Crystal structure of betulinic acid methanol monosolvate.

The title compound [systematic name: 3β-hy-droxy-lup-20(29)-en-28-oic acid methanol monosolvate], C30H48O3·CH3OH, is a solvent pseudopolymorph of a naturally occurring plant-derived lupane-type penta-cyclic triterpenoid, which was isolated from the traditional Chinese medicinal plant Syzygium jambos (L.) Alston. The dihedral angle between the planes of the carb-oxy-lic acid group and the olefinic group is 12.17 (18)°. The A/B, B/C, C/D and D/E ring junctions are all trans-fused. In the crystal, O-H⋯O hydrogen bonds involving the hy-droxy and carb-oxy-lic acid groups and the methanol solvent mol-ecule give rise to a two-dimensional network structure lying parallel to (001).

Related literature

For general background to the synthesis, extraction and pharmceutical activities of the title compound, see: Kashiwada et al. (1996 ▶); Fulda et al. (1999 ▶); Liu et al. (2009 ▶); Safe et al. (2012 ▶); Babalola et al. (2013 ▶); Heidary Navid et al. (2014 ▶); Yadav & Gupta (2014 ▶). For the structure of another methanol solvate of betulinic acid, see: Wang et al. (2014 ▶).

Experimental

Crystal data

C30H48O3·CH4O

M = 488.73

Orthorhombic,

a = 7.0988 (2) Å

b = 12.3864 (3) Å

c = 33.2745 (9) Å

V = 2925.78 (13) Å3

Z = 4

Cu Kα radiation

μ = 0.55 mm−1

T = 293 K

0.28 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini S Ultra CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.748, T max = 1.000

8319 measured reflections

4343 independent reflections

3796 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.112

S = 1.05

4343 reflections

326 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814023848/zs2317sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023848/zs2317Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S1600536814023848/zs2317fig1.tif

The mol­ecular structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.

CCDC reference: 1031558

Additional supporting information: crystallographic information; 3D view; checkCIF report

C30H48O3·CH4O	Dx = 1.110 Mg m−3
Mr = 488.73	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 3107 reflections
a = 7.0988 (2) Å	θ = 3.8–62.4°
b = 12.3864 (3) Å	µ = 0.55 mm−1
c = 33.2745 (9) Å	T = 293 K
V = 2925.78 (13) Å3	Block, colourless
Z = 4	0.28 × 0.25 × 0.20 mm
F(000) = 1080

