3α-Hydroxytirucalla-7,24-dien-21-oic acid: a triterpene from Protium crenatum Sandwith

The crystal structure of the title compound, C₃₀H₄₈O₃, a triterpene extracted from the resin of Protium crenatum Sandwith, is reported. The aliphatic acidic side chain is attached to the tirucallene four-ring system on its α-face and is extended by 7.248 (5) Å in the `left-hand' orientation.

S1. Comment

The title compound, (I), was isolated from the resin of Protium crenatum Sandwith (Burseraceae), a tree about 35 m tall that grows in lowland, lower mountain and riparian forests in northern Brazil, Colombia, Guyana and Venezuela (Daly, 1997). The resin is used by the indigenous peoples as an antiinflamatory agent. Similar tirucallane compounds have been isolated previously from elemi resin (Arigoni et al., 1995; Coterrell et al., 1970; Argay et al., 1997), which is produced by a Burseraceae tree from the Philippine Islands. It has also been reported as a constituent of the oleoresin of Aucoumea klaideana, a large tree from equatorial Africa (Tessier et al., 1982; Guang-Yi et al., 1989). New tirucallane triterpenes have recently been reported as constituents of the bark of Dysoxylum macranthum, a Meliaceae tree from New Caledonia (Mohamad et al., 1999). \sch

The structure of (I) was initially inferred from ¹³C and ¹H NMR data and HMBC (please define), and solved from single-crystal X-ray diffraction, which confirmed its true composition and stereochemistry. However, the absolute structure was not established in this study. The configuration adopted was that occurring in all tirucallene structures found in the Cambridge Structural Database (Allen & Kennard, 1993), which implied refining the structure in the enantiomorphous space group P3₁2₁.

The molecular structure of (I) (Fig. 1) shows that the A, B, C and D rings adopt chair [ΔC₂(2–3)_min = 1.8 (6), ΔC₂(3–4)_max = 9.4 (6), ΔC_s(2)_min = 4.2 (4), ΔC_s(1)_max = 8.9 (5)], half-chair [ΔC₂(7–8) = 6.5 (6)], half-chair [ΔC₂(9–11) = 6.5 (6)], and half-chair [ΔC₂(13–14) = 8.4 (5)] conformations, respectively (Griffin et al., 1984).

The hydroxyl group at position 3, the methyl group at position 13 and the aliphatic chain at position 17 are substituents of the α-face of the triterpene ring system, while the methyl groups at positions 10 and 14 project out of the β-face. A similar arrangement is found in other tirucallene compounds such as Schinol, a triterpene found in the pink peppercorn (Schinus terebinthifolius; Jain et al., 1995), and in Cuachalalic acid, a triterpene from Amphyterygium adstringens (Watson et al., 1987; Soriano-García et al., 1987). This conformation seems to persist in solution, as shown by the ¹H NMR signal from the β hydrogen on C3 at δ 3.50 p.p.m. (singlet). The C7═C8 bond length of 1.353 (5) Å is slightly higher than the average distance of 1.32 (1) Å observed in 15 tirucallene fragments found in the Cambridge Structural Database (Allen & Kennard, 1993).

The side-chain conformation plays an important role in the inhibitory activity of cell membranes (see, for example, Jain et al., 1995). In compound (I), the aliphatic acidic side chain adopts a fully extended configuration in the `left-hand' orientation [C22 anti to C13: C13—C17—C20—C22 - 172.2 (3)°], extending by 7.248 (5) Å out of the tetracyclic nucleus. This orientation is in contrast with that found in the closely related triterpene 3-oxo-5α,13α,14β,17α-lanosta-7,24-dien-20-oic acid methyl ester from elemi resin (Argay et al., 1997), in which the side chain extends towards the`right-hand' side.

