Lupeol

The title compound [systematic name: 3β-lup-20(29)-en-3-ol], C₃₀H₅₀O, was isolated from the leaves of Garcinia brasiliensis (common name: bacupari; a member of the Guttiferae family) and has been shown to have many useful medicinal and biological properties. The lupeol mol­ecule consists of four six-membered rings (adopting chair conformations) and one five-membered ring (with an envelope conformation), all fused in trans fashion. Lupeol is isomorphic with the penta­cyclic triterpene 3β,30-dihydr­oxylup-20(29)-ene, which differs from lupeol due to the presence of an additional hydr­oxy group. The crystal packing is stabilized by van der Waals inter­actions and inter­molecular O—H...O hydrogen bonds, giving rise to an infinite helical chain along the c axis.

S1. Comment

As part of our ongoing studies on the chemical constituents of Brazilian medicinal plants (Da Cruz et al., 2008; Derogis et al., 2008; Martins et al., 2007; Doriguetto et al., 2006; Soares et al., 2006; Lemos et al., 2006; Doriguetto et al., 2001), we have studied lupeol, (I), a natural pentacyclic triterpene isolated from leaves of Garcinia brasiliensis, known popularly as bacupari (Corrêa, 1978). From Garcinia genus (Guttiferae family), biflavonoids, xanthones, proanthocyanins, poliprenilated benzophenones, sesquiterpenes and pentacyclic triterpenes (PCTT) were isolated (Derogis et al., 2008; Dos Santos et al., 2007; Delle Monache et al., 1983). In particular, (I) has shown many interesting biological properties, such as, inhibition of cardiotoxicity induced by cyclosphosphamide (Sudharsan et al., 2006), and hepatoprotective (Sahdeo et al., 2007), anticancer (Laszczyk et al., 2006) and cytotoxic activities (Gauthier et al., 2006). Previous studies have also shown that (I) is a potential anti-inflammatory agent, preventing the production of some pro-inflammatory mediators (Fernández et al., 2001). Other biological targets of (I) are microorganisms such as bacteria and fungi (Shai et al., 2008).

In spite of its biological importance, up until now (I) has been characterized only by spectroscopic and spectrometric analysis (Śliwowski & Kasprzyk, 1974; Shamma et al., 1962). Therefore, in the present paper, we report for the first time the crystal structure of (I) (Fig. 1). The anomalous scattering was not large enough to permit the determination of the enantiomer present and therefore distinguish between the enantiomorphous space groups P4₁ and P4₃ (Flack, 2003). However, P4₃ was chosen because this space group is consistent with the stereochemistry specified by biosynthesis (Śliwowski & Kasprzyk, 1974). Thus, the chiral atoms present the following configurations: C3(S), C5(R), C8(R), C9(S), C10(R), C13(R), C14(R), C17(R), C19(R). Interestingly, another PCTT recently determined by us, 3β,30-dihydroxy-lup-20 (29)-ene, (II) (Pimenta et al., 2006), which differs chemically from (I) by the hydroxy group present at C30, was reported in the enantiomorphous P4₁ (or P4₃) space group [a = 19.038 (1) Å and c = 7.2290 (4) Å]. It is also important to mention that space groups P4₃ and P4₁ are rare for organic and organometallic compounds. Currently, in the Cambridge Structural Data Base (Version 5.29, updated in August 2008; Allen, 2002) there are only 341 and 454 structures deposited with space groups P4₃ and P4₁, respectively. Indeed, (I) is the first PCTT determined in P4₃ based on X-ray diffraction analysis and biosynthesis arguments (Śliwowski & Kasprzyk, 1974).

Fig. 1 shows that (I) contains five rings, all trans-fused, where all of the six-membered rings (A, B, C and D) adopt chair conformations, while the five-membered ring, E, adopts an envelope conformation with atom C17 in the flap position. The hydroxy group is linked at atom C3 in an equatorial position. The intramolecular geometric parameters were analyzed by Mogul check (Bruno et al., 2004). All geometrical values agree with those of other reported PCTT structures (e.g. Pimenta et al., 2006; Madureira et al., 2004; Silva et al., 2002; Nakai et al., 1985).

