C9—C11—O3	109.9 (3)	C28A—O4—C28B—C29B	91 (5)
C8—C9—C11—O3	−136.8 (3)	C3—O4—C28B—C29B	−176 (3)
C10—C9—C11—O3	−10.2 (4)	O7—C30—O6—C6	4.9 (4)
O2—C9—C11—C12	−67.0 (3)	C31—C30—O6—C6	−176.1 (3)
C8—C9—C11—C12	46.3 (4)	C7—C6—O6—C30	131.8 (3)
C10—C9—C11—C12	173.0 (3)	C5—C6—O6—C30	−108.0 (3)
O3—C11—C12—C13	127.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1D···O1	0.84 (4)	1.89 (4)	2.619 (3)	145 (4)
O1—H1C···O7i	0.76 (4)	2.04 (4)	2.782 (3)	166 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1D⋯O1	0.84 (4)	1.89 (4)	2.619 (3)	145 (4)
O1—H1C⋯O7i	0.76 (4)	2.04 (4)	2.782 (3)	166 (4)

Symmetry code: (i) .