(24R)-24,25-Dihydroxycyclo­artan-3-one

In the title compound, C₃₀H₅₀O₃, the three six-membered rings adopt chair, twist and twist-boat conformations. The five-membered ring is in a slightly distorted envelope conformation. The substituent on the five-membered ring is in an extended conformation, with its two hydroxyl O atoms forming an intramolecular hydrogen bond. One of these O atoms also forms an intermolecular hydrogen bond with the oxy­gen of the carbonyl group in a neighbouring mol­ecule.

S1. Comment

The title compound has been isolated from leaves of Aglaia harmsiana Perkins (Meliaceae) collected in Java, Indonesia. Extracts from this plant are used as a Chinese crude drug to treat arthritis, pharyngitis, tonsillitis and other ailments (Inada et al., 1994). NMR spectroscopic investigations of this compound have also been reported (Inada et al., 1995), but in order to establish the structure unequivocally, an X-ray structure analysis has been carried out.

The molecule (Figure 1) contains a methine proton geminal to a hydroxy group at C24; a cyclopropyl methylene group; a secondary methyl group at C20 and the six tertiary methyl groups are present at C4, C13, C14 and C25. Two hydroxyl groups are present in the side chain, at C24 and C25. The differentiation of the 24R and 24S stereomers of cycloartane type triterpenes using ¹³C NMR techniques has been reported by Greca et al. (1994). It has been found that the chemical shifts of the side chain carbons and C17 of the title compound are the same as those of (24R)-cycloartane-3β-24,25-triol and are different from those of the 24S isomer (Inada et al., 1995). Based on this evidence the compound is (24R)-24,25-dihydroxycycloartan-3-one, (I). The structure determination also establishes this fact. \sch

In the steroid skeleton, ring A (see Scheme) adopts a chair conformation while ring B adopts a twist conformation (Honda et al., 1996) with C6 and C7 deviating by 0.391 (2) and −0.418 (2) Å, respectively, from the least-squares mean plane through C5, C8, C9 and C10. Ring C is in a twist boat conformation while in ring D C13, C15, C16 and C17 are almost coplanar with C14 deviating by −0.620 (1) Å from this plane to give a 14α envelope conformation (Anthony et al., 1999). The carbonyl C3 is twisted from the plane of the ring A, the associated torsion angles being −138.3 (1) for C1—C2—C3—O1 and 138.7 (1)° for O1—C3—C4—C5. The cyclpropyl group is axial to the ring B, as demonstrated by the torsion angle C7—C8—C9—C19 of 89.1 (1)°. The side chain at C17 equatorial to the ring D and in an extended conformation (Honda et al., 1996). Ring-puckering parameters (Table 2) were calculated using the method of Cremer & Pople (1975).

O3 from the hydroxyl group attached to the quaternary carbon C25 forms an intramolecular hydrogen bond with O2 from the hydroxyl group on C24; O3 also forms an intermolecular hydrogen bond with the carbonyl oxygen O1 (Table 3). The former interaction generates a five-membered OCCOH ring while the latter links molecules into infinite chains running in the [101] direction.

The value of the Flack parameter obtained is 0.1 (3), which is just adequate to indicate the absolute configuration. Moreover, Greca et al. (1994) and Boar & Damps (1977) have isolated and examined by chemical methods a few cycloartane type triterpenes. Both have determined the absolute configuration at C24 by a modified Horeau's method (Brooks & Gilbert, 1973) and using this method the authors have differentiated between 24-R and 24-S configurations. Inada et al. (1995) found that the chemical shifts of the side chain carbons and C17 of the present compound are the same as those of 24-R isomers of the above mentioned cycloartane type triterpenes. Hence we may say that based on these comparisons, the absolute configuration of the present compound has been confirmed.