Oxford Diffraction Gemini S Ultra CCD-detector diffractometer	4343 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray source	3796 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 16.0288 pixels mm-1	θmax = 62.8°, θmin = 3.8°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −14→14
Tmin = 0.748, Tmax = 1.000	l = −38→30
8319 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0489P)2 + 0.2568P] where P = (Fo2 + 2Fc2)/3
4343 reflections	(Δ/σ)max < 0.001
326 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
C1	0.8725 (3)	0.2245 (2)	0.29320 (7)	0.0558 (5)
H1A	1.0010	0.2303	0.2836	0.067*
H1B	0.8028	0.2859	0.2828	0.067*
C2	0.8736 (4)	0.2301 (2)	0.33899 (8)	0.0599 (6)
H2A	0.9553	0.1741	0.3495	0.072*
H2B	0.9236	0.2994	0.3474	0.072*
C3	0.6797 (3)	0.21606 (19)	0.35581 (7)	0.0529 (5)
H3	0.6016	0.2751	0.3455	0.063*
C4	0.5845 (3)	0.10912 (18)	0.34382 (7)	0.0473 (5)
C5	0.5903 (3)	0.10297 (16)	0.29712 (7)	0.0418 (4)
H5	0.5147	0.1648	0.2883	0.050*
C6	0.4890 (3)	0.00515 (18)	0.27942 (7)	0.0495 (5)
H6A	0.5679	−0.0583	0.2822	0.059*
H6B	0.3730	−0.0076	0.2941	0.059*
C7	0.4445 (3)	0.02402 (17)	0.23522 (7)	0.0489 (5)
H7A	0.3558	0.0833	0.2331	0.059*
H7B	0.3836	−0.0399	0.2245	0.059*
C8	0.6183 (3)	0.04992 (15)	0.20917 (7)	0.0427 (4)
C9	0.7414 (3)	0.13761 (16)	0.23044 (6)	0.0423 (4)
H9	0.6640	0.2031	0.2297	0.051*
C10	0.7845 (3)	0.11993 (17)	0.27634 (7)	0.0438 (5)
C11	0.9151 (3)	0.1655 (2)	0.20478 (7)	0.0563 (6)
H11A	0.9845	0.2234	0.2177	0.068*
H11B	0.9971	0.1030	0.2035	0.068*
C12	0.8635 (3)	0.2003 (2)	0.16204 (7)	0.0543 (5)
H12A	0.8006	0.2698	0.1630	0.065*
H12B	0.9779	0.2089	0.1464	0.065*
C13	0.7357 (3)	0.11911 (17)	0.14128 (7)	0.0458 (5)
H13	0.8056	0.0509	0.1402	0.055*
C14	0.5543 (3)	0.09684 (16)	0.16666 (7)	0.0424 (4)
C15	0.4247 (3)	0.01587 (18)	0.14456 (7)	0.0519 (5)
H15A	0.4808	−0.0554	0.1464	0.062*
H15B	0.3048	0.0133	0.1585	0.062*
C16	0.3869 (3)	0.0408 (2)	0.10007 (8)	0.0564 (5)
H16A	0.3162	−0.0180	0.0881	0.068*
H16B	0.3122	0.1061	0.0979	0.068*
