3[beta],7[alpha],12[alpha]-Tri­formyl­oxy-24-nor-5[beta]-chol-22-ene

The title compound, alternatively called 24-nor-5[beta]-chol-22-ene-3[beta],7[alpha],12[alpha]-triyl triformate, C₂₆H₃₈O₆, has a cis junction between two of the six-membered rings. All three of the six-membered rings have chair conformations that are slightly flattened and the five-membered ring has a 13[beta],14[alpha]-half-chair conformation. The 3[beta], 7[alpha] and 12[alpha] ring substituents are axial and the 17[beta] group is equatorial. The 3[beta]-formyl­oxy group is involved in one weak intermol­ecular C-H...O bond, which links the mol­ecules into dimers in a head-to-head fashion.

S1. Comment

The bile acids, such as cholic acid, have proved particularly useful as `engineering components' for supramolecular chemistry (Davis, 1993). The size, chirality and rigid polycyclic framework of a steroid-based synthetic receptor confers to it a high degree of preorganization. An examination of the structures of the synthetic receptors and their synthetic intermediates, on a crystallographic basis, could help to improve our understanding of molecular-recognition principles. In an attempt to construct a steroid-based synthetic receptor, the title compound, 3β,7α,12α-triformyloxy-24-nor-5β-chol-22-ene, (I), has been synthesized as an intermediate according to ?the method reported by Davis & Walsh (1996)?, although different reactions have been used as described in the experimental section. This cholic acid derivative, without the C(24)OOH group in the 17β side chain, contains three formyloxy groups with a 3β,7α,12α configuration. Cholic and deoxycholic acids provide tunnel-like spaces, reported as a channel-like inclusion ability (Miki et al., 1990; Jones & Nassimbeni, 1990), in which guest molecules can be accommodated. Examination of the crystal structure of (I) shows no guest molecules and a small solvent-accessible volume (i.e. 4 x 15 ų).

An ORTEPII (Johnson, 1976) plot of (I), with the corresponding atomic numbering scheme and ring labels, is shown in Fig.1. Bond lengths and angles are within the expected ranges (Allen et al., 1987), the mean O—Csp³, O—Csp² and O═Csp² distances being 1.467 (3), 1.331 (3) and 1.189 (2) Å in the three formyloxy groups, and the mean Csp³—Csp² and Csp²═Csp² distances being 1.503 (3) and 1.304 (4) Å in the 17β-group. The distance between the terminal atoms, O31—C23, is 13.275 (4) Å and the C19—C10—C13—C18 pseudo-torsion angle is 3.0 (2)°. The A/B ring junction is 5β,10β cis [C1—C10—C5—C4 = 51.3 (3)° and C9—C10—C5—C6 = 55.1 (2)°]. The bowing angle between ring A and the least-squares plane that includes the atoms of B, C and D rings is 63.16 (5)°. Rings A, B and C have slightly flattened chair conformations, with average torsion angles of 52.6 (7), 52.0 (14) and 55.0 (16)°, respectively, as shown by the values [177.0 (3), 8.0 (2) and 6.6 (2)° for A, B and C] of the θ puckering parameter (Cremer & Pople, 1975; Boeyens, 1978). The five-membered ring D assumes a 13β,14α half-chair conformation [puckering parameters, calculated using the atom sequence C13···C17: q₂ = 0.461 (2) Å and ϕ₂ = 195.4 (3)°; pseudo-rotation (Altona et al., 1968) and asymmetry parameters: Δ = −3.8 (2), ϕ_m = 46.8 (1), ΔC_s(13) = 16.0 (2), ΔC_s(14) = 19.4 (2) and ΔC₂(13,14) = 2.7 (2)°]. This unusal ring conformation is different from that observed in cholic acid (Jones & Nassimbeni, 1990). The three 3β,7α,12α-ring substituents are axial (Luger & Bulow, 1983), with angles of 6.3 (2), 9.9 (1) and 4.6 (1)°, respectively. The angle between the planes defined by the 3β-group and the A ring is 80.5 (2)°, and those between the planes of the 7α-,12α-groups and the mean plane of rings B, C and D are 85.6 (3) and 89.6 (2)°, respectively. The 17β-chain is equatorial. The orientation of the C5–C17 reference plane relative to C17/C20/C21 and C2/C22/C23 least-squares planes is 19.54 (19) and 77.30 (19)° respectively, with the angle between these two planes being 85.0 (2)°. Comparing with the structure of cholic acid (Miki et al., 1990; Jones & Nassimbeni, 1990), the absence of the COOH group in the side chain attached to C17 may be responsible for the unusual values of the C17—C20—C22—C23 and C21—C20—C22—C23 torsion angles [−109.7 (3) 126.7 (3)°], corresponding to -ac and +ac descriptors, respectively, instead of -ap and +sc.