S2. Experimental

The dried and crushed leaves (700 g) were extracted with EtOH (3 x 10 litres) and the solvent was removed in vacuo. The EtOH extract (30.2 g) was suspended in H₂O (600 ml) and the aqueous suspension was extracted successively with EtOAc (3 x 300 ml) and n-BuOH (3 x 300 ml). The EtOAc extract (25 g) was chromatographed on Si gel and fractions were further purified by high-pressure liquid chromatography to afford the title compound (140 mg) (Inada et al., 1995). Crystals of the title compound were obtained from a solution of the compound in EtOH-hexane by slow evaporation at room temperature.

S3. Refinement

The methyl H atoms on C18, C21, C26, C27, C28, C29 and C30 and the hydroxyl H atoms attached to O1 and O2 were found from circular difference Fourier synthesis. They were then refined as part of a rigid roating group with U_iso(H) = 1.5U_eq(parent). Other hydrogen atoms were included at geometrically calculated positions and allowed to ride on their parent atoms with U_iso(H) = 1.2U_eq(parent).

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: CADRAL (Daresbury Laboratory, 19XX); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Huttner, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST (Nardelli, 1983).

Figures

Fig. 1. Structure of (I) showing the atom-numbering scheme and 30% probability displacement ellipsoids.

(24R)-cycloartane-24,25-diol-3-one

Crystal data

C30H50O3	Dx = 1.125 Mg m^−3
Mr = 458.70	Melting point: 423 K
Monoclinic, P21	Cu Kα radiation, λ = 1.54180 Å
a = 9.9534 (10) Å	Cell parameters from 25 reflections
b = 10.530 (3) Å	θ = 38–70°
c = 13.837 (2) Å	µ = 0.54 mm^−1
β = 110.942 (10)°	T = 273 K
V = 1354.4 (5) Å^3	Plate, colourless
Z = 2	0.20 × 0.15 × 0.10 mm
F(000) = 508