Compound (I) contains an intermolecular hydrogen bond O—H···O (Fig. 2 and Table 1). This interaction stabilizes the packing and gives rise to an infinite helical chain along the c axis. The molecules are related by 4₃-fold improper symmetry. Additionally, parallel chains are linked together to form a `cogwheel' structure, connected via van der Waals interactions (Fig. 2). These interactions are probably the driving force for the growth of (I) as single crystals with a needle habit.

Comparison of (I) with (II) (Pimenta et al., 2006) by the Kabsch (1976) method showed them to be very similar in terms of intramolecular geometry, with an r.m.s. deviation between homologous atoms of 0.024 (17) Å. The largest deviation between the analogues takes place at atom C30 [the displacement is 0.09 (2) Å]. However the most surprising result highlighted by the X-ray diffraction analysis is that (I) and (II) (Pimenta et al., 2006) are isomorphs: they crystallize in an enantiomorphous space group with almost identical cell parameters and supramolecular structures. Thus, the hydroxy group linked to atom C3 in both molecules is more important in terms of the packing than the hydroxy group linked to atom C30 in (II) (Pimenta et al., 2006). Although a similar supramolecular structure is observed, the forces that stabilize the crystal packing are slightly different in (I) and (II). In Fig. 2, which gives the crystal structure of (I) projected onto the ab plane, we observe the hydrophilic head hydrogen bonded along the [001] direction through the unit-cell center, whereas the hydrophobic tails, linked by weak van der Waals forces, are stacked along the [001] direction through unit-cell corners. These characteristics could explain the difficulty in obtaining single crystals of lupeol and their fragility. In (II) (Pimenta et al., 2006), there are additionally intermolecular hydrogen bonds at the unit-cell corners, which give rise to more mechanical stability in (II) than in (I).

Related literature

For related literature, see: Allen (2002); Bruno et al. (2004); Corrêa (1978); Da Cruz, de Moraes, dos Santos, da Silva, Brigagão, Ellena & Doriguetto (2008); Delle Monache, Delle Monache & Bettolo (1983); Derogis et al. (2008); Doriguetto et al. (2001, 2006); Dos Santos, Corrêa, Rocha, Nagem, Oliveira, Lima & Oliveira (2007); Fernández et al. (2001); Flack (2003); Gauthier et al. (2006); Kabsch (1976); Laszczyk et al. (2006); Lemos et al. (2006); Madureira et al. (2004); Martins et al. (2007); Nakai et al. (1985); Pimenta, Silva, Silva, Barbosa, Ellena & Doriguetto (2006); Sahdeo et al. (2007); Shai et al. (2008); Shamma et al. (1962); Silva et al. (2002); Soares et al. (2006); Śliwowski & Kasprzyk (1974).

S2. Experimental

The leaves of G. brasiliensis were collected in Viçosa, Minas Gerais state, Brazil, in 2006. A voucher specimen (VIC26240) is deposited at herbarium of Universidade Federal de Viçosa. The leaves were dried and submitted to a dichloromethane extraction. The solvent was removed in vacuum and the dichloromethane extract (10 g) was submitted to column chromatography using silica gel. This extract was eluted in increasing amounts of hexane, hexane/ethyl acetate, ethyl acetate and ethyl acetate/ethanol, obtaining 95 fractions. From fraction 26 (hexane/ethyl acetate 9:1 v/v), a white solid was obtained by recrystallization with methanol, yielding lupeol (525 mg). Single crystals were obtained after one week by slow evaporation from a chloroform and methanol (2:1 v/v) solution at 283 K.

S3. Refinement

H atoms bound to C atoms were located from an electron-density difference synthesis and refined as riding on their parent atoms, with U_iso(H) values of 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for the remaining H atoms. The hydroxy H atom was located by difference Fourier synthesis and was refined isotropically. In the absence of significant anomalous scattering, the Friedel pair reflections were merged before final refinement.

Computing details

Data collection: Collect (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of lupeol, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I) projected onto the ab plane showing the hydrophilic head (center) and the hydrophobic tail (corner). H-bonds linking the molecules of (I) form a helix along the c axis. [Symmetry codes: (i) -y + 1, x, z - 1/4; (ii) -x + 1, -y + 1, z - 1/2; (iii) y, -x + 1, z - 3/4; (iv) y, -x + 1, z + 1/4].

