3β-Acetoxy-5α,6β-di­hydroxybisnorcholanic acid 2216 lactone

In the title compound, C₂₄H₃₆O₆, the ester linkage in ring A is equatorial. The six-membered rings A, B and C have chair conformations. The five-membered ring D adopts a 13β,14α-half-chair conformation and the E ring adopts an envelope conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis.

S1. Comment

In connection with our studies on the synthesis and characterization of bioactive steroids, we determined the molecular structure of 3β-acetoxy-5α,6β-dihydroxy-bisnorcholanic acid 22→16 lactone, (I), an intermediate compound in the synthesis of the 3β,5α,6β-triol and 3β,5α-diol-6-keto compounds. The starting material was the steroidal alkaloid solasodine, isolated from Solanum globiferum Dunae, a plant that grows in the fields of Cuba. These products will be tested as plant growth promoters. The absolute configuration was assumed to be the same as that of previous related structures (Novoa de Armas et al., 1999), and confirmed the one predicted beforehand from the synthetic route. scheme

Fig. 1 shows the molecular structure of the title compound, (I), with the corresponding numbering scheme. The C3—O31 bond of the acetoxy group is equatorially oriented and (-)antiperiplanar to the C3—C4 bond. The presence of the acetoxy group bonded to C3 does not disturb the chair conformation of the ring A of the steroidal nucleus. Ring A has a highly symmetrical chair conformation with all asymmetry parameters below 6.4 (3)° (Duax et al., 1976). Rotational symmetry is dominant, a pseudo C₂ axis intercepts the C3—C4 bond with asymmetry parameters ΔC₂(C3—C4) = 3.2 (3), ΔC_S(C1) = 4.4 (2) and ΔC_S(C3) = 0.7 (2)°. The average magnitude of the torsion angles is 55.37 (12)°. Rings B and C have chair conformations, as expected (Pfeiffer et al., 1985). The five-membered ring D adopts a 13β,14α half-chair conformation (Altona et al., 1968) and the E ring, which has a carbonyl group instead of an additional spiro ring, adopts an envelope conformation with the flap at C17 on the opposite side of the mean plane of ring E to the methyl substituent C21. In related steroids reported in the Cambridge Structural Database (Allen & Kennard, 1993) that have a spirostan F ring (Novoa de Armas et al., 1999), the E ring has a half-chair conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis. The bond distances and valence angles are close to the expected values (Honda et al., 1996). The packing of the molecules is assumed to be dictated mainly by intermolecular O—H···O hydrogen bonds, and by intermolecular C—H···O interactions (Taylor & Kennard, 1982). The molecules are linked into an infinite two-dimensional network, with base vectors [100] and [010], by means of the O—H···O hydrogen bonds (Table 2).

S2. Experimental

The starting material was the steroidal alkaloid solasodine. The alkaloid was transformed to 3β,16β-dihydroxy-5-bisnorcholenic acid 22→16 lactone, dissolved in dry pyridine with Ac₂O, and converted to the 3β acetate. The acetate was treated with m-chloroperoxybenzoic acid in CH₂Cl₂ to give a mixture of the α and β-epoxides, with about 30% of the β-component. Upon treatment with 60% HClO₄ in aqueous acetone, the mixture yielded (I) with a melting point of 536–538 K. Crystals were grown by slow evaporation from ethanol.

S3. Refinement

H atoms were calculated geometrically and included in the refinement, but were constrained to ride on their parent atoms. The isotropic displacement parameters of the H atoms were fixed to 1.3 times U_eq of their parent atoms. The number of unique reflections is 2291. The number of Friedel related pairs is 574.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 1990) and PARST (Nardelli, 1983, 1995).

Figures

Fig. 1. Plot showing the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level for non-H atoms; H atoms are omitted for clarity.

3β-acetoxy-5α,6β-dihydroxy-bisnorcholanic acid 22\rigtharrow16 lactone

Crystal data

C24H36O6	Dx = 1.280 Mg m^−3
Mr = 420.53	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 42 reflections
a = 6.3980 (4) Å	θ = 5.0–28.8°
b = 9.7142 (5) Å	µ = 0.73 mm^−1
c = 35.119 (4) Å	T = 293 K
V = 2182.7 (3) Å^3	Prism, colourless
Z = 4	0.38 × 0.22 × 0.18 mm
F(000) = 912