The crystal structure contains no classical hydrogen bonds and thus cohesion of the structure is mainly achieved by van der Waals interactions and C–H···O weak interactions. Four intramolecular C–H···O short contacts are present; one [C4–H4A···O7 at 3.029 (3) Å with bent angle 126°] is probably a destabilizing interaction; the other three may be qualified as weak hydrogen bonds with distances and angles in the ranges 2.750 (4)–2.929 (3) Å and 102–108°, respectively. An intermolecular C31–H31···O31⁽ⁱ⁾ interaction [3.396 (4) Å and 166°; symmetry code: (i) −1/2 + x, 1/2 − y, 1 − z] is also present, linking the molecules head-to-head in dimers.

S2. Experimental

The title compound was prepared according to previously described procedures, starting from formylation of cholic acid (Tserng & Klein, 1977) with formic and perchoric acids, followed by oxidative decarboxylation (Concépcion et al., 1986) with iodosobenzene diacetate, selective 3α-deformylation with sodium acetate in methanol, and finally a C-3 Mitsunobu inversion (Bose et al., 1973) with formate, diethyl azodicarboxylate and triphenylphosphine. Crystals siutable for X-ray analysis were obtained from an ethyl acetate solution by slow evaporation. 3β,7α,12α-triformyloxy-24-nor-5β-chol-22-ene: ¹H NMR (300 MHz, CDCl₃): δ 8.17 (1H, s), 8.09 (1H, s), 8.05 (1H, s), 5.67–5.55 (1H, m), 5.27 (1H, br t), 5.16 (1H, br s), 5.07 (1H, d, J=2.4 Hz), 4.91 (1H, dd, J=17.1; 1.8 Hz), 4.83 (1H, dd, J=10.2; 1.8 Hz), 0.98 (3H, s), 0.95 (3H, d, J=6.6 Hz), 0,78 (3H, s); ¹³C NMR (75.25 MHz, CDCl₃): δ 160.7, 160.5, 144.2, 112.3, 75.2, 71.0, 70.1, 46.8, 45.0, 43.0, 40.5, 37.7, 36.3, 34.5, 32.7, 30.9, 30.1, 28.1, 27.3, 25.8, 24.7, 22.7, 19.5, 12.3.

S3. Refinement

All H atoms were refined as riding on their parent atoms, using SHELXL97 (Sheldrick, 1997) defaults. Friedel pairs were merged because the anomalous dispersion of the light atoms at the Cu Kα wavelength was negligeable, and thus the absolute configuration was not determined from the X-ray data. However, the configuration was known from the synthesis route.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: PLATON (Spek,2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson,1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1.