Data collection

Enraf-Nonius CAD4 diffractometer	2722 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 74.2°, θmin = 3.4°
ω/θ scans	h = −12→9
Absorption correction: ψ scan North et al. (1968)	k = −13→0
Tmin = 0.92, Tmax = 0.95	l = −17→17
6647 measured reflections	2 standard reflections every 200 reflections
2825 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: see text
Least-squares matrix: full	See text
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0796P)^2 + 0.0939P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.114	(Δ/σ)max = 0.022
S = 1.03	Δρmax = 0.37 e Å^−3
2825 reflections	Δρmin = −0.18 e Å^−3
308 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0102 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (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
O1	0.32980 (10)	−0.02918 (12)	0.96230 (7)	0.0769 (3)
O2	1.27381 (10)	0.13557 (14)	0.32933 (7)	0.0798 (3)
H2	1.3506	0.1247	0.3211	0.120*
O3	1.31939 (9)	0.02963 (13)	0.16653 (7)	0.0773 (3)
H3	1.3310	0.0247	0.1109	0.116*
C1	0.43037 (11)	−0.07362 (13)	0.74210 (8)	0.0532 (3)
H1A	0.4902	−0.1445	0.7773	0.064*
H1B	0.3839	−0.0962	0.6698	0.064*
C2	0.31600 (11)	−0.04850 (15)	0.78984 (9)	0.0565 (3)
H2A	0.2439	0.0081	0.7447	0.068*
H2B	0.2688	−0.1280	0.7934	0.068*
C3	0.37397 (12)	0.00871 (14)	0.89585 (8)	0.0548 (3)
C4	0.48229 (12)	0.11676 (13)	0.91534 (8)	0.0532 (3)
C5	0.59382 (11)	0.08117 (12)	0.86412 (8)	0.0468 (3)
H5	0.6410	0.0040	0.8999	0.056*
C6	0.71431 (12)	0.17699 (14)	0.88270 (9)	0.0571 (3)
H6A	0.7640	0.1891	0.9564	0.068*
H6B	0.6751	0.2581	0.8524	0.068*
C7	0.81889 (11)	0.12751 (15)	0.83353 (8)	0.0558 (3)
H7A	0.8468	0.0413	0.8566	0.067*
H7B	0.9049	0.1797	0.8554	0.067*
C8	0.74968 (10)	0.12995 (11)	0.71561 (7)	0.0441 (2)
H8	0.7283	0.2193	0.6965	0.053*
C9	0.60374 (10)	0.05994 (11)	0.67568 (7)	0.0426 (2)
C10	0.52322 (10)	0.04252 (11)	0.75091 (8)	0.0446 (2)
C11	0.58486 (11)	−0.04507 (13)	0.59498 (8)	0.0511 (3)
H11A	0.4829	−0.0529	0.5552	0.061*
H11B	0.6156	−0.1245	0.6318	0.061*
C12	0.66436 (11)	−0.03039 (13)	0.51772 (8)	0.0514 (3)
H12A	0.7160	−0.1084	0.5174	0.062*
H12B	0.5935	−0.0188	0.4488	0.062*
C13	0.77074 (10)	0.08042 (11)	0.54170 (7)	0.0431 (2)
C14	0.85180 (10)	0.08574 (10)	0.66142 (7)	0.0412 (2)
