[alpha]-Onocerin chloro­form hemisolvate

The triterpenoid natural product [alpha]-onocerin [8,14-secogammacera-8(26),14(27)-diene-3,21-diol], determined here as the chloro­form hemisolvate, C₃₀H₅₀O₂·0.5CHCl₃, consists of two independent symmetric trans-decalin C₁₅ building blocks. Hydro­gen bonds between the hydroxyl groups form an infinite two-dimensional network perpendicular to the c axis.

S1. Comment

The roots of Ononis spinosa L. (Fabaceae) are medicinally used as a diuretic drug. Phytochemical identification, diagnosis of drug adulterations and the standardization of extracts is performed using pure α-onocerin as a reference compound. While isolated already in 1855, its constitution was assigned using chemical methods in 1955 (Barton & Overton, 1955, and references therein). However, only the structure of the related 8,(26),14 (27)-diketones have been studied by X-ray so far (Tsuda et al., 1983). We report here the first X-ray structure of a 3,21-onoceradiene-3,21-diol, (I). This is in continuation of the comprehensive spectral evaluation of α-onocerin focusing on NMR and MS spectral methods which was published recently (Pauli, 2000) and which supported the presence of two trans-decalin C₁₅ building blocks symmetrically linked over a bimethylene bridge.

The structural investigation of (I) confirms the assumed geometry. The framework consists mainly of Csp³—Csp³ bonds [1.498 (6)–1.576 (5) Å], with only C11—C111 and C21—C–211 [1.317 (7) and 1.329 (7) Å] being clearly Csp³—Csp³ bonds. Also, both bonds to the hydroxyl groups are in the expected range for a single C—O bond [1.445 (5) and 1.441 (5) Å]. Furthermore, the geometries of both trans-decalin C₁₅ building blocks are quite similar and comparable with the same skeleton found in gummozine (Nasirov et al., 1977) and 3-α-hydroxymanool hydrate (Kagawa et al., 1993).

Hydrogen bonds between the hydroxyl groups form an infinite two-dimensional network perpendicular to the c axis (Table 2). Besides these, there are no further contacts closer than van der Waals distances.

The recently published NMR spectroscopic evidence for a symmetric constitution of α-onocerin is now definitively roborized by the crystallographic data. Therefore, it becomes clear that the C₃₀ skeleton consists of two halves that are stereochemically identical. Compared to typical pentacyclic triterpene skeletons, such as oleanolic acid, however, this must be rated a very unusual feature with respect to the designated triterpenoid origin of α-onocerin which has not been supported by biogenetic studies so far. It must be mentioned, that no diastereomeric analogues, e.g. isomers with inversion of one or more stereocenters, could be detected by NMR (Pauli, 2000). The biogenetic assignment may be challenged in three points: the necessity for fully stereospecific alterations such as (i) the hydrogenation of the 12,13 double bond and (ii) the hydroxylation of the C-21 position, and most important, (iii) an inversion of the decalin ring fusion being [D/E]cis in oleanolic acid. Therefore, the classification of α-onocerin as a dimeric sesquiterpene is equally justified at this point and should not be omitted. Concerning the numbering of the α-onocerin framework, which in the literature is again based on the assumption that it represents a triterpene, at this point, revision should be avoided unless the biosynthesis has been investigated.

S2. Experimental

The title compound was obtained from the dried roots of Ononis spinosa (sample No. 9200280, PhytoLab, Vestenbergsgreuth) upon Soxhlet extraction with petrol ether, cleaning-up with active charcoal, in vacuo precipitation, and repeated crystallization from petrol ether, CH₂Cl₂/EtOAc (1:1), and CHCl₃ in a final yield of 0.05%. Colorless crystals were obtained from CHCl₃. Calculated mass for C₃₀H₅₀O₂: 442.7. Mass spectrum (El; m/z): 442 (M⁺), 427 ([M—CH₃]⁺), 409 ([M—CH₃—H₂O]⁺), 391 ([M—CH₃-2 H₂O]⁺), 381 ([M—CH₃—CO—H₂O]⁺). ¹H NMR (CDCl₃): δ, 1.572 (qddd, 1[19] A = eq), 0.952 (ddd, 1[19]B = ax), 1.552 (dddd, 2[20] A = eq), 1.441 (dddd, 2[20]B = a), 3.090 (dd, 3[21]a), 0.946 (dd, 5[17]ax), 1.604 ([d]dddd, 6[16] A = eq), 1.239 (dddd, 6[16]B = ax), 2.268 (ddd, 7[15] A = eq), 1.839 (dddddt, 7[15]B = ax), 1.369 (m, 9[13]), 1.369 (m[dddd], 11[12] A), 1.055 (m[dddd], 11[12]B), 0.845 (s, 23[30]), 0.616 (s, 24[29]), 0.505 (br s/d, 25[28]), 4.695 (dd, 26[27] A), 4.442 (ddd, 26[27]B). ¹³C NMR (CDCl₃): 36.84 (1[19]), 27.27 (2[20]), 78.43 (3[21]), 38.84 (4[22]), 54.50 (5[17]), 23.81 (6[16]), 38.03 (7[15]), 148.28 (8[14]), 57.28 (9[13]), 39.00 (10[18]), 22.30 (11[12], 27.91 (23[30]), 15.09 (24[29]), 14.21 (25[28]), 106.35 (26[27]).