24-nor-5β-chol-22-ene-3β,7α,12α-triyl triformate

Crystal data

C26H38O6	F(000) = 968
Mr = 446.56	Dx = 1.221 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.365 (3) Å	θ = 22.7–28.7°
b = 15.5549 (12) Å	µ = 0.69 mm^−1
c = 21.199 (4) Å	T = 293 K
V = 2428.6 (10) Å^3	Prism, colourless
Z = 4	0.37 × 0.24 × 0.24 mm

Data collection

Enraf–Nonius MACH-3 diffractometer	2293 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 71.9°, θmin = 4.2°
profile data from ω–2θ scans	h = 0→9
Absorption correction: ψ scan North et al., 1968	k = 0→19
Tmin = 0.744, Tmax = 0.847	l = −26→26
4523 measured reflections	3 standard reflections every 200 reflections
2731 independent reflections	intensity decay: 9.9%

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0653P)^2 + 0.1429P] where P = (Fo^2 + 2Fc^2)/3
2731 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.13 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	0.0370 (3)	0.24038 (11)	0.37737 (8)	0.0618 (4)
O7	0.4243 (2)	0.50124 (10)	0.26668 (7)	0.0508 (4)
O12	0.5049 (2)	0.31762 (9)	0.09711 (7)	0.0514 (4)
O31	0.1860 (4)	0.27531 (13)	0.46646 (9)	0.0798 (6)
O71	0.4452 (5)	0.63027 (15)	0.31288 (13)	0.1208 (11)
O121	0.4815 (4)	0.20550 (12)	0.03007 (11)	0.0856 (7)
C1	0.0132 (4)	0.25933 (16)	0.23814 (12)	0.0602 (6)
H1A	−0.1000	0.2495	0.2604	0.090*
H1B	0.0045	0.2307	0.1976	0.090*
C2	0.1675 (4)	0.21842 (14)	0.27578 (12)	0.0598 (6)
H2A	0.1404	0.1581	0.2826	0.090*
H2B	0.2788	0.2219	0.2514	0.090*
C3	0.1960 (3)	0.26166 (14)	0.33864 (11)	0.0514 (5)
H3	0.3055	0.2384	0.3586	0.062*
C4	0.2162 (3)	0.35778 (13)	0.33076 (10)	0.0463 (5)
H4A	0.3319	0.3694	0.3106	0.070*
H4B	0.2188	0.3841	0.3722	0.070*
C5	0.0652 (3)	0.40013 (13)	0.29184 (10)	0.0461 (5)
H5	−0.0478	0.3928	0.3157	0.069*
C6	0.0974 (3)	0.49711 (15)	0.28592 (11)	0.0550 (6)
H6A	−0.0150	0.5242	0.2728	0.082*
H6B	0.1283	0.5197	0.3272	0.082*
C7	0.2455 (3)	0.52208 (13)	0.23995 (10)	0.0479 (5)
H7	0.2392	0.5843	0.2328	0.058*
C8	0.2309 (3)	0.47658 (12)	0.17678 (9)	0.0409 (4)
H8	0.1261	0.5009	0.1546	0.061*
C9	0.1986 (3)	0.37844 (12)	0.18302 (10)	0.0400 (4)
H9	0.3071	0.3541	0.2029	0.060*