C15	0.97414 (11)	0.17975 (12)	0.67227 (8)	0.0503 (3)
H15A	1.0564	0.1624	0.7345	0.060*
H15B	0.9427	0.2664	0.6752	0.060*
C16	1.01281 (12)	0.15935 (14)	0.57536 (9)	0.0541 (3)
H16A	1.1077	0.1218	0.5943	0.065*
H16B	1.0129	0.2399	0.5413	0.065*
C17	0.89870 (10)	0.06969 (12)	0.50250 (7)	0.0455 (2)
H17	0.9367	−0.0167	0.5186	0.055*
C18	0.68710 (13)	0.20298 (14)	0.50082 (9)	0.0578 (3)
H18A	0.7509	0.2744	0.5225	0.087*
H18B	0.6110	0.2112	0.5277	0.087*
H18C	0.6470	0.2002	0.4266	0.087*
C19	0.47400 (11)	0.14080 (14)	0.66592 (8)	0.0529 (3)
H19A	0.4904	0.2294	0.6857	0.063*
H19B	0.3857	0.1241	0.6081	0.063*
C20	0.87606 (11)	0.09302 (13)	0.38787 (8)	0.0525 (3)
H20	0.8471	0.1816	0.3709	0.063*
C21	0.76014 (15)	0.0069 (2)	0.31583 (10)	0.0790 (5)
H21A	0.6685	0.0290	0.3194	0.118*
H21B	0.7820	−0.0799	0.3366	0.118*
H21C	0.7569	0.0175	0.2461	0.118*
C22	1.01995 (12)	0.07117 (15)	0.37323 (8)	0.0559 (3)
H22A	1.0914	0.1256	0.4214	0.067*
H22B	1.0492	−0.0160	0.3922	0.067*
C23	1.02284 (12)	0.09485 (14)	0.26523 (8)	0.0546 (3)
H23A	0.9479	0.0449	0.2154	0.066*
H23B	1.0026	0.1837	0.2477	0.066*
C24	1.16657 (12)	0.06076 (14)	0.25764 (9)	0.0553 (3)
H24	1.1865	−0.0278	0.2798	0.066*
C25	1.17439 (12)	0.07041 (15)	0.14944 (9)	0.0587 (3)
C26	1.06977 (16)	−0.02014 (17)	0.07500 (10)	0.0723 (4)
H26A	0.9733	0.0095	0.0602	0.108*
H26B	1.0803	−0.1031	0.1056	0.108*
H26C	1.0893	−0.0243	0.0120	0.108*
C27	1.15302 (19)	0.20501 (19)	0.10782 (12)	0.0831 (4)
H27A	1.1723	0.2083	0.0447	0.125*
H27B	1.2176	0.2610	0.1578	0.125*
H27C	1.0556	0.2309	0.0946	0.125*
C28	0.91880 (12)	−0.04354 (13)	0.70453 (9)	0.0514 (3)
H28A	0.9742	−0.0741	0.6650	0.077*
H28B	0.8438	−0.1032	0.6998	0.077*
H28C	0.9803	−0.0340	0.7756	0.077*
C29	0.55935 (15)	0.13526 (19)	1.03193 (9)	0.0733 (4)
H29A	0.6215	0.2079	1.0440	0.110*
H29B	0.6154	0.0611	1.0608	0.110*
H29C	0.4895	0.1483	1.0641	0.110*
C30	0.39618 (15)	0.23698 (15)	0.86843 (12)	0.0698 (4)
H30A	0.3473	0.2251	0.7954	0.105*
H30B	0.4605	0.3080	0.8799	0.105*
H30C	0.3269	0.2530	0.9006	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0952 (4)	0.0874 (7)	0.0716 (4)	−0.0159 (5)	0.0584 (3)	−0.0056 (4)
O2	0.0689 (4)	0.1071 (8)	0.0700 (5)	−0.0147 (6)	0.0328 (4)	−0.0174 (6)