C17	0.5722 (3)	0.05540 (19)	0.07771 (7)	0.0523 (5)
C18	0.6821 (3)	0.14719 (17)	0.09793 (7)	0.0479 (5)
H18	0.5934	0.2076	0.0999	0.057*
C19	0.8349 (3)	0.1842 (2)	0.06760 (7)	0.0553 (5)
H19	0.9505	0.1429	0.0724	0.066*
C20	0.8807 (4)	0.3028 (2)	0.06820 (8)	0.0686 (7)
C21	0.7510 (4)	0.1508 (2)	0.02599 (8)	0.0705 (7)
H21A	0.7358	0.2137	0.0090	0.085*
H21B	0.8343	0.1002	0.0126	0.085*
C22	0.5582 (4)	0.0977 (2)	0.03415 (8)	0.0651 (6)
H22A	0.5354	0.0389	0.0155	0.078*
H22B	0.4573	0.1501	0.0316	0.078*
C23	0.3767 (3)	0.1168 (2)	0.35735 (8)	0.0648 (6)
H23A	0.3143	0.1724	0.3423	0.097*
H23B	0.3716	0.1338	0.3855	0.097*
H23C	0.3152	0.0490	0.3527	0.097*
C24	0.6753 (4)	0.0131 (2)	0.36544 (8)	0.0646 (6)
H24A	0.6265	−0.0530	0.3546	0.097*
H24B	0.6470	0.0168	0.3936	0.097*
H24C	0.8094	0.0154	0.3617	0.097*
C25	0.9274 (3)	0.0275 (2)	0.28368 (8)	0.0589 (6)
H25A	0.9862	0.0372	0.3094	0.088*
H25B	1.0217	0.0286	0.2630	0.088*
H25C	0.8628	−0.0405	0.2832	0.088*
C26	0.7285 (4)	−0.05744 (18)	0.20362 (8)	0.0577 (6)
H26A	0.6720	−0.0987	0.1824	0.087*
H26B	0.7244	−0.0982	0.2282	0.087*
H26C	0.8571	−0.0418	0.1969	0.087*
C27	0.4397 (3)	0.20241 (17)	0.17149 (7)	0.0496 (5)
H27A	0.3419	0.1917	0.1910	0.074*
H27B	0.3845	0.2217	0.1461	0.074*
H27C	0.5217	0.2593	0.1803	0.074*
C28	0.6745 (4)	−0.0533 (2)	0.07527 (7)	0.0577 (6)
C29	1.0572 (6)	0.3352 (3)	0.07162 (10)	0.0984 (12)
H29A	1.0859	0.4083	0.0703	0.118*
H29B	1.1527	0.2848	0.0754	0.118*
C30	0.7208 (7)	0.3804 (3)	0.06214 (16)	0.1213 (16)
H30A	0.6549	0.3625	0.0378	0.182*
H30B	0.7693	0.4526	0.0602	0.182*
H30C	0.6358	0.3758	0.0845	0.182*
C31	0.9582 (9)	−0.3072 (4)	0.0316 (2)	0.154 (2)
H31A	0.8962	−0.2769	0.0086	0.232*
H31B	0.8714	−0.3521	0.0461	0.232*
H31C	1.0637	−0.3498	0.0230	0.232*
O1	0.6889 (3)	0.22739 (17)	0.39892 (5)	0.0708 (5)
H1	0.5933	0.2576	0.4070	0.106*
O2	0.5943 (3)	−0.13820 (15)	0.07479 (8)	0.0919 (7)
O3	0.8560 (3)	−0.04848 (17)	0.07166 (10)	0.0961 (8)
H3A	0.8982	−0.1095	0.0683	0.144*
O4	1.0176 (5)	−0.2288 (2)	0.05516 (11)	0.1310 (12)
H4	1.1022	−0.2514	0.0697	0.197*