C10	0.0354 (3)	0.35731 (15)	0.22679 (10)	0.0474 (5)
C11	0.1837 (3)	0.33797 (15)	0.11684 (10)	0.0513 (5)
H11A	0.1757	0.2760	0.1214	0.077*
H11B	0.0718	0.3575	0.0974	0.077*
C12	0.3409 (3)	0.35871 (13)	0.07256 (9)	0.0436 (5)
H12	0.3142	0.3359	0.0305	0.052*
C13	0.3791 (3)	0.45545 (12)	0.06769 (9)	0.0392 (4)
C14	0.3970 (3)	0.49118 (12)	0.13539 (9)	0.0391 (4)
H14	0.4968	0.4594	0.1552	0.059*
C15	0.4659 (4)	0.58273 (13)	0.12531 (10)	0.0529 (6)
H15A	0.5291	0.6037	0.1624	0.079*
H15B	0.3667	0.6215	0.1155	0.079*
C16	0.5961 (4)	0.57386 (14)	0.06910 (10)	0.0550 (6)
H16A	0.7209	0.5795	0.0831	0.082*
H16B	0.5719	0.6184	0.0382	0.082*
C17	0.5647 (3)	0.48375 (13)	0.03969 (9)	0.0413 (4)
H17	0.6573	0.4454	0.0573	0.062*
C18	0.2224 (3)	0.49746 (17)	0.03086 (11)	0.0549 (5)
H18A	0.2112	0.4705	−0.0097	0.082*
H18B	0.2470	0.5576	0.0254	0.082*
H18C	0.1112	0.4904	0.0539	0.082*
C19	−0.1458 (3)	0.3886 (2)	0.19834 (13)	0.0723 (8)
H19A	−0.2407	0.3823	0.2290	0.108*
H19B	−0.1743	0.3548	0.1617	0.108*
H19C	−0.1350	0.4479	0.1866	0.108*
C20	0.5918 (3)	0.48459 (14)	−0.03252 (9)	0.0456 (5)
H20	0.5073	0.5263	−0.0510	0.068*
C21	0.5581 (4)	0.39676 (15)	−0.06291 (10)	0.0577 (6)
H21A	0.5913	0.3990	−0.1067	0.087*
H21B	0.4318	0.3822	−0.0593	0.087*
H21C	0.6299	0.3540	−0.0419	0.087*
C22	0.7822 (3)	0.51279 (17)	−0.04687 (11)	0.0570 (6)
H22	0.8743	0.4743	−0.0368	0.068*
C23	0.8321 (4)	0.5855 (2)	−0.07201 (13)	0.0746 (8)
H23A	0.7453	0.6263	−0.0830	0.090*
H23B	0.9545	0.5967	−0.0789	0.090*
C31	0.0556 (5)	0.24857 (17)	0.43939 (13)	0.0670 (7)
H31	−0.0425	0.2318	0.4641	0.080*
C71	0.5043 (5)	0.56067 (18)	0.30160 (12)	0.0744 (9)
H71	0.6166	0.5469	0.3189	0.089*
C121	0.5552 (4)	0.24346 (14)	0.07129 (13)	0.0643 (7)
H121	0.6602	0.2185	0.0874	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0637 (11)	0.0610 (10)	0.0607 (10)	−0.0044 (9)	0.0051 (8)	0.0080 (8)
O7	0.0585 (9)	0.0465 (8)	0.0474 (7)	−0.0070 (7)	−0.0060 (7)	−0.0093 (6)
O12	0.0578 (9)	0.0372 (7)	0.0592 (9)	0.0086 (7)	−0.0053 (8)	−0.0056 (6)
O31	0.0967 (16)	0.0787 (13)	0.0640 (11)	0.0100 (13)	−0.0094 (12)	0.0008 (10)