Computing details

Data collection: EXPRESS (Nonius, 1994); cell refinement: EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. DIAMOND (50% probability) plot (Brandenburg, 1996) of the title compound with the atomic numbering scheme.

8(26),14 (27)-Onoceradiene-3,21-diol

Crystal data

C30H50O2·0.5CHCl3	Dx = 1.124 Mg m^−3
Mr = 502.38	Melting point: 483 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
a = 7.470 (1) Å	Cell parameters from 25 reflections
b = 14.681 (2) Å	θ = 22.5–46.1°
c = 27.079 (4) Å	µ = 1.72 mm^−1
V = 2969.7 (7) Å^3	T = 223 K
Z = 4	Block, colourless
F(000) = 1100	0.30 × 0.20 × 0.15 mm

Data collection

Enraf Nonius CAD-4 diffractometer	2318 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 74.3°, θmin = 5.8°
ω/2θ scans	h = 0→9
Absorption correction: empirical (using intensity measurements) via ψ scan (Fair, 1990)	k = 0→18
Tmin = 0.627, Tmax = 0.783	l = 0→33
3450 measured reflections	3 standard reflections every 250 reflections
3450 independent reflections	intensity decay: 6.7%

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)] = 0.076	H-atom parameters constrained
wR(F^2) = 0.228	w = 1/[σ^2(Fo^2) + (0.1687P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
3450 reflections	Δρmax = 0.70 e Å^−3
313 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (19)