O3	0.0688 (4)	0.1066 (8)	0.0727 (4)	0.0089 (5)	0.0450 (3)	−0.0062 (5)
C1	0.0529 (4)	0.0614 (6)	0.0532 (5)	−0.0088 (5)	0.0286 (4)	−0.0073 (5)
C2	0.0500 (4)	0.0714 (7)	0.0561 (5)	−0.0063 (5)	0.0289 (4)	−0.0006 (5)
C3	0.0585 (4)	0.0617 (7)	0.0561 (4)	0.0031 (5)	0.0350 (4)	0.0026 (5)
C4	0.0570 (5)	0.0590 (6)	0.0522 (4)	0.0012 (5)	0.0300 (4)	−0.0035 (5)
C5	0.0489 (4)	0.0510 (5)	0.0447 (4)	0.0019 (4)	0.0220 (3)	−0.0019 (4)
C6	0.0585 (5)	0.0692 (7)	0.0509 (4)	−0.0129 (5)	0.0287 (4)	−0.0165 (5)
C7	0.0484 (4)	0.0758 (7)	0.0465 (4)	−0.0110 (5)	0.0211 (4)	−0.0134 (5)
C8	0.0454 (4)	0.0453 (5)	0.0462 (4)	−0.0035 (4)	0.0221 (3)	−0.0042 (4)
C9	0.0409 (4)	0.0500 (5)	0.0409 (4)	−0.0013 (4)	0.0193 (3)	0.0001 (4)
C10	0.0421 (4)	0.0516 (5)	0.0445 (4)	−0.0019 (4)	0.0207 (3)	−0.0015 (4)
C11	0.0496 (4)	0.0608 (6)	0.0493 (4)	−0.0139 (5)	0.0255 (3)	−0.0104 (5)
C12	0.0503 (4)	0.0629 (6)	0.0457 (4)	−0.0106 (5)	0.0228 (4)	−0.0094 (4)
C13	0.0421 (4)	0.0478 (5)	0.0427 (4)	0.0002 (4)	0.0192 (3)	0.0010 (4)
C14	0.0395 (4)	0.0458 (5)	0.0418 (4)	0.0001 (4)	0.0189 (3)	−0.0003 (4)
C15	0.0483 (4)	0.0546 (6)	0.0530 (5)	−0.0089 (5)	0.0241 (4)	−0.0055 (4)
C16	0.0500 (4)	0.0670 (7)	0.0514 (4)	−0.0082 (5)	0.0257 (4)	−0.0012 (5)
C17	0.0471 (4)	0.0488 (5)	0.0460 (4)	0.0024 (4)	0.0233 (3)	0.0035 (4)
C18	0.0566 (5)	0.0655 (7)	0.0573 (5)	0.0157 (5)	0.0275 (4)	0.0163 (5)
C19	0.0470 (4)	0.0638 (6)	0.0518 (5)	0.0073 (5)	0.0226 (4)	0.0067 (5)
C20	0.0542 (4)	0.0631 (7)	0.0475 (4)	0.0019 (5)	0.0272 (4)	0.0040 (5)
C21	0.0679 (6)	0.1261 (13)	0.0473 (5)	−0.0230 (8)	0.0259 (5)	−0.0130 (7)
C22	0.0585 (5)	0.0679 (7)	0.0501 (4)	0.0004 (5)	0.0302 (4)	0.0008 (5)
C23	0.0600 (5)	0.0616 (7)	0.0524 (4)	0.0000 (5)	0.0325 (4)	0.0005 (5)
C24	0.0611 (5)	0.0611 (6)	0.0528 (5)	0.0005 (5)	0.0315 (4)	0.0003 (5)
C25	0.0654 (5)	0.0684 (7)	0.0551 (5)	0.0026 (6)	0.0373 (4)	−0.0029 (5)
C26	0.0822 (7)	0.0827 (10)	0.0571 (6)	0.0010 (8)	0.0311 (5)	−0.0121 (6)
C27	0.1150 (8)	0.0787 (10)	0.0783 (6)	0.0007 (8)	0.0623 (6)	0.0141 (7)
C28	0.0497 (4)	0.0553 (6)	0.0524 (5)	0.0060 (5)	0.0220 (4)	0.0079 (5)
C29	0.0835 (6)	0.0943 (10)	0.0546 (5)	−0.0159 (8)	0.0400 (5)	−0.0148 (6)
C30	0.0781 (6)	0.0606 (7)	0.0897 (7)	0.0111 (6)	0.0534 (5)	0.0000 (6)