	U11	U22	U33	U12	U13	U23
C1	0.0482 (11)	0.0607 (13)	0.0586 (12)	−0.0167 (11)	0.0012 (11)	−0.0014 (11)
C2	0.0538 (12)	0.0635 (14)	0.0624 (13)	−0.0131 (11)	−0.0032 (12)	−0.0061 (12)
C3	0.0494 (11)	0.0542 (12)	0.0551 (12)	0.0044 (10)	−0.0024 (10)	−0.0023 (10)
C4	0.0382 (10)	0.0501 (11)	0.0536 (11)	0.0031 (9)	0.0006 (10)	0.0055 (10)
C5	0.0333 (9)	0.0362 (9)	0.0558 (11)	0.0030 (8)	−0.0002 (9)	0.0064 (9)
C6	0.0418 (10)	0.0434 (10)	0.0633 (13)	−0.0080 (9)	0.0052 (10)	0.0061 (10)
C7	0.0391 (9)	0.0451 (11)	0.0624 (12)	−0.0124 (9)	0.0012 (10)	0.0008 (10)
C8	0.0339 (9)	0.0364 (9)	0.0577 (12)	0.0011 (8)	0.0019 (9)	−0.0014 (9)
C9	0.0308 (9)	0.0417 (10)	0.0544 (11)	−0.0009 (8)	−0.0008 (9)	0.0001 (9)
C10	0.0313 (9)	0.0450 (10)	0.0552 (11)	0.0001 (9)	0.0003 (9)	0.0018 (9)
C11	0.0365 (10)	0.0771 (15)	0.0554 (12)	−0.0146 (11)	0.0012 (10)	0.0001 (12)
C12	0.0413 (10)	0.0671 (14)	0.0545 (12)	−0.0157 (10)	0.0043 (10)	0.0011 (11)
C13	0.0360 (9)	0.0471 (10)	0.0543 (11)	0.0006 (9)	0.0025 (9)	−0.0007 (10)
C14	0.0334 (8)	0.0382 (9)	0.0554 (11)	−0.0008 (8)	0.0023 (9)	0.0001 (9)
C15	0.0421 (10)	0.0515 (11)	0.0621 (13)	−0.0098 (9)	−0.0009 (10)	−0.0032 (11)
C16	0.0453 (11)	0.0591 (12)	0.0649 (13)	−0.0047 (10)	−0.0115 (11)	−0.0046 (11)
C17	0.0506 (11)	0.0522 (11)	0.0540 (12)	−0.0008 (10)	−0.0075 (10)	0.0000 (10)
C18	0.0441 (10)	0.0452 (11)	0.0543 (12)	−0.0007 (9)	0.0005 (10)	0.0002 (10)
C19	0.0563 (12)	0.0568 (12)	0.0528 (12)	−0.0060 (11)	0.0053 (11)	−0.0016 (11)
C20	0.0894 (19)	0.0612 (14)	0.0554 (13)	−0.0172 (15)	0.0160 (14)	−0.0033 (12)
C21	0.0819 (17)	0.0765 (16)	0.0532 (13)	−0.0124 (15)	0.0004 (14)	0.0000 (13)
C22	0.0743 (15)	0.0646 (14)	0.0564 (13)	−0.0050 (13)	−0.0122 (13)	0.0033 (12)
C23	0.0435 (11)	0.0870 (17)	0.0638 (14)	0.0008 (12)	0.0080 (11)	0.0005 (14)
C24	0.0694 (15)	0.0607 (14)	0.0638 (14)	0.0060 (12)	−0.0038 (13)	0.0145 (12)
C25	0.0409 (10)	0.0737 (15)	0.0621 (13)	0.0179 (11)	−0.0013 (11)	0.0006 (12)
C26	0.0615 (13)	0.0457 (11)	0.0659 (13)	0.0131 (11)	−0.0074 (12)	−0.0047 (11)
C27	0.0421 (10)	0.0464 (11)	0.0602 (12)	0.0072 (9)	0.0012 (10)	0.0027 (10)
C28	0.0654 (14)	0.0521 (13)	0.0555 (12)	−0.0026 (12)	0.0008 (11)	−0.0065 (11)
C29	0.127 (3)	0.100 (2)	0.0679 (17)	−0.058 (2)	−0.011 (2)	0.0139 (17)
C30	0.139 (3)	0.0624 (17)	0.162 (4)	0.013 (2)	0.058 (3)	0.019 (2)
C31	0.161 (5)	0.122 (4)	0.180 (5)	0.010 (4)	−0.045 (5)	−0.058 (4)
O1	0.0632 (10)	0.0922 (13)	0.0571 (9)	0.0064 (10)	0.0017 (8)	−0.0142 (9)
O2	0.1020 (15)	0.0548 (10)	0.1188 (17)	−0.0123 (11)	0.0369 (15)	−0.0120 (11)
O3	0.0664 (11)	0.0634 (10)	0.159 (2)	0.0099 (9)	−0.0085 (14)	−0.0236 (14)
O4	0.135 (2)	0.1133 (19)	0.144 (2)	0.0652 (18)	−0.068 (2)	−0.0608 (19)