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	Occ. (<1)
C1	0.7940 (6)	0.6807 (3)	0.16169 (17)	0.0478 (11)
H1A	0.8743	0.6684	0.1338	0.057*
H1B	0.8551	0.6613	0.1919	0.057*
C10	0.6236 (6)	0.6246 (3)	0.15541 (15)	0.0404 (9)
H10	0.5609	0.6511	0.1266	0.048*
C11	0.4939 (7)	0.6318 (3)	0.19791 (16)	0.0499 (11)
C111	0.5309 (10)	0.6606 (3)	0.24282 (17)	0.0672 (17)
H11A	0.4430	0.6580	0.2676	0.081*
H11B	0.6452	0.6838	0.2501	0.081*
C12	0.3113 (7)	0.5944 (3)	0.18555 (18)	0.0557 (12)
H12A	0.2570	0.6309	0.1592	0.067*
H12B	0.2338	0.5978	0.2147	0.067*
C13	0.3279 (7)	0.4947 (3)	0.16856 (18)	0.0536 (12)
H13A	0.3622	0.4567	0.1967	0.064*
H13B	0.2113	0.4735	0.1566	0.064*
C14	0.4663 (6)	0.4843 (3)	0.12771 (15)	0.0387 (9)
H14	0.4252	0.5265	0.1015	0.046*
C15	0.4619 (6)	0.3872 (3)	0.10240 (16)	0.0421 (10)
C151	0.4959 (8)	0.3084 (3)	0.13845 (19)	0.0561 (13)
H15A	0.4150	0.3136	0.1663	0.084*
H15B	0.6186	0.3110	0.1501	0.084*
H15C	0.4756	0.2509	0.1217	0.084*
C152	0.2726 (6)	0.3743 (3)	0.07917 (19)	0.0538 (12)
H15D	0.2408	0.4283	0.0605	0.081*
H15E	0.1854	0.3647	0.1052	0.081*
H15F	0.2738	0.3218	0.0574	0.081*
C16	0.5980 (6)	0.3875 (3)	0.06068 (15)	0.0414 (10)
H16	0.5566	0.4340	0.0368	0.050*
O16	0.5973 (5)	0.3017 (2)	0.03454 (12)	0.0532 (9)
H16A	0.6702	0.2664	0.0476	0.080*
C17	0.7821 (6)	0.4159 (3)	0.07636 (19)	0.0476 (11)
H17A	0.8629	0.4140	0.0479	0.057*
H17B	0.8274	0.3733	0.1013	0.057*
C18	0.7788 (6)	0.5125 (3)	0.09783 (16)	0.0451 (10)
H18A	0.7399	0.5552	0.0721	0.054*
H18B	0.9004	0.5297	0.1078	0.054*
C19	0.6535 (6)	0.5211 (3)	0.14254 (15)	0.0387 (9)
C191	0.7372 (8)	0.4734 (3)	0.18709 (17)	0.0566 (13)
H19A	0.7640	0.4106	0.1786	0.085*
H19B	0.6540	0.4747	0.2146	0.085*
H19C	0.8468	0.5044	0.1963	0.085*
C2	0.7586 (7)	0.7836 (3)	0.16447 (18)	0.0469 (11)
H2A	0.6673	0.7999	0.1400	0.056*
H2B	0.7111	0.7985	0.1972	0.056*
C20	0.9264 (6)	0.8403 (3)	0.15507 (15)	0.0384 (9)
H20	0.9771	0.8173	0.1237	0.046*
C21	1.0739 (7)	0.8296 (3)	0.19325 (17)	0.0497 (11)
C211	1.0497 (10)	0.7937 (3)	0.23782 (18)	0.0652 (16)
H21A	1.1442	0.7935	0.2608	0.078*
H21B	0.9383	0.7685	0.2464	0.078*
C22	1.2492 (8)	0.8708 (3)	0.1775 (2)	0.0595 (13)
H22A	1.2947	0.8387	0.1483	0.071*
H22B	1.3373	0.8643	0.2041	0.071*
C23	1.2227 (7)	0.9722 (3)	0.16537 (19)	0.0511 (11)
H23A	1.1965	1.0055	0.1959	0.061*
H23B	1.3339	0.9968	0.1515	0.061*
C24	1.0706 (5)	0.9869 (3)	0.12863 (14)	0.0350 (8)
H24	1.1044	0.9488	0.1000	0.042*
C25	1.0650 (6)	1.0860 (3)	0.10719 (16)	0.0394 (9)
C251	1.0435 (8)	1.1604 (3)	0.14660 (17)	0.0524 (12)
H25A	1.1326	1.1518	0.1722	0.079*
H25B	0.9248	1.1565	0.1609	0.079*
H25C	1.0596	1.2197	0.1315	0.079*
C252	1.2414 (6)	1.1028 (3)	0.0792 (2)	0.0531 (11)
H25D	1.2326	1.1592	0.0607	0.080*
H25E	1.2633	1.0527	0.0566	0.080*
H25F	1.3393	1.1071	0.1026	0.080*
C26	0.9113 (6)	1.0910 (3)	0.06958 (15)	0.0400 (9)
H26	0.9445	1.0522	0.0411	0.048*
O26	0.8871 (5)	1.1824 (2)	0.05139 (12)	0.0499 (8)
H26A	0.9822	1.2008	0.0391	0.075*
C27	0.7336 (6)	1.0575 (3)	0.08883 (18)	0.0454 (10)