Geometric parameters (Å, º)

O1—C3	1.2192 (17)	C15—H15A	0.9700
O2—C24	1.4096 (16)	C15—H15B	0.9700
O2—H2	0.8200	C16—C17	1.5424 (16)
O3—C25	1.4420 (16)	C16—H16A	0.9700
O3—H3	0.8200	C16—H16B	0.9700
C1—C10	1.5113 (17)	C17—C20	1.5399 (15)
C1—C2	1.5296 (17)	C17—H17	0.9800
C1—H1A	0.9700	C18—H18A	0.9600
C1—H1B	0.9700	C18—H18B	0.9600
C2—C3	1.4975 (17)	C18—H18C	0.9600
C2—H2A	0.9700	C19—H19A	0.9700
C2—H2B	0.9700	C19—H19B	0.9700
C3—C4	1.5237 (19)	C20—C21	1.525 (2)
C4—C29	1.5310 (16)	C20—C22	1.5338 (17)
C4—C30	1.537 (2)	C20—H20	0.9800
C4—C5	1.5614 (17)	C21—H21A	0.9600
C5—C6	1.5172 (18)	C21—H21B	0.9600
C5—C10	1.5252 (14)	C21—H21C	0.9600
C5—H5	0.9800	C22—C23	1.5253 (17)
C6—C7	1.5245 (18)	C22—H22A	0.9700
C6—H6A	0.9700	C22—H22B	0.9700
C6—H6B	0.9700	C23—C24	1.5146 (17)
C7—C8	1.5278 (14)	C23—H23A	0.9700
C7—H7A	0.9700	C23—H23B	0.9700
C7—H7B	0.9700	C24—C25	1.5301 (17)
C8—C14	1.5352 (15)	C24—H24	0.9800
C8—C9	1.5444 (14)	C25—C26	1.513 (2)
C8—H8	0.9800	C25—C27	1.516 (2)
C9—C19	1.5120 (16)	C26—H26A	0.9600
C9—C11	1.5346 (16)	C26—H26B	0.9600
C9—C10	1.5349 (15)	C26—H26C	0.9600
C10—C19	1.5107 (17)	C27—H27A	0.9600
C11—C12	1.5484 (17)	C27—H27B	0.9600
C11—H11A	0.9700	C27—H27C	0.9600
C11—H11B	0.9700	C28—H28A	0.9600
C12—C13	1.5303 (17)	C28—H28B	0.9600
C12—H12A	0.9700	C28—H28C	0.9600
C12—H12B	0.9700	C29—H29A	0.9600
C13—C18	1.5304 (17)	C29—H29B	0.9600
C13—C17	1.5566 (15)	C29—H29C	0.9600
C13—C14	1.5629 (13)	C30—H30A	0.9600
C14—C15	1.5345 (16)	C30—H30B	0.9600
C14—C28	1.5393 (17)	C30—H30C	0.9600
C15—C16	1.5366 (17)
C24—O2—H2	109.5	C15—C16—H16A	110.2
C25—O3—H3	109.5	C17—C16—H16A	110.2
C10—C1—C2	110.69 (11)	C15—C16—H16B	110.2
C10—C1—H1A	109.5	C17—C16—H16B	110.2
C2—C1—H1A	109.5	H16A—C16—H16B	108.5
C10—C1—H1B	109.5	C20—C17—C16	112.22 (10)
C2—C1—H1B	109.5	C20—C17—C13	120.70 (8)
H1A—C1—H1B	108.1	C16—C17—C13	103.35 (9)
C3—C2—C1	114.01 (9)	C20—C17—H17	106.6
C3—C2—H2A	108.8	C16—C17—H17	106.6
C1—C2—H2A	108.8	C13—C17—H17	106.6
C3—C2—H2B	108.8	C13—C18—H18A	109.5
C1—C2—H2B	108.8	C13—C18—H18B	109.5
H2A—C2—H2B	107.6	H18A—C18—H18B	109.5
O1—C3—C2	119.37 (12)	C13—C18—H18C	109.5
O1—C3—C4	122.27 (11)	H18A—C18—H18C	109.5
C2—C3—C4	118.31 (11)	H18B—C18—H18C	109.5
C3—C4—C29	109.74 (11)	C10—C19—C9	61.03 (8)
C3—C4—C30	106.73 (10)	C10—C19—H19A	117.7
C29—C4—C30	109.51 (12)	C9—C19—H19A	117.7
C3—C4—C5	108.26 (10)	C10—C19—H19B	117.7
C29—C4—C5	109.82 (9)	C9—C19—H19B	117.7
C30—C4—C5	112.69 (11)	H19A—C19—H19B	114.8
C6—C5—C10	113.43 (10)	C21—C20—C22	110.40 (11)
C6—C5—C4	114.25 (10)	C21—C20—C17	112.12 (11)
C10—C5—C4	112.88 (8)	C22—C20—C17	108.20 (8)
C6—C5—H5	105.0	C21—C20—H20	108.7