Data collection

Siemens P4 four-circle diffractometer	Rint = 0.024
ω/2θ scans	θmax = 69.1°
Absorption correction: ψ scan (North et al., 1968)	h = −1→6
Tmin = 0.679, Tmax = 0.877	k = −1→11
3136 measured reflections	l = −1→42
2865 independent reflections	3 standard reflections every 100 reflections
2668 reflections with F^2 > 2σ(F^2)	intensity decay: 4.0%

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0791P)^2 + 0.6321P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.046	(Δ/σ)max = 0.001
wR(F^2) = 0.133	Δρmax = 0.39 e Å^−3
S = 1.05	Δρmin = −0.24 e Å^−3
2865 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin((2θ)]^-1/4
278 parameters	Extinction coefficient: 0.0037 (5)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
C1	0.3186 (5)	1.0030 (3)	0.31552 (7)	0.0436 (8)*
C2	0.3475 (5)	1.0009 (3)	0.27193 (7)	0.0491 (9)*
C3	0.3361 (5)	0.8548 (3)	0.25668 (7)	0.0456 (8)*
C4	0.1419 (5)	0.7783 (3)	0.27007 (7)	0.0455 (8)*
O5	0.2977 (3)	0.7171 (2)	0.33032 (5)	0.0475 (6)*
C5	0.1164 (4)	0.7840 (3)	0.31341 (6)	0.0376 (7)*
O6	−0.2547 (3)	0.7396 (3)	0.30701 (5)	0.0637 (8)*
C6	−0.0704 (5)	0.6974 (3)	0.32694 (7)	0.0444 (8)*
C7	−0.0985 (5)	0.7057 (3)	0.36998 (7)	0.0431 (9)*
C8	−0.1049 (4)	0.8534 (2)	0.38502 (6)	0.0342 (8)*
C9	0.0950 (4)	0.9313 (2)	0.37262 (6)	0.0339 (7)*
C10	0.1131 (4)	0.9353 (3)	0.32829 (6)	0.0341 (7)*
C11	0.1160 (5)	1.0737 (3)	0.39139 (7)	0.0410 (8)*
C12	0.0840 (4)	1.0711 (3)	0.43481 (7)	0.0414 (8)*
C13	−0.1236 (4)	1.0033 (2)	0.44505 (6)	0.0333 (7)*
C14	−0.1238 (4)	0.8566 (2)	0.42834 (6)	0.0337 (7)*
C15	−0.3109 (4)	0.7875 (3)	0.44763 (6)	0.0392 (7)*
C16	−0.3025 (4)	0.8466 (2)	0.48822 (7)	0.0366 (7)*
C17	−0.1469 (4)	0.9677 (2)	0.48789 (6)	0.0346 (7)*
C18	−0.3067 (5)	1.0908 (3)	0.43071 (7)	0.0410 (8)*
C19	−0.0674 (5)	1.0193 (3)	0.31126 (7)	0.0471 (8)*
C20	−0.2475 (4)	1.0717 (3)	0.51512 (6)	0.0387 (7)*
C21	−0.1645 (5)	1.0582 (3)	0.55596 (7)	0.0520 (9)*
O22	−0.6236 (4)	1.0970 (2)	0.52643 (7)	0.0641 (8)*
C22	−0.4762 (5)	1.0326 (3)	0.51471 (7)	0.0425 (8)*
O23	−0.5029 (3)	0.9064 (2)	0.49954 (5)	0.0433 (6)*
O31	0.3162 (4)	0.8533 (2)	0.21499 (5)	0.0540 (7)*
O32	0.6399 (5)	0.9319 (4)	0.20565 (8)	0.092 (1)*
C32	0.4777 (7)	0.8905 (4)	0.19356 (9)	0.063 (1)*
C33	0.4327 (8)	0.8781 (4)	0.15219 (9)	0.085 (2)*
H1A	0.4349	0.9553	0.3273	0.054*
H1B	0.3210	1.0977	0.3243	0.054*
H2A	0.2395	1.0563	0.2601	0.061*
H2B	0.4819	1.0407	0.2655	0.061*
H3	0.4615	0.8038	0.2643	0.057*
H4A	0.1510	0.6829	0.2621	0.057*
H4B	0.0195	0.8184	0.2581	0.057*
H5	0.3076	0.6384	0.3221	0.059*
H6	−0.3553	0.7362	0.3214	0.080*
H6A	−0.0425	0.6012	0.3203	0.055*
H7A	0.0156	0.6570	0.3822	0.054*
H7B	−0.2276	0.6596	0.3769	0.054*
H8	−0.2266	0.9001	0.3740	0.043*
H9	0.2135	0.8764	0.3817	0.042*
H11A	0.2538	1.1103	0.3859	0.051*