H27A	0.6433	1.0618	0.0627	0.054*
H27B	0.6949	1.0959	0.1164	0.054*
C28	0.7493 (6)	0.9588 (3)	0.10612 (16)	0.0436 (10)
H28A	0.7794	0.9203	0.0777	0.052*
H28B	0.6328	0.9387	0.1187	0.052*
C29	0.8912 (6)	0.9450 (3)	0.14658 (15)	0.0377 (9)
C291	0.8225 (7)	0.9865 (3)	0.19540 (16)	0.0550 (12)
H29A	0.7782	1.0476	0.1893	0.082*
H29B	0.9196	0.9889	0.2191	0.082*
H29C	0.7264	0.9491	0.2084	0.082*
C30	1.033 (3)	0.7038 (19)	0.0083 (8)	0.137 (7)*	0.50
H30	0.9515	0.7190	0.0360	0.164*	0.50
Cl31	0.885 (2)	0.6546 (11)	−0.0291 (6)	0.322 (7)*	0.50
Cl32	1.068 (2)	0.7942 (14)	−0.0092 (5)	0.342 (7)*	0.50
Cl33	1.1703 (17)	0.6498 (9)	0.0365 (5)	0.277 (5)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.053 (3)	0.034 (2)	0.056 (2)	−0.009 (2)	0.000 (2)	−0.0007 (18)
C10	0.044 (2)	0.0336 (19)	0.043 (2)	−0.0088 (19)	0.0028 (19)	0.0024 (16)
C11	0.063 (3)	0.038 (2)	0.048 (2)	−0.010 (2)	0.006 (2)	0.0025 (18)
C111	0.099 (5)	0.056 (3)	0.047 (2)	−0.028 (3)	0.009 (3)	−0.001 (2)
C12	0.063 (3)	0.049 (3)	0.055 (3)	−0.010 (2)	0.012 (3)	−0.003 (2)
C13	0.061 (3)	0.045 (2)	0.055 (3)	−0.019 (2)	0.009 (2)	−0.001 (2)
C14	0.042 (2)	0.0325 (18)	0.042 (2)	−0.0058 (17)	−0.0029 (19)	0.0050 (16)
C15	0.045 (2)	0.0309 (19)	0.050 (2)	−0.0061 (18)	−0.012 (2)	0.0039 (16)
C151	0.072 (3)	0.031 (2)	0.066 (3)	−0.010 (2)	−0.011 (3)	0.009 (2)
C152	0.049 (3)	0.043 (2)	0.069 (3)	−0.011 (2)	−0.014 (2)	−0.002 (2)
C16	0.048 (2)	0.0303 (19)	0.046 (2)	0.0016 (18)	−0.012 (2)	−0.0009 (16)
O16	0.060 (2)	0.0392 (16)	0.0602 (18)	0.0052 (15)	−0.0180 (18)	−0.0117 (14)
C17	0.042 (2)	0.040 (2)	0.061 (3)	0.0005 (19)	−0.003 (2)	−0.007 (2)
C18	0.041 (2)	0.039 (2)	0.056 (2)	−0.0084 (18)	−0.004 (2)	−0.0013 (19)
C19	0.044 (2)	0.0320 (18)	0.040 (2)	−0.0061 (18)	−0.0091 (19)	0.0023 (16)
C191	0.076 (3)	0.039 (2)	0.055 (3)	−0.005 (2)	−0.020 (3)	0.0046 (19)
C2	0.055 (3)	0.028 (2)	0.057 (2)	−0.0107 (19)	0.010 (2)	−0.0042 (18)
C20	0.044 (2)	0.0289 (18)	0.0417 (19)	−0.0052 (17)	0.0006 (18)	−0.0032 (15)
C21	0.063 (3)	0.0270 (19)	0.059 (2)	−0.007 (2)	−0.013 (2)	−0.0002 (18)
C211	0.098 (4)	0.046 (3)	0.052 (3)	−0.025 (3)	−0.019 (3)	−0.001 (2)
C22	0.061 (3)	0.046 (3)	0.072 (3)	−0.006 (2)	−0.024 (3)	0.003 (2)
C23	0.049 (3)	0.042 (2)	0.062 (3)	−0.013 (2)	−0.011 (2)	0.005 (2)
C24	0.0325 (19)	0.0318 (18)	0.0408 (19)	−0.0027 (16)	0.0016 (17)	−0.0026 (15)
C25	0.035 (2)	0.034 (2)	0.049 (2)	−0.0055 (17)	0.0051 (19)	−0.0036 (17)
C251	0.067 (3)	0.031 (2)	0.059 (2)	−0.008 (2)	−0.001 (3)	−0.0073 (19)
C252	0.042 (2)	0.043 (2)	0.074 (3)	−0.007 (2)	0.005 (2)	0.006 (2)
C26	0.047 (2)	0.0303 (19)	0.043 (2)	0.0005 (18)	0.005 (2)	−0.0021 (16)
O26	0.0524 (18)	0.0362 (15)	0.0610 (18)	0.0077 (14)	0.0121 (16)	0.0081 (13)
C27	0.035 (2)	0.044 (2)	0.057 (2)	−0.0008 (19)	0.005 (2)	0.003 (2)
C28	0.035 (2)	0.043 (2)	0.053 (2)	−0.0063 (19)	0.001 (2)	−0.0023 (18)
C29	0.041 (2)	0.0316 (18)	0.041 (2)	−0.0058 (17)	0.0083 (18)	−0.0065 (16)
C291	0.070 (3)	0.043 (2)	0.052 (2)	−0.004 (2)	0.023 (3)	−0.005 (2)