3β-lup-20 (29)-en-3-ol

Crystal data

C30H50O	Dx = 1.077 Mg m^−3
Mr = 426.7	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43	Cell parameters from 8982 reflections
Hall symbol: P 4cw	θ = 2.9–25.7°
a = 19.1006 (14) Å	µ = 0.06 mm^−1
c = 7.2128 (4) Å	T = 298 K
V = 2631.5 (3) Å^3	Needle, colourless
Z = 4	0.40 × 0.06 × 0.04 mm
F(000) = 952

Data collection

Nonius KappaCCD diffractometer	1943 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.080
Horizonally mounted graphite crystal monochromator	θmax = 25.7°, θmin = 3.2°
Detector resolution: 9 pixels mm^-1	h = −23→18
ϕ scans and ω scans winth κ offsets	k = −23→20
7896 measured reflections	l = −8→7
2655 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0606P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.113	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.1 e Å^−3
2655 reflections	Δρmin = −0.10 e Å^−3
284 parameters

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.

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

	x	y	z	Uiso*/Ueq
O1	0.42390 (11)	0.48740 (11)	0.7438 (3)	0.0655 (5)
C1	0.26606 (14)	0.39431 (15)	0.9341 (4)	0.0584 (7)
H1A	0.2528	0.3853	1.0617	0.07*
H1B	0.2733	0.3494	0.8741	0.07*
C2	0.33495 (14)	0.43490 (16)	0.9326 (4)	0.0606 (7)
H2A	0.3294	0.478	1.0022	0.073*
H2B	0.371	0.4072	0.9926	0.073*
C3	0.35750 (13)	0.45196 (14)	0.7372 (4)	0.0559 (7)
H3	0.3646	0.4076	0.6718	0.067*
C4	0.30280 (14)	0.49429 (14)	0.6280 (4)	0.0542 (6)
C5	0.23229 (13)	0.45354 (13)	0.6396 (3)	0.0486 (6)
H5	0.2421	0.4087	0.5787	0.058*
C6	0.17303 (14)	0.48551 (14)	0.5247 (4)	0.0568 (7)
H6A	0.1542	0.526	0.5889	0.068*
H6B	0.1913	0.5011	0.4062	0.068*
C7	0.11475 (14)	0.43232 (14)	0.4926 (4)	0.0532 (6)
H7A	0.1333	0.3936	0.4208	0.064*
H7B	0.078	0.4542	0.4201	0.064*
C8	0.08270 (13)	0.40340 (12)	0.6742 (3)	0.0467 (6)
C9	0.14331 (13)	0.37950 (13)	0.8053 (3)	0.0470 (6)
H9	0.1648	0.3396	0.7414	0.056*
C10	0.20527 (13)	0.43256 (13)	0.8362 (3)	0.0490 (6)
C11	0.11373 (14)	0.34848 (14)	0.9858 (4)	0.0565 (7)
H11A	0.1521	0.3318	1.062	0.068*
H11B	0.0896	0.3849	1.0541	0.068*
C12	0.06315 (14)	0.28812 (15)	0.9494 (4)	0.0555 (7)
H12A	0.0886	0.2492	0.8954	0.067*
H12B	0.0433	0.2725	1.0661	0.067*
C13	0.00426 (13)	0.30984 (14)	0.8190 (4)	0.0517 (6)