H11B	0.0140	1.1355	0.3802	0.051*
H12A	0.1976	1.0207	0.4466	0.052*
H12B	0.0862	1.1645	0.4446	0.052*
H14	0.0013	0.8109	0.4383	0.042*
H15A	−0.2959	0.6881	0.4478	0.049*
H15B	−0.4407	0.8117	0.4350	0.049*
H16	−0.2584	0.7759	0.5064	0.046*
H17	−0.0120	0.9376	0.4981	0.043*
H18A	−0.2963	1.1819	0.4411	0.051*
H18B	−0.4361	1.0497	0.4386	0.051*
H18C	−0.3025	1.0955	0.4034	0.051*
H19A	−0.0451	1.1154	0.3162	0.059*
H19B	−0.1968	0.9908	0.3226	0.059*
H19C	−0.0733	1.0043	0.2843	0.059*
H20	−0.2284	1.1658	0.5057	0.048*
H21A	−0.1808	0.9649	0.5645	0.065*
H21B	−0.2416	1.1185	0.5724	0.065*
H21C	−0.0192	1.0827	0.5565	0.065*
H33A	0.4379	0.7829	0.1449	0.106*
H33B	0.5350	0.9290	0.1380	0.106*
H33C	0.2961	0.9143	0.1470	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.038 (2)	0.053 (1)	0.040 (1)	−0.008 (1)	0.005 (1)	−0.001 (1)
C2	0.045 (2)	0.062 (2)	0.041 (1)	−0.009 (2)	0.005 (1)	0.001 (1)
C3	0.043 (2)	0.061 (2)	0.033 (1)	−0.002 (2)	0.002 (1)	0.002 (1)
C4	0.045 (2)	0.056 (1)	0.036 (1)	−0.004 (1)	0.003 (1)	−0.006 (1)
O5	0.042 (1)	0.051 (1)	0.050 (1)	0.009 (1)	0.0009 (9)	−0.0010 (8)
C5	0.032 (1)	0.046 (1)	0.035 (1)	−0.002 (1)	−0.001 (1)	0.000 (1)
O6	0.036 (1)	0.112 (2)	0.0427 (9)	−0.015 (1)	−0.0022 (9)	−0.007 (1)
C6	0.042 (2)	0.050 (1)	0.041 (1)	−0.011 (1)	0.004 (1)	−0.008 (1)
C7	0.049 (2)	0.042 (1)	0.039 (1)	−0.010 (1)	0.004 (1)	−0.003 (1)
C8	0.033 (1)	0.037 (1)	0.033 (1)	−0.004 (1)	−0.002 (1)	0.0004 (9)
C9	0.028 (1)	0.041 (1)	0.033 (1)	−0.002 (1)	−0.002 (1)	0.0017 (9)
C10	0.026 (1)	0.043 (1)	0.033 (1)	−0.003 (1)	−0.001 (1)	0.0007 (9)
C11	0.040 (2)	0.043 (1)	0.040 (1)	−0.012 (1)	0.004 (1)	−0.002 (1)
C12	0.036 (2)	0.048 (1)	0.040 (1)	−0.010 (1)	0.001 (1)	−0.007 (1)
C13	0.030 (1)	0.037 (1)	0.033 (1)	−0.005 (1)	0.000 (1)	−0.0014 (9)
C14	0.032 (1)	0.038 (1)	0.032 (1)	−0.001 (1)	0.001 (1)	−0.0012 (9)
C15	0.041 (2)	0.038 (1)	0.038 (1)	−0.009 (1)	0.005 (1)	0.000 (1)
C16	0.037 (1)	0.036 (1)	0.037 (1)	0.002 (1)	0.006 (1)	0.0042 (9)
C17	0.032 (1)	0.039 (1)	0.033 (1)	0.002 (1)	−0.001 (1)	−0.0011 (9)
C18	0.039 (2)	0.043 (1)	0.041 (1)	0.003 (1)	−0.002 (1)	0.006 (1)
C19	0.044 (2)	0.060 (2)	0.038 (1)	0.006 (2)	−0.001 (1)	0.009 (1)
C20	0.038 (2)	0.041 (1)	0.037 (1)	0.001 (1)	0.002 (1)	−0.003 (1)
C21	0.052 (2)	0.067 (2)	0.037 (1)	0.005 (2)	−0.001 (1)	−0.009 (1)
O22	0.045 (1)	0.065 (1)	0.082 (1)	0.011 (1)	0.012 (1)	−0.017 (1)
C22	0.039 (2)	0.046 (1)	0.043 (1)	0.003 (1)	0.002 (1)	−0.003 (1)
O23	0.034 (1)	0.0434 (9)	0.0524 (9)	−0.0022 (9)	0.0103 (9)	−0.0041 (8)
O31	0.057 (1)	0.072 (1)	0.0325 (8)	−0.005 (1)	0.0100 (9)	0.0000 (8)
O32	0.074 (2)	0.126 (3)	0.077 (2)	−0.029 (2)	0.028 (2)	−0.014 (2)
C32	0.072 (3)	0.062 (2)	0.054 (2)	−0.005 (2)	0.023 (2)	−0.005 (1)
C33	0.135 (4)	0.074 (2)	0.046 (2)	0.013 (3)	0.028 (2)	0.007 (2)