The geometrical data for the principal intermolecular contacts of (I) are reported in Table 1 and these interactions are shown in Fig. 2. Chains of molecules related by a unit-cell translation along the a and b axes are linked by O—H···O═C hydrogen bonds and additional weak van der Waals C22—H22a···O1ⁱⁱⁱ contacts of 3.404 (6) Å [symmetry code: (iii) x - 1, y - 1, z]. A second hydrogen bond, of the type C—O—H···O═C involving the carboxylic groups of molecules related by the 3₁ screw axes, results in an extended ribbon of molecules running in the [110] direction. The borders of each ribbon consist of hydrophobic methyl groups which do not form any inter-ribbon contacts.

Related literature

For related literature, see: Allen & Kennard (1993); Argay et al. (1997); Arigoni et al. (1995); Coterrell et al. (1970); Daly (1997); Griffin et al. (1984); Guang-Yi, Gray, Patalinghug, Skelton, Waterman & White (1989); Jain et al. (1995); Mohamad et al. (1999); Soriano-García, Toscano, Ortíz, Navarrete, Sanchez-Obregon, Barrios & Yuste (1987); Tessier et al. (1982); Watson et al. (1987).

S2. Experimental

The resin from Protium crenatum Sandwith was obtained by making incisions in the bark of trees found at the Forest Reserve of Ticoporo, Barinas State, Venezuela, at an altitude of about 200 m. The resin was dissolved in diethyl ether and filtered to remove solid impurities. It was then fractionated over silica gel, eluting with hexane and hexane–diethyl ether mixtures. Fractions eluted with 8% Et₂O were subjected to preparative thin layer chromatography, yielding 310 mg of pure 3α-hydroxytirucalla-7,24-diene-21-oic acid (m.p. 473–475 K), suitable for X-ray analysis. Spectroscopic data: IR (KBr, ν_max, cm^-1): 3470, 1688; EIMS: M⁺, 456 (C₃₀H₄₈O₃, 11°). Assignment of ¹H NMR and ¹³C NMR signals was made by use of standard two-dimensional NMR techniques. ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 5.24 (1H, br s, H7), 5.09 (1H, t, J = 7.2 Hz, H24), 3.50 (1H, br s, H3), 2.32 (1H, m, H9), 2.30 (1H, dt, J = 9.8, 4.1 Hz, H20), 2.05 (1H, d, J = 8.3 Hz, H6α), 1.99 (1H, m, H17), 1.96 (1H, m, H22a), 1.94 (1H, m, H23a), 1.90 (1H, m, H2α), 1.85 (1H, m, H22b), 1.77 (1H, m, H6β), 1.72 (1H, dd, J = 11.8, 5.6 Hz, H5), 1.70 (1H, m, H15α), 1.67 (3H, s, H27), 1.62 (1H, m, H23b), 1.60 (1H, dd, J = 3.2, 7.9 Hz), 1.57 (3H, s, H26), 1.52 (1H, m, H1α), 1.51 (1H, m, H15β), 1.45 (1H, m, H16α), 1.42 (1H, m, H12α), 1.40 (1H, m, H12β), 1.32 (1H, d, J = 3.2 Hz, H1β), 1.26 (1H, m, H11α), 0.95 (3H, s, H30), 0.94 (3H, s, H29), 0.92 (3H, s, H18), 0.84 (1H, m, H11β), 0.80 (3H, s, H28), 0.72 (3H, s, H19); ¹³C NMR (400 MHz, CDCl₃, δ, p.p.m.): 181.8 (C21), 145.3 (C8), 132.1 (C25), 123.7 (C24), 118.2 (C7), 76.5 (C3), 51.0 (C14), 49.7 (C17), 48.2 (C9), 47.8 (C20), 44.5 (C5), 43.3 (C13), 37.3 (C4), 34.8 (C10), 33.4 (C12), 32.4 (C22), 31.2 (C1), 30.2 (C15), 27.7 (C28), 27.3 (C30), 27.0 (C11), 25.7 (C27), 25.3 (C2), 23.9 (C6), 21.8 (C18), 21.7 (C29), 17.6 (C26), 17.5 (C16), 12.9 (C19).

S3. Refinement

All H atoms were placed in geometrically calculated positions and their isotropic displacement parameters were set to 1.2 times (1.5 times for CH₃ groups) the equivalent displacement parameter of their parent atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: PLATON (Spek, 2000) and SHELXL97.