C1—C2	1.525 (3)	C16—H16B	0.9700
C1—C10	1.544 (3)	C17—C28	1.532 (3)
C1—H1A	0.9700	C17—C18	1.534 (3)
C1—H1B	0.9700	C17—C22	1.544 (4)
C2—C3	1.496 (3)	C18—C19	1.551 (3)
C2—H2A	0.9700	C18—H18	0.9800
C2—H2B	0.9700	C19—C20	1.505 (4)
C3—O1	1.443 (3)	C19—C21	1.563 (4)
C3—C4	1.540 (3)	C19—H19	0.9800
C3—H3	0.9800	C20—C29	1.320 (5)
C4—C24	1.532 (3)	C20—C30	1.501 (5)
C4—C23	1.545 (3)	C21—C22	1.542 (4)
C4—C5	1.556 (3)	C21—H21A	0.9700
C5—C6	1.527 (3)	C21—H21B	0.9700
C5—C10	1.557 (3)	C22—H22A	0.9700
C5—H5	0.9800	C22—H22B	0.9700
C6—C7	1.522 (3)	C23—H23A	0.9600
C6—H6A	0.9700	C23—H23B	0.9600
C6—H6B	0.9700	C23—H23C	0.9600
C7—C8	1.542 (3)	C24—H24A	0.9600
C7—H7A	0.9700	C24—H24B	0.9600
C7—H7B	0.9700	C24—H24C	0.9600
C8—C26	1.554 (3)	C25—H25A	0.9600
C8—C9	1.563 (3)	C25—H25B	0.9600
C8—C14	1.595 (3)	C25—H25C	0.9600
C9—C11	1.539 (3)	C26—H26A	0.9600
C9—C10	1.573 (3)	C26—H26B	0.9600
C9—H9	0.9800	C26—H26C	0.9600
C10—C25	1.549 (3)	C27—H27A	0.9600
C11—C12	1.531 (3)	C27—H27B	0.9600
C11—H11A	0.9700	C27—H27C	0.9600
C11—H11B	0.9700	C28—O2	1.196 (3)
C12—C13	1.521 (3)	C28—O3	1.295 (3)
C12—H12A	0.9700	C29—H29A	0.9300
C12—H12B	0.9700	C29—H29B	0.9300
C13—C18	1.532 (3)	C30—H30A	0.9600
C13—C14	1.564 (3)	C30—H30B	0.9600
C13—H13	0.9800	C30—H30C	0.9600
C14—C15	1.547 (3)	C31—O4	1.317 (6)
C14—C27	1.548 (3)	C31—H31A	0.9600
C15—C16	1.536 (4)	C31—H31B	0.9600
C15—H15A	0.9700	C31—H31C	0.9600
C15—H15B	0.9700	O1—H1	0.8200
C16—C17	1.522 (3)	O3—H3A	0.8200
C16—H16A	0.9700	O4—H4	0.8200
C2—C1—C10	113.8 (2)	C17—C16—C15	110.12 (18)
C2—C1—H1A	108.8	C17—C16—H16A	109.6
C10—C1—H1A	108.8	C15—C16—H16A	109.6
C2—C1—H1B	108.8	C17—C16—H16B	109.6
C10—C1—H1B	108.8	C15—C16—H16B	109.6
H1A—C1—H1B	107.7	H16A—C16—H16B	108.2
C3—C2—C1	111.3 (2)	C16—C17—C28	109.31 (19)
C3—C2—H2A	109.4	C16—C17—C18	108.26 (19)
C1—C2—H2A	109.4	C28—C17—C18	115.70 (19)
C3—C2—H2B	109.4	C16—C17—C22	116.3 (2)
C1—C2—H2B	109.4	C28—C17—C22	106.2 (2)
H2A—C2—H2B	108.0	C18—C17—C22	101.12 (19)
O1—C3—C2	108.62 (19)	C13—C18—C17	111.77 (18)
O1—C3—C4	111.2 (2)	C13—C18—C19	120.43 (18)
C2—C3—C4	114.0 (2)	C17—C18—C19	106.80 (18)
O1—C3—H3	107.6	C13—C18—H18	105.6
C2—C3—H3	107.6	C17—C18—H18	105.6
C4—C3—H3	107.6	C19—C18—H18	105.6
C24—C4—C3	111.19 (19)	C20—C19—C18	115.5 (2)
C24—C4—C23	108.2 (2)	C20—C19—C21	110.7 (2)
C3—C4—C23	106.88 (19)	C18—C19—C21	103.41 (19)
C24—C4—C5	114.82 (19)	C20—C19—H19	109.0