C10—C5—H5	105.0	C22—C20—H20	108.7
C4—C5—H5	105.0	C17—C20—H20	108.7
C5—C6—C7	108.75 (11)	C20—C21—H21A	109.5
C5—C6—H6A	109.9	C20—C21—H21B	109.5
C7—C6—H6A	109.9	H21A—C21—H21B	109.5
C5—C6—H6B	109.9	C20—C21—H21C	109.5
C7—C6—H6B	109.9	H21A—C21—H21C	109.5
H6A—C6—H6B	108.3	H21B—C21—H21C	109.5
C6—C7—C8	110.59 (9)	C23—C22—C20	116.77 (9)
C6—C7—H7A	109.5	C23—C22—H22A	108.1
C8—C7—H7A	109.5	C20—C22—H22A	108.1
C6—C7—H7B	109.5	C23—C22—H22B	108.1
C8—C7—H7B	109.5	C20—C22—H22B	108.1
H7A—C7—H7B	108.1	H22A—C22—H22B	107.3
C7—C8—C14	113.08 (8)	C24—C23—C22	112.22 (9)
C7—C8—C9	112.42 (9)	C24—C23—H23A	109.2
C14—C8—C9	112.51 (9)	C22—C23—H23A	109.2
C7—C8—H8	106.0	C24—C23—H23B	109.2
C14—C8—H8	106.0	C22—C23—H23B	109.2
C9—C8—H8	106.0	H23A—C23—H23B	107.9
C19—C9—C11	117.53 (8)	O2—C24—C23	108.37 (11)
C19—C9—C10	59.44 (7)	O2—C24—C25	111.15 (11)
C11—C9—C10	116.71 (9)	C23—C24—C25	115.58 (9)
C19—C9—C8	115.30 (10)	O2—C24—H24	107.1
C11—C9—C8	117.33 (9)	C23—C24—H24	107.1
C10—C9—C8	117.83 (8)	C25—C24—H24	107.1
C19—C10—C1	118.21 (8)	O3—C25—C26	109.21 (12)
C19—C10—C5	121.26 (10)	O3—C25—C27	109.70 (13)
C1—C10—C5	110.05 (9)	C26—C25—C27	111.20 (11)
C19—C10—C9	59.53 (7)	O3—C25—C24	102.58 (9)
C1—C10—C9	119.64 (10)	C26—C25—C24	111.16 (12)
C5—C10—C9	120.26 (8)	C27—C25—C24	112.61 (12)
C9—C11—C12	118.07 (10)	C25—C26—H26A	109.5
C9—C11—H11A	107.8	C25—C26—H26B	109.5
C12—C11—H11A	107.8	H26A—C26—H26B	109.5
C9—C11—H11B	107.8	C25—C26—H26C	109.5
C12—C11—H11B	107.8	H26A—C26—H26C	109.5
H11A—C11—H11B	107.1	H26B—C26—H26C	109.5
C13—C12—C11	114.28 (10)	C25—C27—H27A	109.5
C13—C12—H12A	108.7	C25—C27—H27B	109.5
C11—C12—H12A	108.7	H27A—C27—H27B	109.5
C13—C12—H12B	108.7	C25—C27—H27C	109.5
C11—C12—H12B	108.7	H27A—C27—H27C	109.5
H12A—C12—H12B	107.6	H27B—C27—H27C	109.5
C12—C13—C18	108.67 (9)	C14—C28—H28A	109.5
C12—C13—C17	117.26 (10)	C14—C28—H28B	109.5
C18—C13—C17	109.70 (10)	H28A—C28—H28B	109.5
C12—C13—C14	108.19 (9)	C14—C28—H28C	109.5
C18—C13—C14	111.60 (9)	H28A—C28—H28C	109.5
C17—C13—C14	101.26 (7)	H28B—C28—H28C	109.5
C15—C14—C8	113.42 (9)	C4—C29—H29A	109.5
C15—C14—C28	108.29 (8)	C4—C29—H29B	109.5
C8—C14—C28	110.46 (9)	H29A—C29—H29B	109.5
C15—C14—C13	102.58 (8)	C4—C29—H29C	109.5
C8—C14—C13	110.33 (7)	H29A—C29—H29C	109.5
C28—C14—C13	111.53 (9)	H29B—C29—H29C	109.5
C14—C15—C16	105.19 (9)	C4—C30—H30A	109.5
C14—C15—H15A	110.7	C4—C30—H30B	109.5
C16—C15—H15A	110.7	H30A—C30—H30B	109.5
C14—C15—H15B	110.7	C4—C30—H30C	109.5
C16—C15—H15B	110.7	H30A—C30—H30C	109.5
H15A—C15—H15B	108.8	H30B—C30—H30C	109.5
C15—C16—C17	107.48 (10)
C10—C1—C2—C3	−49.17 (15)	C11—C12—C13—C17	154.07 (9)
C1—C2—C3—O1	−138.27 (13)	C11—C12—C13—C14	40.45 (12)