Figures

	Fig. 1. The molecular view of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The hydrogen-bonding scheme for (I) [symmetry codes: (i) 1 + x, 1 + y, z; (ii) -x, -x + y, 1/3 - z].

3α-hydroxytirucalla-7,24-diene-21-oic acid

Crystal data

C30H48O3	Dx = 1.106 Mg m^−3
Mr = 456.68	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121	Cell parameters from 3464 reflections
Hall symbol: P 31 2"	θ = 3.0–50.7°
a = 11.3717 (6) Å	µ = 0.07 mm^−1
c = 36.739 (3) Å	T = 293 K
V = 4114.4 (4) Å^3	Plate, colourless
Z = 6	0.4 × 0.3 × 0.3 mm
F(000) = 1512

Data collection

Siemens SMART CCD area-detector diffractometer	1621 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.088
Graphite monochromator	θmax = 25.4°, θmin = 1.7°
ω scans	h = −11→13
22258 measured reflections	k = −13→13
2915 independent reflections	l = −44→44

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 0.90	Calculated w = 1/[σ^2(Fo^2) + (0.0844P)^2] where P = (Fo^2 + 2Fc^2)/3
2915 reflections	(Δ/σ)max < 0.001
295 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

Experimental. X-ray data were collected on a Siemens SMART CCD diffractometer equipped with a normal focus 2.4 kW sealed tube X-ray source (Mo Kα radiation, λ = 0.71073 Å) operating at 40 kV and 30 mA. The data collection covered about 1.3 hemispheres of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 90, 180°) for the crystal and each exposure of 14 s covered 0.3° in ω to give a total of 1321 frames. The crystal-to-detector distance was 5.029 cm and the detector swing angle was 30°. Coverage of the unique set was over 99% complete. Crystal decay was monitored by repeating fifty frames from the initial set at the end of the data collection.