Geometric parameters (Å, º)

C1—C10	1.525 (6)	C20—C21	1.519 (6)
C1—C2	1.536 (6)	C20—C29	1.576 (5)
C10—C11	1.508 (6)	C21—C211	1.329 (7)
C10—C19	1.575 (5)	C21—C22	1.505 (7)
C11—C111	1.317 (7)	C22—C23	1.537 (6)
C11—C12	1.507 (7)	C23—C24	1.526 (6)
C12—C13	1.538 (7)	C24—C29	1.553 (6)
C13—C14	1.522 (6)	C24—C25	1.567 (5)
C14—C19	1.552 (6)	C25—C251	1.535 (6)
C14—C15	1.583 (6)	C25—C26	1.537 (6)
C15—C16	1.520 (6)	C25—C252	1.540 (6)
C15—C151	1.534 (6)	C26—O26	1.441 (5)
C15—C152	1.559 (6)	C26—C27	1.509 (6)
C16—O16	1.445 (5)	C27—C28	1.527 (6)
C16—C17	1.498 (6)	C28—C29	1.538 (6)
C17—C18	1.533 (6)	C29—C291	1.544 (5)
C18—C19	1.535 (6)	C30—Cl32	1.43 (2)
C19—C191	1.529 (6)	C30—Cl33	1.51 (2)
C2—C20	1.526 (6)	C30—Cl31	1.66 (3)
C10—C1—C2	113.1 (4)	C21—C20—C29	108.7 (3)
C11—C10—C1	114.4 (4)	C2—C20—C29	114.8 (4)
C11—C10—C19	109.1 (3)	C211—C21—C22	122.3 (5)
C1—C10—C19	115.3 (4)	C211—C21—C20	124.1 (5)
C111—C11—C12	120.8 (5)	C22—C21—C20	113.4 (4)
C111—C11—C10	126.3 (5)	C21—C22—C23	109.7 (4)
C12—C11—C10	112.7 (4)	C24—C23—C22	111.9 (4)
C11—C12—C13	109.9 (4)	C23—C24—C29	112.5 (3)
C14—C13—C12	111.5 (4)	C23—C24—C25	113.1 (3)
C13—C14—C19	112.9 (3)	C29—C24—C25	117.5 (3)
C13—C14—C15	113.0 (3)	C251—C25—C26	110.4 (4)
C19—C14—C15	116.4 (3)	C251—C25—C252	108.6 (4)
C16—C15—C151	111.4 (4)	C26—C25—C252	107.8 (4)
C16—C15—C152	107.9 (4)	C251—C25—C24	113.9 (3)
C151—C15—C152	108.4 (4)	C26—C25—C24	108.0 (3)
C16—C15—C14	107.8 (3)	C252—C25—C24	108.0 (3)
C151—C15—C14	113.6 (3)	O26—C26—C27	108.2 (3)
C152—C15—C14	107.6 (3)	O26—C26—C25	111.4 (3)
O16—C16—C17	112.6 (3)	C27—C26—C25	114.4 (3)
O16—C16—C15	111.0 (3)	C26—C27—C28	110.4 (4)
C17—C16—C15	113.8 (4)	C27—C28—C29	113.3 (3)
C16—C17—C18	110.5 (4)	C28—C29—C291	109.2 (4)
C17—C18—C19	112.6 (3)	C28—C29—C24	108.6 (3)
C191—C19—C18	109.6 (4)	C291—C29—C24	113.5 (3)
C191—C19—C14	114.4 (4)	C28—C29—C20	110.3 (3)
C18—C19—C14	108.5 (3)	C291—C29—C20	108.4 (3)
C191—C19—C10	109.0 (3)	C24—C29—C20	106.8 (3)
C18—C19—C10	109.9 (3)	Cl32—C30—Cl33	122 (2)
C14—C19—C10	105.4 (3)	Cl32—C30—Cl31	108.9 (18)
C20—C2—C1	112.7 (4)	Cl33—C30—Cl31	122 (2)
C21—C20—C2	115.2 (4)
C2—C1—C10—C11	−63.1 (5)	C1—C2—C20—C21	−64.6 (5)
C2—C1—C10—C19	169.2 (3)	C1—C2—C20—C29	168.0 (3)
C1—C10—C11—C111	−18.3 (7)	C2—C20—C21—C211	−16.6 (6)