C1—C2—C3—C4	44.24 (17)	C7—C8—C14—C15	−70.01 (12)
O1—C3—C4—C29	18.82 (18)	C9—C8—C14—C15	161.28 (8)
C2—C3—C4—C29	−163.77 (12)	C7—C8—C14—C28	51.77 (12)
O1—C3—C4—C30	−99.77 (14)	C9—C8—C14—C28	−76.94 (10)
C2—C3—C4—C30	77.65 (14)	C7—C8—C14—C13	175.56 (10)
O1—C3—C4—C5	138.67 (12)	C9—C8—C14—C13	46.84 (12)
C2—C3—C4—C5	−43.91 (14)	C12—C13—C14—C15	168.48 (9)
C3—C4—C5—C6	−176.55 (9)	C18—C13—C14—C15	−72.02 (11)
C29—C4—C5—C6	−56.74 (15)	C17—C13—C14—C15	44.63 (11)
C30—C4—C5—C6	65.64 (12)	C12—C13—C14—C8	−70.39 (11)
C3—C4—C5—C10	51.88 (13)	C18—C13—C14—C8	49.11 (12)
C29—C4—C5—C10	171.69 (12)	C17—C13—C14—C8	165.76 (9)
C30—C4—C5—C10	−65.93 (13)	C12—C13—C14—C28	52.77 (11)
C10—C5—C6—C7	−51.58 (13)	C18—C13—C14—C28	172.28 (9)
C4—C5—C6—C7	177.11 (9)	C17—C13—C14—C28	−71.08 (11)
C5—C6—C7—C8	69.51 (14)	C8—C14—C15—C16	−151.81 (9)
C6—C7—C8—C14	177.87 (11)	C28—C14—C15—C16	85.21 (10)
C6—C7—C8—C9	−53.37 (15)	C13—C14—C15—C16	−32.82 (11)
C7—C8—C9—C19	89.08 (12)	C14—C15—C16—C17	8.38 (12)
C14—C8—C9—C19	−141.86 (9)	C15—C16—C17—C20	151.07 (10)
C7—C8—C9—C11	−125.86 (11)	C15—C16—C17—C13	19.49 (12)
C14—C8—C9—C11	3.20 (13)	C12—C13—C17—C20	77.09 (14)
C7—C8—C9—C10	21.81 (14)	C18—C13—C17—C20	−47.45 (14)
C14—C8—C9—C10	150.87 (9)	C14—C13—C17—C20	−165.48 (11)
C2—C1—C10—C19	−87.67 (12)	C12—C13—C17—C16	−156.55 (9)
C2—C1—C10—C5	57.67 (11)	C18—C13—C17—C16	78.91 (10)
C2—C1—C10—C9	−156.75 (9)	C14—C13—C17—C16	−39.12 (11)
C6—C5—C10—C19	−49.13 (14)	C1—C10—C19—C9	−109.60 (11)
C4—C5—C10—C19	82.84 (13)	C5—C10—C19—C9	109.08 (11)
C6—C5—C10—C1	166.76 (10)	C11—C9—C19—C10	106.31 (11)
C4—C5—C10—C1	−61.27 (13)	C8—C9—C19—C10	−108.70 (10)
C6—C5—C10—C9	21.44 (15)	C16—C17—C20—C21	−178.35 (12)
C4—C5—C10—C9	153.41 (10)	C13—C17—C20—C21	−56.17 (16)
C11—C9—C10—C19	−107.68 (10)	C16—C17—C20—C22	59.67 (14)
C8—C9—C10—C19	104.44 (11)	C13—C17—C20—C22	−178.15 (11)
C19—C9—C10—C1	107.23 (10)	C21—C20—C22—C23	59.45 (17)
C11—C9—C10—C1	−0.45 (13)	C17—C20—C22—C23	−177.52 (11)
C8—C9—C10—C1	−148.32 (10)	C20—C22—C23—C24	−175.61 (12)
C19—C9—C10—C5	−110.71 (12)	C22—C23—C24—O2	−59.76 (15)
C11—C9—C10—C5	141.60 (10)	C22—C23—C24—C25	174.75 (12)
C8—C9—C10—C5	−6.27 (15)	O2—C24—C25—O3	57.48 (15)
C19—C9—C11—C12	112.19 (11)	C23—C24—C25—O3	−178.47 (12)
C10—C9—C11—C12	179.88 (9)	O2—C24—C25—C26	174.09 (12)
C8—C9—C11—C12	−32.08 (13)	C23—C24—C25—C26	−61.86 (17)
C9—C11—C12—C13	8.26 (13)	O2—C24—C25—C27	−60.36 (15)
C11—C12—C13—C18	−80.88 (11)	C23—C24—C25—C27	63.69 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	2.28	2.693 (2)	112
O3—H3···O1^i	0.82	2.13	2.930 (2)	166

Symmetry code: (i) x+1, y, z−1.