H13	−0.0199	0.3492	0.8784	0.062*
C14	0.03361 (13)	0.33778 (13)	0.6315 (3)	0.0489 (6)
C15	−0.02787 (14)	0.35906 (14)	0.5015 (4)	0.0618 (7)
H15A	−0.0475	0.4028	0.5461	0.074*
H15B	−0.0091	0.3677	0.3786	0.074*
C16	−0.08757 (15)	0.30504 (15)	0.4849 (4)	0.0667 (8)
H16A	−0.1257	0.3253	0.4142	0.08*
H16B	−0.0707	0.2643	0.4181	0.08*
C17	−0.11480 (14)	0.28221 (15)	0.6751 (5)	0.0641 (8)
C18	−0.05153 (14)	0.25305 (13)	0.7842 (4)	0.0537 (7)
H18	−0.0295	0.2181	0.7036	0.064*
C19	−0.08340 (15)	0.21241 (15)	0.9469 (5)	0.0633 (7)
H19	−0.0894	0.2447	1.0513	0.076*
C20	−0.04282 (17)	0.14889 (15)	1.0145 (5)	0.0671 (8)
C21	−0.15751 (16)	0.19062 (18)	0.8756 (5)	0.0767 (9)
H21A	−0.1627	0.1401	0.8778	0.092*
H21B	−0.1938	0.2112	0.9523	0.092*
C22	−0.16245 (16)	0.21806 (17)	0.6776 (5)	0.0756 (9)
H22A	−0.2102	0.2309	0.6473	0.091*
H22B	−0.1464	0.1831	0.5897	0.091*
C23	0.29855 (16)	0.57027 (14)	0.6948 (5)	0.0697 (8)
H23A	0.2927	0.5711	0.8269	0.105*
H23B	0.2594	0.593	0.637	0.105*
H23C	0.3409	0.5944	0.6622	0.105*
C24	0.32698 (17)	0.49550 (18)	0.4236 (4)	0.0727 (9)
H24A	0.2994	0.5288	0.3556	0.109*
H24B	0.3211	0.4498	0.3703	0.109*
H24C	0.3754	0.5087	0.4179	0.109*
C25	0.18454 (16)	0.49564 (15)	0.9588 (4)	0.0608 (7)
H25A	0.1531	0.4803	1.0543	0.091*
H25B	0.1619	0.5305	0.8838	0.091*
H25C	0.2258	0.5153	1.0142	0.091*
C26	0.03930 (14)	0.46306 (13)	0.7617 (5)	0.0598 (7)
H26A	0.0669	0.5051	0.7653	0.09*
H26B	0.026	0.4502	0.8854	0.09*
H26C	−0.002	0.471	0.6886	0.09*
C27	0.07381 (15)	0.27927 (14)	0.5296 (4)	0.0589 (7)
H27A	0.1102	0.2616	0.6084	0.088*
H27B	0.0941	0.2978	0.4181	0.088*
H27C	0.0421	0.242	0.4989	0.088*
C28	−0.15228 (16)	0.34300 (17)	0.7735 (6)	0.0827 (10)
H28A	−0.1936	0.3554	0.7054	0.124*
H28B	−0.1215	0.3827	0.7798	0.124*
H28C	−0.1651	0.3289	0.8966	0.124*
C29	0.00880 (17)	0.11831 (17)	0.9239 (5)	0.0787 (9)
H29A	0.0296	0.0782	0.972	0.094*
H29B	0.0244	0.1368	0.8121	0.094*
C30	−0.0681 (2)	0.1188 (2)	1.1962 (6)	0.1070 (13)
H30A	−0.0424	0.0768	1.2237	0.161*
H30B	−0.1171	0.1081	1.1871	0.161*
H30C	−0.0608	0.1524	1.2934	0.161*
H1	0.4509 (19)	0.465 (2)	0.677 (6)	0.099 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0531 (12)	0.0744 (14)	0.0691 (13)	−0.0050 (10)	0.0029 (10)	−0.0179 (11)
C1	0.0580 (16)	0.0668 (17)	0.0504 (15)	−0.0008 (13)	−0.0096 (13)	0.0085 (13)