Geometric parameters (Å, º)

O5—C5	1.456 (3)	C32—C33	1.486 (5)
O6—C6	1.431 (4)	C1—H1A	0.9699
O22—C22	1.204 (4)	C1—H1B	0.9703
O23—C16	1.463 (3)	C2—H2A	0.9698
O23—C22	1.348 (3)	C2—H2B	0.9700
O31—C3	1.470 (3)	C3—H3	0.9801
O31—C32	1.328 (5)	C4—H4A	0.9702
O32—C32	1.191 (5)	C4—H4B	0.9697
O5—H5	0.8195	C6—H6A	0.9797
O6—H6	0.8201	C7—H7A	0.9703
C1—C2	1.542 (4)	C7—H7B	0.9698
C1—C10	1.537 (4)	C8—H8	0.9799
C2—C3	1.518 (4)	C9—H9	0.9804
C3—C4	1.523 (4)	C11—H11A	0.9700
C4—C5	1.532 (3)	C11—H11B	0.9702
C5—C10	1.560 (4)	C12—H12A	0.9700
C5—C6	1.537 (4)	C12—H12B	0.9704
C6—C7	1.524 (4)	C14—H14	0.9799
C7—C8	1.529 (3)	C15—H15A	0.9699
C8—C14	1.526 (3)	C15—H15B	0.9698
C8—C9	1.549 (3)	C16—H16	0.9800
C9—C11	1.538 (3)	C17—H17	0.9797
C9—C10	1.562 (3)	C18—H18A	0.9597
C10—C19	1.535 (4)	C18—H18B	0.9601
C11—C12	1.539 (3)	C18—H18C	0.9599
C12—C13	1.526 (4)	C19—H19A	0.9601
C13—C18	1.532 (4)	C19—H19B	0.9602
C13—C14	1.541 (3)	C19—H19C	0.9600
C13—C17	1.551 (3)	C20—H20	0.9795
C14—C15	1.531 (3)	C21—H21A	0.9600
C15—C16	1.538 (3)	C21—H21B	0.9600
C16—C17	1.541 (3)	C21—H21C	0.9600
C17—C20	1.533 (3)	C33—H33A	0.9604
C20—C21	1.535 (3)	C33—H33B	0.9599
C20—C22	1.512 (4)	C33—H33C	0.9599
C16—O23—C22	110.9 (2)	C4—C3—H3	109.68
C3—O31—C32	119.6 (3)	C3—C4—H4A	109.18
C5—O5—H5	109.50	C3—C4—H4B	109.19
C6—O6—H6	109.46	C5—C4—H4A	109.19
C2—C1—C10	112.7 (2)	C5—C4—H4B	109.20
C1—C2—C3	110.9 (2)	H4A—C4—H4B	107.90
C2—C3—C4	112.8 (2)	O6—C6—H6A	107.89
O31—C3—C2	111.4 (2)	C5—C6—H6A	107.90
O31—C3—C4	103.4 (2)	C7—C6—H6A	107.90
C3—C4—C5	112.1 (2)	C6—C7—H7A	108.91
O5—C5—C10	107.14 (19)	C6—C7—H7B	108.93
O5—C5—C4	107.7 (2)	C8—C7—H7A	108.90
O5—C5—C6	104.4 (2)	C8—C7—H7B	108.94
C6—C5—C10	113.7 (2)	H7A—C7—H7B	107.74
C4—C5—C10	111.6 (2)	C7—C8—H8	108.61
C4—C5—C6	111.7 (2)	C9—C8—H8	108.64
O6—C6—C7	111.9 (2)	C14—C8—H8	108.63
O6—C6—C5	109.4 (2)	C8—C9—H9	106.35
C5—C6—C7	111.7 (2)	C10—C9—H9	106.33
C6—C7—C8	113.3 (2)	C11—C9—H9	106.36
C7—C8—C9	109.8 (2)	C9—C11—H11A	108.91
C9—C8—C14	109.62 (18)	C9—C11—H11B	108.87
C7—C8—C14	111.43 (17)	C12—C11—H11A	108.88
C8—C9—C11	113.0 (2)	C12—C11—H11B	108.85
C8—C9—C10	110.72 (19)	H11A—C11—H11B	107.71
C10—C9—C11	113.48 (19)	C11—C12—H12A	109.47