O71	0.174 (3)	0.0777 (15)	0.1104 (18)	−0.0260 (18)	−0.013 (2)	−0.0489 (14)
O121	0.1141 (18)	0.0525 (9)	0.0903 (13)	−0.0053 (12)	0.0278 (14)	−0.0266 (10)
C1	0.0632 (15)	0.0586 (13)	0.0587 (13)	−0.0206 (12)	0.0003 (13)	−0.0055 (11)
C2	0.0741 (16)	0.0389 (10)	0.0664 (14)	−0.0030 (12)	0.0082 (14)	−0.0032 (10)
C3	0.0539 (13)	0.0439 (11)	0.0564 (12)	0.0026 (10)	0.0017 (11)	0.0027 (10)
C4	0.0490 (12)	0.0402 (10)	0.0498 (11)	0.0010 (10)	−0.0033 (10)	−0.0021 (9)
C5	0.0413 (11)	0.0465 (11)	0.0503 (11)	0.0072 (9)	0.0063 (9)	−0.0004 (9)
C6	0.0629 (14)	0.0458 (12)	0.0562 (12)	0.0169 (11)	0.0104 (11)	−0.0032 (10)
C7	0.0604 (13)	0.0336 (9)	0.0498 (11)	0.0070 (10)	0.0033 (10)	−0.0053 (8)
C8	0.0416 (10)	0.0366 (9)	0.0445 (10)	0.0065 (9)	−0.0045 (8)	−0.0032 (8)
C9	0.0372 (10)	0.0386 (9)	0.0442 (10)	−0.0010 (8)	−0.0033 (8)	−0.0044 (8)
C10	0.0365 (10)	0.0548 (11)	0.0507 (11)	−0.0027 (10)	−0.0042 (9)	−0.0001 (10)
C11	0.0510 (13)	0.0519 (12)	0.0511 (11)	−0.0114 (10)	−0.0038 (10)	−0.0127 (10)
C12	0.0463 (11)	0.0436 (10)	0.0409 (10)	−0.0034 (9)	−0.0066 (9)	−0.0087 (8)
C13	0.0391 (10)	0.0395 (10)	0.0388 (9)	0.0031 (8)	−0.0067 (8)	−0.0029 (8)
C14	0.0430 (11)	0.0339 (9)	0.0406 (9)	0.0012 (9)	−0.0053 (8)	−0.0040 (7)
C15	0.0692 (15)	0.0386 (10)	0.0509 (11)	−0.0075 (11)	0.0039 (11)	−0.0053 (9)
C16	0.0698 (16)	0.0460 (11)	0.0491 (11)	−0.0132 (11)	0.0005 (12)	−0.0041 (9)
C17	0.0421 (10)	0.0415 (9)	0.0402 (9)	0.0002 (9)	−0.0061 (8)	−0.0009 (8)
C18	0.0469 (12)	0.0651 (13)	0.0525 (12)	0.0089 (12)	−0.0107 (10)	0.0029 (11)
C19	0.0369 (12)	0.111 (2)	0.0691 (16)	0.0025 (14)	−0.0049 (12)	0.0091 (16)
C20	0.0471 (11)	0.0482 (11)	0.0414 (10)	0.0068 (10)	−0.0041 (9)	0.0024 (9)
C21	0.0738 (16)	0.0580 (13)	0.0415 (10)	0.0037 (13)	−0.0028 (11)	−0.0059 (10)
C22	0.0512 (13)	0.0695 (15)	0.0504 (12)	0.0083 (12)	0.0006 (10)	0.0026 (11)
C23	0.0645 (17)	0.0846 (19)	0.0747 (17)	−0.0059 (16)	0.0108 (15)	0.0047 (15)
C31	0.0812 (19)	0.0569 (14)	0.0628 (15)	0.0119 (15)	0.0100 (15)	0.0098 (12)
C71	0.098 (2)	0.0724 (17)	0.0522 (13)	−0.0291 (17)	−0.0047 (15)	−0.0159 (12)
C121	0.0804 (18)	0.0373 (11)	0.0752 (16)	0.0066 (12)	0.0256 (15)	0.0028 (11)