C2	0.0560 (16)	0.0702 (18)	0.0557 (17)	0.0033 (14)	−0.0093 (13)	0.0024 (13)
C3	0.0520 (15)	0.0589 (16)	0.0569 (17)	−0.0049 (12)	0.0026 (12)	−0.0088 (13)
C4	0.0576 (15)	0.0560 (15)	0.0491 (15)	−0.0039 (13)	−0.0027 (12)	0.0018 (12)
C5	0.0570 (15)	0.0471 (14)	0.0417 (13)	0.0016 (11)	−0.0029 (12)	−0.0013 (11)
C6	0.0663 (17)	0.0529 (15)	0.0513 (16)	−0.0004 (13)	−0.0055 (13)	0.0064 (12)
C7	0.0587 (16)	0.0573 (16)	0.0437 (13)	0.0024 (12)	−0.0104 (12)	0.0053 (12)
C8	0.0508 (14)	0.0441 (13)	0.0451 (14)	0.0062 (11)	−0.0031 (11)	−0.0018 (11)
C9	0.0532 (14)	0.0489 (14)	0.0390 (14)	0.0038 (11)	−0.0026 (11)	−0.0010 (11)
C10	0.0516 (14)	0.0517 (15)	0.0437 (14)	0.0019 (11)	−0.0027 (11)	−0.0018 (11)
C11	0.0615 (16)	0.0643 (17)	0.0436 (15)	−0.0069 (13)	−0.0065 (13)	0.0034 (12)
C12	0.0585 (16)	0.0622 (16)	0.0459 (15)	−0.0060 (13)	−0.0062 (12)	0.0040 (12)
C13	0.0546 (15)	0.0486 (14)	0.0517 (15)	0.0031 (11)	−0.0014 (12)	−0.0052 (11)
C14	0.0516 (14)	0.0482 (13)	0.0469 (15)	0.0049 (11)	−0.0064 (12)	−0.0029 (11)
C15	0.0636 (17)	0.0612 (16)	0.0607 (17)	0.0017 (13)	−0.0158 (14)	0.0029 (14)
C16	0.0663 (18)	0.0642 (18)	0.0694 (19)	0.0025 (14)	−0.0224 (15)	−0.0006 (15)
C17	0.0546 (16)	0.0594 (17)	0.078 (2)	0.0044 (13)	−0.0111 (14)	−0.0054 (15)
C18	0.0535 (15)	0.0500 (14)	0.0576 (16)	0.0012 (12)	−0.0026 (12)	−0.0062 (13)
C19	0.0633 (17)	0.0621 (17)	0.0647 (18)	−0.0066 (14)	0.0038 (14)	−0.0064 (14)
C20	0.0720 (19)	0.0592 (17)	0.0702 (19)	−0.0146 (15)	−0.0089 (16)	0.0047 (15)
C21	0.0585 (18)	0.080 (2)	0.092 (2)	−0.0091 (16)	0.0011 (17)	−0.0035 (19)
C22	0.0604 (18)	0.073 (2)	0.093 (2)	−0.0054 (16)	−0.0135 (17)	−0.0027 (18)
C23	0.0685 (18)	0.0536 (17)	0.087 (2)	−0.0050 (13)	−0.0068 (16)	−0.0025 (15)
C24	0.074 (2)	0.090 (2)	0.0539 (17)	−0.0155 (17)	0.0027 (15)	0.0075 (16)
C25	0.0658 (17)	0.0668 (18)	0.0498 (16)	−0.0051 (14)	0.0005 (13)	−0.0140 (13)
C26	0.0623 (16)	0.0522 (15)	0.0648 (18)	0.0074 (12)	−0.0032 (14)	−0.0075 (13)
C27	0.0687 (17)	0.0538 (15)	0.0543 (16)	0.0005 (13)	−0.0011 (14)	−0.0090 (12)
C28	0.0627 (18)	0.073 (2)	0.113 (3)	0.0144 (15)	−0.0037 (19)	−0.013 (2)
C29	0.075 (2)	0.0648 (19)	0.096 (2)	0.0025 (17)	−0.0115 (19)	0.0140 (18)
C30	0.142 (4)	0.090 (3)	0.089 (3)	−0.015 (3)	0.009 (3)	0.017 (2)