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	0.6514 (3)	0.8987 (4)	0.1073 (1)	0.117 (1)
O2	0.1191 (3)	0.0090 (3)	0.12822 (6)	0.0665 (7)
O3	−0.1017 (3)	−0.0722 (3)	0.13326 (6)	0.0682 (8)
C1	0.4061 (4)	0.7267 (5)	0.1486 (1)	0.075 (1)
C2	0.5009 (5)	0.8781 (5)	0.1556 (1)	0.089 (2)
C3	0.5726 (5)	0.9507 (5)	0.1210 (1)	0.079 (1)
C4	0.4740 (4)	0.9379 (4)	0.0909 (1)	0.067 (1)
C5	0.3720 (4)	0.7848 (4)	0.08495 (9)	0.057 (1)
C6	0.2703 (4)	0.7586 (4)	0.0545 (1)	0.080 (1)
C7	0.1735 (4)	0.6115 (5)	0.0489 (1)	0.075 (1)
C8	0.1573 (4)	0.5128 (4)	0.07231 (9)	0.056 (1)
C9	0.2395 (4)	0.5477 (4)	0.10661 (9)	0.059 (1)
C10	0.2998 (4)	0.6963 (4)	0.11885 (9)	0.058 (1)
C11	0.1717 (5)	0.4400 (4)	0.13608 (9)	0.068 (1)
C12	0.1100 (5)	0.2928 (4)	0.12471 (9)	0.066 (1)
C13	0.0957 (3)	0.2698 (4)	0.08331 (8)	0.0511 (9)
C14	0.0501 (4)	0.3658 (4)	0.06645 (9)	0.055 (1)
C15	0.0194 (5)	0.3142 (4)	0.0272 (1)	0.077 (1)
C16	−0.0398 (4)	0.1597 (4)	0.02985 (9)	0.071 (1)
C17	−0.0186 (4)	0.1288 (4)	0.07000 (8)	0.055 (1)
C18	0.2314 (4)	0.2961 (5)	0.0673 (1)	0.073 (1)
C19	0.1862 (5)	0.7187 (5)	0.1339 (2)	0.096 (2)
C20	0.0000 (4)	0.0049 (4)	0.07446 (9)	0.0558 (9)
C21	0.0013 (4)	−0.0240 (4)	0.1147 (1)	0.0540 (9)
C22	−0.1113 (4)	−0.1222 (4)	0.0556 (9)	0.060 (1)
C23	−0.0908 (5)	−0.2444 (5)	0.0581 (1)	0.081 (1)
C24	−0.1921 (5)	−0.3640 (5)	0.0363 (1)	0.084 (1)
C25	−0.3025 (5)	−0.4710 (5)	0.0477 (1)	0.087 (1)
C26	−0.3459 (7)	−0.4949 (8)	0.0861 (2)	0.158 (3)
C27	−0.3944 (4)	−0.5847 (4)	0.0220 (1)	0.138 (2)
C28	0.4098 (4)	1.0248 (4)	0.1010 (1)	0.108 (2)
C29	0.5555 (5)	0.9971 (5)	0.0555 (1)	0.098 (2)
C30	−0.0832 (4)	0.3475 (5)	0.0833 (1)	0.085 (1)
H1	0.7163	0.9197	0.1208	0.175*
H2	0.1110	−0.0100	0.1499	0.100*
H1A	0.3595	0.6841	0.1711	0.090*
H1B	0.4603	0.6861	0.1417	0.090*
H2A	0.4488	0.9178	0.1650	0.106*
H2B	0.5677	0.8898	0.1738	0.106*
H3	0.6321	1.0472	0.1265	0.095*
H5	0.4278	0.7479	0.0756	0.069*
H6A	0.2196	0.8039	0.0603	0.096*
H6B	0.3193	0.7973	0.0320	0.096*
H7	0.1207	0.5857	0.0279	0.090*
H9	0.3191	0.5410	0.0997	0.071*
H11A	0.2387	0.4579	0.1548	0.082*
H11B	0.1006	0.4516	0.1471	0.082*
H12A	0.0209	0.2411	0.1357	0.079*
H12B	0.1660	0.2576	0.1342	0.079*
H15A	0.1016	0.3555	0.0127	0.092*
H15B	−0.0457	0.3350	0.0163	0.092*
H16A	0.0067	0.1305	0.0132	0.085*
H16B	−0.1357	0.1123	0.0238	0.085*
H17	−0.1010	0.1089	0.0834	0.066*
H18A	0.2566	0.2352	0.0782	0.109*
H18B	0.3003	0.3881	0.0722	0.109*
H18C	0.2222	0.2815	0.0415	0.109*
H19A	0.1196	0.6987	0.1152	0.144*
H19B	0.2240	0.8115	0.1414	0.144*
H19C	0.1440	0.6599	0.1543	0.144*
H20	0.0879	0.0266	0.0640	0.067*
H22A	−0.1982	−0.1457	0.0664	0.072*
H22B	−0.1146	−0.1016	0.0301	0.072*
H23A	−0.0001	−0.2181	0.0497	0.097*
H23B	−0.0973	−0.2712	0.0834	0.097*
H24	−0.1740	−0.3616	0.0115	0.101*