Geometric parameters (Å, º)

O12—C121	1.329 (3)	C17—C16	1.551 (3)
O12—C12	1.462 (3)	C17—H17	0.9800
O7—C71	1.323 (3)	C2—C1	1.528 (4)
O7—C7	1.470 (3)	C2—H2A	0.9700
C12—C11	1.525 (3)	C2—H2B	0.9700
C12—C13	1.534 (3)	C18—H18A	0.9600
C12—H12	0.9800	C18—H18B	0.9600
O3—C31	1.328 (3)	C18—H18C	0.9600
O3—C3	1.468 (3)	C15—C16	1.536 (3)
C9—C11	1.542 (3)	C15—H15A	0.9700
C9—C8	1.551 (3)	C15—H15B	0.9700
C9—C10	1.553 (3)	C21—C20	1.531 (3)
C9—H9	0.9800	C21—H21A	0.9600
C14—C8	1.523 (3)	C21—H21B	0.9600
C14—C15	1.527 (3)	C21—H21C	0.9600
C14—C13	1.545 (3)	C1—H1A	0.9700
C14—H14	0.9800	C1—H1B	0.9700
C8—C7	1.519 (3)	C20—C22	1.500 (3)
C8—H8	0.9800	C20—H20	0.9800
C3—C2	1.507 (3)	C121—O121	1.186 (4)
C3—C4	1.512 (3)	C121—H121	0.9300
C3—H3	0.9800	C22—C23	1.304 (4)
C6—C7	1.513 (3)	C22—H22	0.9300
C6—C5	1.532 (3)	C71—O71	1.191 (4)
C6—H6A	0.9700	C71—H71	0.9300
C6—H6B	0.9700	C19—H19A	0.9600
C7—H7	0.9800	C19—H19B	0.9600
C13—C18	1.539 (3)	C19—H19C	0.9600
C13—C17	1.554 (3)	C16—H16A	0.9700
C5—C4	1.534 (3)	C16—H16B	0.9700
C5—C10	1.547 (3)	C4—H4A	0.9700
C5—H5	0.9800	C4—H4B	0.9700
C11—H11A	0.9700	C23—H23A	0.9300
C11—H11B	0.9700	C23—H23B	0.9300
C10—C19	1.543 (3)	C31—O31	1.193 (4)
C10—C1	1.552 (3)	C31—H31	0.9300
C17—C20	1.544 (3)
C121—O12—C12	117.6 (2)	C20—C17—H17	107.1
C71—O7—C7	117.4 (2)	C16—C17—H17	107.1
O12—C12—C11	108.40 (17)	C13—C17—H17	107.1
O12—C12—C13	107.53 (16)	C3—C2—C1	112.3 (2)
C11—C12—C13	112.84 (18)	C3—C2—H2A	109.1
O12—C12—H12	109.3	C1—C2—H2A	109.1
C11—C12—H12	109.3	C3—C2—H2B	109.1
C13—C12—H12	109.3	C1—C2—H2B	109.1
C31—O3—C3	116.7 (2)	H2A—C2—H2B	107.9
C11—C9—C8	109.58 (17)	C13—C18—H18A	109.5
C11—C9—C10	113.73 (17)	C13—C18—H18B	109.5
C8—C9—C10	112.22 (17)	H18A—C18—H18B	109.5
C11—C9—H9	107.0	C13—C18—H18C	109.5
C8—C9—H9	107.0	H18A—C18—H18C	109.5
C10—C9—H9	107.0	H18B—C18—H18C	109.5
C8—C14—C15	119.13 (17)	C14—C15—C16	103.43 (16)
C8—C14—C13	114.41 (16)	C14—C15—H15A	111.1
C15—C14—C13	103.54 (16)	C16—C15—H15A	111.1
C8—C14—H14	106.3	C14—C15—H15B	111.1
C15—C14—H14	106.3	C16—C15—H15B	111.1
C13—C14—H14	106.3	H15A—C15—H15B	109.0
C7—C8—C14	112.46 (17)	C20—C21—H21A	109.5
C7—C8—C9	113.24 (16)	C20—C21—H21B	109.5
C14—C8—C9	108.64 (16)	H21A—C21—H21B	109.5
C7—C8—H8	107.4	C20—C21—H21C	109.5
C14—C8—H8	107.4	H21A—C21—H21C	109.5
C9—C8—H8	107.4	H21B—C21—H21C	109.5
O3—C3—C2	106.4 (2)	C2—C1—C10	114.3 (2)