Geometric parameters (Å, º)

O1—C3	1.438 (3)	C15—H15B	0.97
O1—H1	0.82 (4)	C16—C17	1.531 (5)
C1—C2	1.527 (4)	C16—H16A	0.97
C1—C10	1.543 (3)	C16—H16B	0.97
C1—H1A	0.97	C17—C22	1.527 (4)
C1—H1B	0.97	C17—C28	1.537 (4)
C2—C3	1.509 (4)	C17—C18	1.546 (4)
C2—H2A	0.97	C18—C19	1.533 (4)
C2—H2B	0.97	C18—H18	0.98
C3—C4	1.538 (4)	C19—C20	1.520 (4)
C3—H3	0.98	C19—C21	1.563 (4)
C4—C23	1.531 (4)	C19—H19	0.98
C4—C24	1.545 (4)	C20—C29	1.319 (5)
C4—C5	1.558 (4)	C20—C30	1.510 (5)
C5—C6	1.530 (4)	C21—C22	1.524 (5)
C5—C10	1.561 (3)	C21—H21A	0.97
C5—H5	0.98	C21—H21B	0.97
C6—C7	1.525 (4)	C22—H22A	0.97
C6—H6A	0.97	C22—H22B	0.97
C6—H6B	0.97	C23—H23A	0.96
C7—C8	1.548 (4)	C23—H23B	0.96
C7—H7A	0.97	C23—H23C	0.96
C7—H7B	0.97	C24—H24A	0.96
C8—C26	1.544 (3)	C24—H24B	0.96
C8—C9	1.563 (3)	C24—H24C	0.96
C8—C14	1.595 (3)	C25—H25A	0.96
C9—C11	1.538 (4)	C25—H25B	0.96
C9—C10	1.574 (3)	C25—H25C	0.96
C9—H9	0.98	C26—H26A	0.96
C10—C25	1.546 (4)	C26—H26B	0.96
C11—C12	1.527 (4)	C26—H26C	0.96
C11—H11A	0.97	C27—H27A	0.96
C11—H11B	0.97	C27—H27B	0.96
C12—C13	1.524 (4)	C27—H27C	0.96
C12—H12A	0.97	C28—H28A	0.96
C12—H12B	0.97	C28—H28B	0.96
C13—C18	1.541 (4)	C28—H28C	0.96
C13—C14	1.558 (4)	C29—H29A	0.93
C13—H13	0.98	C29—H29B	0.93
C14—C27	1.543 (4)	C30—H30A	0.96
C14—C15	1.557 (3)	C30—H30B	0.96
C15—C16	1.542 (4)	C30—H30C	0.96
C15—H15A	0.97
C3—O1—H1	107 (2)	C16—C15—H15B	108.4
C2—C1—C10	113.9 (2)	C14—C15—H15B	108.4
C2—C1—H1A	108.8	H15A—C15—H15B	107.5
C10—C1—H1A	108.8	C17—C16—C15	111.9 (2)
C2—C1—H1B	108.8	C17—C16—H16A	109.2
C10—C1—H1B	108.8	C15—C16—H16A	109.2
H1A—C1—H1B	107.7	C17—C16—H16B	109.2
C3—C2—C1	111.2 (2)	C15—C16—H16B	109.2
C3—C2—H2A	109.4	H16A—C16—H16B	107.9
C1—C2—H2A	109.4	C22—C17—C16	116.2 (3)
C3—C2—H2B	109.4	C22—C17—C28	108.9 (3)
C1—C2—H2B	109.4	C16—C17—C28	110.9 (3)
H2A—C2—H2B	108	C22—C17—C18	99.8 (2)
O1—C3—C2	108.8 (2)	C16—C17—C18	107.0 (2)
O1—C3—C4	111.6 (2)	C28—C17—C18	113.7 (3)
C2—C3—C4	113.4 (2)	C19—C18—C13	120.4 (2)
O1—C3—H3	107.6	C19—C18—C17	105.2 (2)
C2—C3—H3	107.6	C13—C18—C17	111.7 (2)
C4—C3—H3	107.6	C19—C18—H18	106.2
C23—C4—C3	111.9 (2)	C13—C18—H18	106.2
C23—C4—C24	107.6 (2)	C17—C18—H18	106.2
C3—C4—C24	107.1 (2)	C20—C19—C18	116.6 (2)
C23—C4—C5	114.3 (2)	C20—C19—C21	110.8 (2)
C3—C4—C5	107.3 (2)	C18—C19—C21	104.0 (2)
C24—C4—C5	108.5 (2)	C20—C19—H19	108.4
C6—C5—C4	114.3 (2)	C18—C19—H19	108.4
C6—C5—C10	110.5 (2)	C21—C19—H19	108.4
C4—C5—C10	117.6 (2)	C29—C20—C30	120.0 (3)
C6—C5—H5	104.3	C29—C20—C19	125.1 (3)