H26A	−0.4299	−0.5793	0.0881	0.236*
H26B	−0.3585	−0.4221	0.0946	0.236*
H26C	−0.2777	−0.4989	0.1005	0.236*
H27A	−0.4701	−0.6537	0.0353	0.207*
H27B	−0.3443	−0.6230	0.0111	0.207*
H27C	−0.4269	−0.5492	0.0033	0.207*
H28A	0.3479	1.0175	0.0822	0.162*
H28B	0.4798	1.1179	0.1035	0.162*
H28C	0.3615	0.9931	0.1236	0.162*
H29A	0.4952	0.9906	0.0363	0.146*
H29B	0.5995	0.9469	0.0488	0.146*
H29C	0.6227	1.0906	0.0593	0.146*
H30A	−0.1546	0.2553	0.0800	0.128*
H30B	−0.1075	0.4075	0.0714	0.128*
H30C	−0.0699	0.3684	0.1088	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.065 (2)	0.174 (4)	0.110 (3)	0.058 (2)	−0.017 (2)	−0.020 (2)
O2	0.060 (2)	0.095 (2)	0.054 (1)	0.046 (2)	−0.004 (1)	0.001 (1)
O3	0.052 (2)	0.095 (2)	0.047 (1)	0.029 (2)	−0.001 (1)	0.006 (1)
C1	0.075 (3)	0.081 (3)	0.055 (2)	0.028 (3)	−0.007 (2)	−0.008 (2)
C2	0.087 (3)	0.088 (4)	0.064 (3)	0.024 (3)	−0.010 (3)	−0.011 (3)
C3	0.055 (3)	0.085 (3)	0.075 (3)	0.020 (3)	0.001 (2)	−0.013 (3)
C4	0.048 (2)	0.067 (3)	0.072 (3)	0.019 (2)	0.001 (2)	0.000 (2)
C5	0.044 (2)	0.062 (2)	0.061 (2)	0.023 (2)	−0.007 (2)	0.001 (2)
C6	0.061 (3)	0.070 (3)	0.090 (3)	0.017 (2)	−0.022 (2)	0.014 (2)
C7	0.059 (3)	0.074 (3)	0.066 (3)	0.014 (2)	−0.025 (2)	0.006 (2)
C8	0.042 (2)	0.063 (3)	0.053 (2)	0.018 (2)	−0.0055 (17)	0.013 (2)
C9	0.064 (2)	0.063 (3)	0.047 (2)	0.029 (2)	−0.009 (2)	0.007 (2)
C10	0.046 (2)	0.065 (3)	0.058 (2)	0.026 (2)	−0.002 (2)	−0.004 (2)
C11	0.081 (3)	0.070 (3)	0.038 (2)	0.026 (2)	−0.002 (2)	0.000 (2)
C12	0.081 (3)	0.066 (3)	0.043 (2)	0.030 (2)	−0.009 (2)	0.001 (2)
C13	0.046 (2)	0.066 (2)	0.036 (2)	0.024 (2)	0.001 (2)	0.003 (2)
C14	0.043 (2)	0.063 (3)	0.045 (2)	0.017 (2)	−0.007 (2)	0.004 (2)
C15	0.083 (3)	0.074 (3)	0.052 (2)	0.023 (3)	−0.020 (2)	0.008 (2)
C16	0.072 (3)	0.077 (3)	0.048 (2)	0.025 (2)	−0.014 (2)	−0.002 (2)
C17	0.050 (2)	0.062 (3)	0.044 (2)	0.022 (2)	−0.000 (2)	0.004 (2)
C18	0.048 (3)	0.077 (3)	0.082 (3)	0.023 (2)	0.002 (2)	−0.005 (2)
C19	0.071 (3)	0.076 (3)	0.136 (4)	0.034 (3)	0.029 (3)	0.014 (3)
C20	0.052 (2)	0.072 (3)	0.042 (2)	0.031 (2)	0.003 (2)	−0.000 (2)
C21	0.053 (3)	0.063 (3)	0.052 (2)	0.034 (2)	−0.001 (2)	−0.001 (2)
C22	0.067 (3)	0.069 (3)	0.042 (2)	0.032 (2)	−0.004 (2)	−0.004 (2)
C23	0.079 (3)	0.075 (3)	0.088 (3)	0.038 (3)	0.000 (3)	−0.004 (3)
C24	0.099 (4)	0.075 (3)	0.071 (3)	0.038 (3)	0.003 (3)	−0.013 (3)
C25	0.088 (4)	0.082 (3)	0.087 (3)	0.038 (3)	0.003 (3)	0.000 (3)
C26	0.127 (5)	0.173 (7)	0.107 (5)	0.026 (5)	0.044 (4)	0.024 (4)
C27	0.125 (5)	0.087 (4)	0.178 (6)	0.035 (4)	−0.026 (4)	−0.042 (4)
C28	0.085 (4)	0.059 (3)	0.167 (5)	0.026 (3)	0.009 (3)	0.006 (3)
C29	0.066 (3)	0.087 (3)	0.087 (3)	−0.001 (3)	−0.004 (3)	0.012 (3)
C30	0.052 (3)	0.074 (3)	0.123 (4)	0.026 (2)	−0.005 (3)	0.006 (3)