C19—C10—C11—C111	112.5 (5)	C29—C20—C21—C211	113.8 (5)
C1—C10—C11—C12	166.4 (4)	C2—C20—C21—C22	168.1 (4)
C19—C10—C11—C12	−62.8 (5)	C29—C20—C21—C22	−61.4 (5)
C111—C11—C12—C13	−118.9 (5)	C211—C21—C22—C23	−118.5 (5)
C10—C11—C12—C13	56.6 (5)	C20—C21—C22—C23	56.8 (5)
C11—C12—C13—C14	−51.8 (5)	C21—C22—C23—C24	−52.4 (6)
C12—C13—C14—C19	56.0 (5)	C22—C23—C24—C29	55.8 (5)
C12—C13—C14—C15	−169.3 (4)	C22—C23—C24—C25	−168.2 (4)
C13—C14—C15—C16	176.8 (4)	C23—C24—C25—C251	−58.9 (5)
C19—C14—C15—C16	−50.1 (4)	C29—C24—C25—C251	74.7 (5)
C13—C14—C15—C151	−59.3 (5)	C23—C24—C25—C26	178.0 (4)
C19—C14—C15—C151	73.8 (5)	C29—C24—C25—C26	−48.3 (4)
C13—C14—C15—C152	60.7 (5)	C23—C24—C25—C252	61.7 (5)
C19—C14—C15—C152	−166.2 (4)	C29—C24—C25—C252	−164.6 (4)
C151—C15—C16—O16	56.8 (4)	C251—C25—C26—O26	49.7 (5)
C152—C15—C16—O16	−62.0 (4)	C252—C25—C26—O26	−68.7 (4)
C14—C15—C16—O16	−178.0 (3)	C24—C25—C26—O26	174.8 (3)
C151—C15—C16—C17	−71.5 (4)	C251—C25—C26—C27	−73.4 (4)
C152—C15—C16—C17	169.6 (4)	C252—C25—C26—C27	168.2 (4)
C14—C15—C16—C17	53.7 (4)	C24—C25—C26—C27	51.8 (4)
O16—C16—C17—C18	172.7 (3)	O26—C26—C27—C28	177.0 (3)
C15—C16—C17—C18	−59.8 (5)	C25—C26—C27—C28	−58.2 (5)
C16—C17—C18—C19	58.8 (5)	C26—C27—C28—C29	58.1 (5)
C17—C18—C19—C191	72.6 (5)	C27—C28—C29—C291	72.0 (5)
C17—C18—C19—C14	−53.0 (5)	C27—C28—C29—C24	−52.2 (5)
C17—C18—C19—C10	−167.7 (4)	C27—C28—C29—C20	−169.0 (3)
C13—C14—C19—C191	60.7 (5)	C23—C24—C29—C28	−177.0 (3)
C15—C14—C19—C191	−72.4 (5)	C25—C24—C29—C28	49.0 (4)
C13—C14—C19—C18	−176.6 (4)	C23—C24—C29—C291	61.3 (5)
C15—C14—C19—C18	50.3 (4)	C25—C24—C29—C291	−72.7 (5)
C13—C14—C19—C10	−59.0 (4)	C23—C24—C29—C20	−58.1 (4)
C15—C14—C19—C10	167.9 (3)	C25—C24—C29—C20	168.0 (3)
C11—C10—C19—C191	−62.4 (5)	C21—C20—C29—C28	177.1 (3)
C1—C10—C19—C191	67.9 (5)	C2—C20—C29—C28	−52.3 (5)
C11—C10—C19—C18	177.5 (3)	C21—C20—C29—C291	−63.4 (5)
C1—C10—C19—C18	−52.2 (5)	C2—C20—C29—C291	67.2 (5)
C11—C10—C19—C14	60.8 (4)	C21—C20—C29—C24	59.2 (4)
C1—C10—C19—C14	−168.8 (3)	C2—C20—C29—C24	−170.1 (3)
C10—C1—C2—C20	−162.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16A···O26^i	0.83	2.04	2.822 (5)	157
O26—H26A···O16^ii	0.83	2.17	2.817 (5)	135

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