C4—C5—H5	104.3	C30—C20—C19	114.8 (3)
C10—C5—H5	104.3	C22—C21—C19	105.8 (3)
C7—C6—C5	110.9 (2)	C22—C21—H21A	110.6
C7—C6—H6A	109.5	C19—C21—H21A	110.6
C5—C6—H6A	109.5	C22—C21—H21B	110.6
C7—C6—H6B	109.5	C19—C21—H21B	110.6
C5—C6—H6B	109.5	H21A—C21—H21B	108.7
H6A—C6—H6B	108	C21—C22—C17	104.5 (3)
C6—C7—C8	113.4 (2)	C21—C22—H22A	110.9
C6—C7—H7A	108.9	C17—C22—H22A	110.9
C8—C7—H7A	108.9	C21—C22—H22B	110.9
C6—C7—H7B	108.9	C17—C22—H22B	110.9
C8—C7—H7B	108.9	H22A—C22—H22B	108.9
H7A—C7—H7B	107.7	C4—C23—H23A	109.5
C26—C8—C7	107.1 (2)	C4—C23—H23B	109.5
C26—C8—C9	111.5 (2)	H23A—C23—H23B	109.5
C7—C8—C9	108.86 (19)	C4—C23—H23C	109.5
C26—C8—C14	110.06 (19)	H23A—C23—H23C	109.5
C7—C8—C14	110.47 (19)	H23B—C23—H23C	109.5
C9—C8—C14	108.82 (18)	C4—C24—H24A	109.5
C11—C9—C8	110.6 (2)	C4—C24—H24B	109.5
C11—C9—C10	113.85 (19)	H24A—C24—H24B	109.5
C8—C9—C10	117.04 (19)	C4—C24—H24C	109.5
C11—C9—H9	104.6	H24A—C24—H24C	109.5
C8—C9—H9	104.6	H24B—C24—H24C	109.5
C10—C9—H9	104.6	C10—C25—H25A	109.5
C1—C10—C25	107.5 (2)	C10—C25—H25B	109.5
C1—C10—C5	106.8 (2)	H25A—C25—H25B	109.5
C25—C10—C5	113.8 (2)	C10—C25—H25C	109.5
C1—C10—C9	109.0 (2)	H25A—C25—H25C	109.5
C25—C10—C9	113.0 (2)	H25B—C25—H25C	109.5
C5—C10—C9	106.57 (18)	C8—C26—H26A	109.5
C12—C11—C9	112.2 (2)	C8—C26—H26B	109.5
C12—C11—H11A	109.2	H26A—C26—H26B	109.5
C9—C11—H11A	109.2	C8—C26—H26C	109.5
C12—C11—H11B	109.2	H26A—C26—H26C	109.5
C9—C11—H11B	109.2	H26B—C26—H26C	109.5
H11A—C11—H11B	107.9	C14—C27—H27A	109.5
C13—C12—C11	111.6 (2)	C14—C27—H27B	109.5
C13—C12—H12A	109.3	H27A—C27—H27B	109.5
C11—C12—H12A	109.3	C14—C27—H27C	109.5
C13—C12—H12B	109.3	H27A—C27—H27C	109.5
C11—C12—H12B	109.3	H27B—C27—H27C	109.5
H12A—C12—H12B	108	C17—C28—H28A	109.5
C12—C13—C18	114.8 (2)	C17—C28—H28B	109.5
C12—C13—C14	111.3 (2)	H28A—C28—H28B	109.5
C18—C13—C14	110.4 (2)	C17—C28—H28C	109.5
C12—C13—H13	106.6	H28A—C28—H28C	109.5
C18—C13—H13	106.6	H28B—C28—H28C	109.5
C14—C13—H13	106.6	C20—C29—H29A	120
C27—C14—C15	106.1 (2)	C20—C29—H29B	120
C27—C14—C13	110.2 (2)	H29A—C29—H29B	120
C15—C14—C13	109.9 (2)	C20—C30—H30A	109.5
C27—C14—C8	111.6 (2)	C20—C30—H30B	109.5
C15—C14—C8	110.76 (19)	H30A—C30—H30B	109.5
C13—C14—C8	108.25 (19)	C20—C30—H30C	109.5
C16—C15—C14	115.4 (2)	H30A—C30—H30C	109.5
C16—C15—H15A	108.4	H30B—C30—H30C	109.5
C14—C15—H15A	108.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1^i	0.82 (4)	1.94 (4)	2.756 (3)	171 (4)

Symmetry code: (i) −y+1, x, z−1/4.