C1—C10—C9	111.4 (2)	C11—C12—H12B	109.45
C1—C10—C5	107.1 (2)	C13—C12—H12A	109.49
C5—C10—C19	112.4 (2)	C13—C12—H12B	109.47
C9—C10—C19	110.2 (2)	H12A—C12—H12B	108.02
C5—C10—C9	108.15 (19)	C8—C14—H14	106.39
C1—C10—C19	107.6 (2)	C13—C14—H14	106.39
C9—C11—C12	113.5 (2)	C15—C14—H14	106.38
C11—C12—C13	110.9 (2)	C14—C15—H15A	111.21
C12—C13—C18	110.4 (2)	C14—C15—H15B	111.22
C12—C13—C14	108.1 (2)	C16—C15—H15A	111.24
C12—C13—C17	114.1 (2)	C16—C15—H15B	111.24
C17—C13—C18	111.7 (2)	H15A—C15—H15B	109.17
C14—C13—C17	99.39 (15)	O23—C16—H16	110.70
C14—C13—C18	112.8 (2)	C15—C16—H16	110.69
C8—C14—C13	113.47 (16)	C17—C16—H16	110.71
C8—C14—C15	119.62 (19)	C13—C17—H17	109.75
C13—C14—C15	103.75 (19)	C16—C17—H17	109.78
C14—C15—C16	102.7 (2)	C20—C17—H17	109.74
C15—C16—C17	107.49 (19)	C13—C18—H18A	109.50
O23—C16—C17	105.39 (16)	C13—C18—H18B	109.45
O23—C16—C15	111.7 (2)	C13—C18—H18C	109.46
C13—C17—C20	119.91 (18)	H18A—C18—H18B	109.48
C13—C17—C16	103.86 (18)	H18A—C18—H18C	109.49
C16—C17—C20	103.1 (2)	H18B—C18—H18C	109.44
C17—C20—C22	103.6 (2)	C10—C19—H19A	109.48
C17—C20—C21	112.4 (2)	C10—C19—H19B	109.47
C21—C20—C22	108.8 (2)	C10—C19—H19C	109.49
O22—C22—C20	128.6 (3)	H19A—C19—H19B	109.44
O23—C22—C20	110.8 (2)	H19A—C19—H19C	109.47
O22—C22—O23	120.6 (3)	H19B—C19—H19C	109.47
O32—C32—C33	123.0 (4)	C17—C20—H20	110.62
O31—C32—O32	124.6 (3)	C21—C20—H20	110.60
O31—C32—C33	112.4 (4)	C22—C20—H20	110.60
C2—C1—H1A	109.04	C20—C21—H21A	109.49
C2—C1—H1B	109.01	C20—C21—H21B	109.48
C10—C1—H1A	109.07	C20—C21—H21C	109.45
C10—C1—H1B	109.07	H21A—C21—H21B	109.47
H1A—C1—H1B	107.79	H21A—C21—H21C	109.47
C1—C2—H2A	109.46	H21B—C21—H21C	109.47
C1—C2—H2B	109.46	C32—C33—H33A	109.47
C3—C2—H2A	109.45	C32—C33—H33B	109.49
C3—C2—H2B	109.45	C32—C33—H33C	109.51
H2A—C2—H2B	108.05	H33A—C33—H33B	109.43
O31—C3—H3	109.66	H33A—C33—H33C	109.44
C2—C3—H3	109.72	H33B—C33—H33C	109.49
C22—O23—C16—C17	−15.4 (2)	C14—C8—C9—C11	−48.9 (2)
C16—O23—C22—O22	−178.5 (2)	C14—C8—C9—C10	−177.48 (18)
C22—O23—C16—C15	−131.8 (2)	C7—C8—C9—C10	59.8 (2)
C16—O23—C22—C20	0.0 (3)	C8—C9—C10—C19	64.8 (3)
C32—O31—C3—C4	−168.3 (3)	C8—C9—C10—C5	−58.4 (2)