Geometric parameters (Å, º)

O1—C3	1.392 (6)	C10—C19	1.539 (6)
O2—C21	1.296 (4)	C11—C12	1.515 (5)
O3—C21	1.223 (4)	C12—C13	1.538 (5)
C1—C2	1.528 (6)	C13—C18	1.535 (5)
C1—C10	1.536 (5)	C13—C14	1.552 (5)
C2—C3	1.514 (6)	C13—C17	1.554 (5)
C3—C4	1.529 (6)	C14—C15	1.530 (5)
C4—C28	1.539 (6)	C14—C30	1.551 (6)
C4—C29	1.542 (6)	C15—C16	1.539 (6)
C4—C5	1.551 (5)	C16—C17	1.563 (4)
C5—C6	1.529 (5)	C17—C20	1.535 (5)
C5—C10	1.553 (5)	C20—C21	1.516 (5)
C6—C7	1.486 (6)	C20—C22	1.53 (2)
C7—C8	1.353 (5)	C22—C23	1.522 (6)
C8—C9	1.499 (5)	C23—C24	1.502 (6)
C8—C14	1.513 (5)	C24—C25	1.305 (6)
C9—C11	1.523 (5)	C25—C26	1.474 (6)
C9—C10	1.539 (5)	C25—C27	1.518 (6)
C2—C1—C10	113.9 (4)	C18—C13—C12	109.6 (3)
C3—C2—C1	111.0 (3)	C18—C13—C14	111.5 (3)
O1—C3—C2	111.0 (4)	C12—C13—C14	108.6 (3)
O1—C3—C4	107.2 (3)	C18—C13—C17	108.7 (3)
C2—C3—C4	112.7 (4)	C12—C13—C17	116.7 (3)
C3—C4—C28	109.0 (3)	C14—C13—C17	101.5 (3)
C3—C4—C29	108.4 (3)	C8—C14—C15	117.5 (3)
C28—C4—C29	107.4 (4)	C8—C14—C30	106.5 (3)
C3—C4—C5	108.0 (3)	C15—C14—C30	107.6 (3)
C28—C4—C5	115.2 (3)	C8—C14—C13	110.7 (3)
C29—C4—C5	108.7 (3)	C15—C14—C13	101.5 (3)
C6—C5—C4	112.9 (3)	C30—C14—C13	113.2 (3)
C6—C5—C10	111.0 (3)	C14—C15—C16	105.3 (3)
C4—C5—C10	118.1 (3)	C15—C16—C17	106.7 (3)
C7—C6—C5	112.5 (3)	C20—C17—C13	119.1 (3)
C8—C7—C6	124.2 (3)	C20—C17—C16	114.5 (3)
C7—C8—C9	120.5 (3)	C13—C17—C16	102.1 (3)
C7—C8—C14	121.8 (3)	C21—C20—C22	109 (3)
C9—C8—C14	117.6 (3)	C21—C20—C17	108.9 (3)
C8—C9—C11	112.8 (3)	C22—C20—C17	112.9 (3)
C8—C9—C10	114.4 (3)	O3—C21—O2	122.4 (3)
C11—C9—C10	116.3 (3)	O3—C21—C20	122.0 (3)
C1—C10—C19	109.8 (3)	O2—C21—C20	115.6 (3)
C1—C10—C9	108.9 (3)	C23—C22—C20	114 (1)
C19—C10—C9	109.6 (3)	C24—C23—C22	113.4 (9)
C1—C10—C5	108.9 (3)	C25—C24—C23	128.1 (4)
C19—C10—C5	113.3 (4)	C24—C25—C26	123.8 (5)
C9—C10—C5	106.2 (3)	C24—C25—C27	121.7 (4)
C12—C11—C9	117.4 (3)	C26—C25—C27	114.4 (5)
C11—C12—C13	114.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.82	2.08	2.825 (4)	151
O2—H2···O3^ii	0.82	1.91	2.666 (3)	153

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