O3—C3—C4	111.31 (19)	C2—C1—H1A	108.7
C2—C3—C4	110.94 (19)	C10—C1—H1A	108.7
O3—C3—H3	109.4	C2—C1—H1B	108.7
C2—C3—H3	109.4	C10—C1—H1B	108.7
C4—C3—H3	109.4	H1A—C1—H1B	107.6
C7—C6—C5	114.67 (17)	C22—C20—C21	109.1 (2)
C7—C6—H6A	108.6	C22—C20—C17	108.92 (18)
C5—C6—H6A	108.6	C21—C20—C17	112.87 (18)
C7—C6—H6B	108.6	C22—C20—H20	108.6
C5—C6—H6B	108.6	C21—C20—H20	108.6
H6A—C6—H6B	107.6	C17—C20—H20	108.6
O7—C7—C6	109.93 (17)	O121—C121—O12	127.4 (3)
O7—C7—C8	107.47 (16)	O121—C121—H121	116.3
C6—C7—C8	113.42 (19)	O12—C121—H121	116.3
O7—C7—H7	108.6	C23—C22—C20	126.9 (3)
C6—C7—H7	108.6	C23—C22—H22	116.6
C8—C7—H7	108.6	C20—C22—H22	116.6
C12—C13—C18	108.24 (18)	O71—C71—O7	125.8 (4)
C12—C13—C14	107.82 (16)	O71—C71—H71	117.1
C18—C13—C14	112.49 (18)	O7—C71—H71	117.1
C12—C13—C17	117.70 (17)	C10—C19—H19A	109.5
C18—C13—C17	110.23 (16)	C10—C19—H19B	109.5
C14—C13—C17	100.24 (15)	H19A—C19—H19B	109.5
C6—C5—C4	110.76 (19)	C10—C19—H19C	109.5
C6—C5—C10	111.89 (18)	H19A—C19—H19C	109.5
C4—C5—C10	113.41 (18)	H19B—C19—H19C	109.5
C6—C5—H5	106.8	C15—C16—C17	107.46 (17)
C4—C5—H5	106.8	C15—C16—H16A	110.2
C10—C5—H5	106.8	C17—C16—H16A	110.2
C12—C11—C9	114.84 (17)	C15—C16—H16B	110.2
C12—C11—H11A	108.6	C17—C16—H16B	110.2
C9—C11—H11A	108.6	H16A—C16—H16B	108.5
C12—C11—H11B	108.6	C3—C4—C5	114.38 (19)
C9—C11—H11B	108.6	C3—C4—H4A	108.7
H11A—C11—H11B	107.5	C5—C4—H4A	108.7
C19—C10—C5	109.6 (2)	C3—C4—H4B	108.7
C19—C10—C1	106.2 (2)	C5—C4—H4B	108.7
C5—C10—C1	107.43 (19)	H4A—C4—H4B	107.6
C19—C10—C9	111.65 (18)	C22—C23—H23A	120.0
C5—C10—C9	109.38 (17)	C22—C23—H23B	120.0
C1—C10—C9	112.46 (19)	H23A—C23—H23B	120.0
C20—C17—C16	111.81 (17)	O31—C31—O3	126.3 (3)
C20—C17—C13	119.66 (17)	O31—C31—H31	116.8
C16—C17—C13	103.50 (17)	O3—C31—H31	116.8
C1—C10—C5—C4	51.3 (3)	C13—C17—C20—C21	−57.8 (3)
C9—C10—C5—C6	55.1 (2)	C17—C20—C22—C23	−109.7 (3)
C19—C10—C13—C18	3.0 (2)	C13—C17—C20—C22	−179.10 (18)
C3—O3—C31—O31	3.7 (4)	C13—C17—C20—C21	−57.8 (3)
C7—O7—C71—O71	−0.9 (4)	C16—C17—C20—C21	−178.9 (2)
C12—O12—C121—O121	−0.3 (4)	C21—C20—C22—C23	126.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O7	0.97	2.35	3.029 (3)	126
C12—H12···O121	0.98	2.37	2.750 (3)	102
C14—H14···O12	0.98	2.53	2.929 (2)	104
C17—H17···O12	0.98	2.43	2.890 (3)	108
C31—H31···O31^i	0.93	2.49	3.396 (4)	166

Symmetry code: (i) x−1/2, −y+1/2, −z+1.