C3—O31—C32—C33	178.0 (3)	C11—C9—C10—C1	55.8 (3)
C32—O31—C3—C2	70.3 (4)	C8—C9—C10—C1	−175.9 (2)
C3—O31—C32—O32	−3.4 (6)	C10—C9—C11—C12	176.3 (2)
C2—C1—C10—C19	−62.5 (3)	C11—C9—C10—C5	173.2 (2)
C2—C1—C10—C9	176.6 (2)	C8—C9—C11—C12	49.1 (3)
C10—C1—C2—C3	−56.5 (3)	C11—C9—C10—C19	−63.6 (3)
C2—C1—C10—C5	58.5 (3)	C9—C11—C12—C13	−53.9 (3)
C1—C2—C3—O31	167.3 (2)	C11—C12—C13—C17	167.4 (2)
C1—C2—C3—C4	51.5 (3)	C11—C12—C13—C14	57.9 (3)
C2—C3—C4—C5	−52.1 (3)	C11—C12—C13—C18	−65.9 (3)
O31—C3—C4—C5	−172.6 (2)	C18—C13—C17—C20	−34.3 (3)
C3—C4—C5—O5	−61.6 (3)	C18—C13—C14—C15	−70.4 (2)
C3—C4—C5—C10	55.8 (3)	C18—C13—C14—C8	61.0 (3)
C3—C4—C5—C6	−175.7 (2)	C18—C13—C17—C16	80.0 (2)
C4—C5—C10—C19	60.2 (3)	C17—C13—C14—C8	179.4 (2)
C4—C5—C6—O6	−54.3 (3)	C17—C13—C14—C15	48.0 (2)
C10—C5—C6—O6	73.1 (3)	C12—C13—C17—C16	−153.9 (2)
C4—C5—C6—C7	−178.7 (2)	C14—C13—C17—C20	−153.5 (2)
C6—C5—C10—C1	174.7 (2)	C14—C13—C17—C16	−39.2 (2)
O5—C5—C6—C7	65.1 (3)	C12—C13—C14—C15	167.33 (18)
C10—C5—C6—C7	−51.3 (3)	C12—C13—C17—C20	91.8 (3)
C4—C5—C10—C9	−178.0 (2)	C12—C13—C14—C8	−61.3 (3)
C4—C5—C10—C1	−57.8 (3)	C8—C14—C15—C16	−165.29 (19)
O5—C5—C10—C1	59.9 (2)	C13—C14—C15—C16	−37.7 (2)
O5—C5—C6—O6	−170.5 (2)	C14—C15—C16—O23	127.42 (19)
O5—C5—C10—C9	−60.3 (2)	C14—C15—C16—C17	12.3 (2)
O5—C5—C10—C19	177.84 (19)	C15—C16—C17—C20	142.97 (19)
C6—C5—C10—C19	−67.3 (3)	O23—C16—C17—C20	23.7 (2)
C6—C5—C10—C9	54.6 (3)	C15—C16—C17—C13	17.2 (2)
C5—C6—C7—C8	51.4 (3)	O23—C16—C17—C13	−102.1 (2)
O6—C6—C7—C8	−71.6 (3)	C16—C17—C20—C21	94.1 (2)
C6—C7—C8—C9	−55.9 (3)	C13—C17—C20—C21	−151.2 (2)
C6—C7—C8—C14	−177.5 (2)	C16—C17—C20—C22	−23.2 (2)
C7—C8—C9—C11	−171.7 (2)	C13—C17—C20—C22	91.5 (3)
C9—C8—C14—C13	56.3 (3)	C21—C20—C22—O22	73.9 (4)
C7—C8—C14—C13	178.1 (2)	C21—C20—C22—O23	−104.5 (2)
C9—C8—C14—C15	179.3 (2)	C17—C20—C22—O23	15.3 (3)
C7—C8—C14—C15	−58.9 (3)	C17—C20—C22—O22	−166.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O32^i	0.82	2.26	3.071 (4)	173
O6—H6···O5^ii	0.82	2.25	2.986 (3)	150
C3—H3···O6^iii	0.98	2.44	3.352 (4)	155
C16—H16···O23^iv	0.98	2.42	3.146 (3)	131

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x+1/2, −y+3/2, −z+1.