C3—C4—C5	106.82 (18)	C18—C19—H19	109.0
C23—C4—C5	108.60 (18)	C21—C19—H19	109.0
C6—C5—C4	114.31 (18)	C29—C20—C30	122.4 (3)
C6—C5—C10	110.66 (17)	C29—C20—C19	120.2 (3)
C4—C5—C10	117.39 (17)	C30—C20—C19	117.4 (3)
C6—C5—H5	104.3	C22—C21—C19	107.2 (2)
C4—C5—H5	104.3	C22—C21—H21A	110.3
C10—C5—H5	104.3	C19—C21—H21A	110.3
C7—C6—C5	110.40 (18)	C22—C21—H21B	110.3
C7—C6—H6A	109.6	C19—C21—H21B	110.3
C5—C6—H6A	109.6	H21A—C21—H21B	108.5
C7—C6—H6B	109.6	C21—C22—C17	104.6 (2)
C5—C6—H6B	109.6	C21—C22—H22A	110.8
H6A—C6—H6B	108.1	C17—C22—H22A	110.8
C6—C7—C8	114.14 (18)	C21—C22—H22B	110.8
C6—C7—H7A	108.7	C17—C22—H22B	110.8
C8—C7—H7A	108.7	H22A—C22—H22B	108.9
C6—C7—H7B	108.7	C4—C23—H23A	109.5
C8—C7—H7B	108.7	C4—C23—H23B	109.5
H7A—C7—H7B	107.6	H23A—C23—H23B	109.5
C7—C8—C26	106.96 (18)	C4—C23—H23C	109.5
C7—C8—C9	109.73 (17)	H23A—C23—H23C	109.5
C26—C8—C9	111.53 (16)	H23B—C23—H23C	109.5
C7—C8—C14	110.27 (16)	C4—C24—H24A	109.5
C26—C8—C14	110.46 (18)	C4—C24—H24B	109.5
C9—C8—C14	107.91 (15)	H24A—C24—H24B	109.5
C11—C9—C8	110.68 (18)	C4—C24—H24C	109.5
C11—C9—C10	114.46 (16)	H24A—C24—H24C	109.5
C8—C9—C10	116.83 (17)	H24B—C24—H24C	109.5
C11—C9—H9	104.4	C10—C25—H25A	109.5
C8—C9—H9	104.4	C10—C25—H25B	109.5
C10—C9—H9	104.4	H25A—C25—H25B	109.5
C1—C10—C25	107.34 (18)	C10—C25—H25C	109.5
C1—C10—C5	108.07 (18)	H25A—C25—H25C	109.5
C25—C10—C5	114.23 (18)	H25B—C25—H25C	109.5
C1—C10—C9	108.34 (17)	C8—C26—H26A	109.5
C25—C10—C9	112.54 (18)	C8—C26—H26B	109.5
C5—C10—C9	106.13 (16)	H26A—C26—H26B	109.5
C12—C11—C9	112.75 (18)	C8—C26—H26C	109.5
C12—C11—H11A	109.0	H26A—C26—H26C	109.5
C9—C11—H11A	109.0	H26B—C26—H26C	109.5
C12—C11—H11B	109.0	C14—C27—H27A	109.5
C9—C11—H11B	109.0	C14—C27—H27B	109.5
H11A—C11—H11B	107.8	H27A—C27—H27B	109.5
C13—C12—C11	112.25 (19)	C14—C27—H27C	109.5
C13—C12—H12A	109.2	H27A—C27—H27C	109.5
C11—C12—H12A	109.2	H27B—C27—H27C	109.5
C13—C12—H12B	109.2	O2—C28—O3	120.8 (3)
C11—C12—H12B	109.2	O2—C28—C17	123.2 (2)
H12A—C12—H12B	107.9	O3—C28—C17	115.8 (2)
C12—C13—C18	115.19 (18)	C20—C29—H29A	120.0
C12—C13—C14	111.25 (18)	C20—C29—H29B	120.0
C18—C13—C14	110.13 (17)	H29A—C29—H29B	120.0
C12—C13—H13	106.6	C20—C30—H30A	109.5
C18—C13—H13	106.6	C20—C30—H30B	109.5
C14—C13—H13	106.6	H30A—C30—H30B	109.5
C15—C14—C27	106.52 (17)	C20—C30—H30C	109.5
C15—C14—C13	110.32 (17)	H30A—C30—H30C	109.5
C27—C14—C13	109.85 (16)	H30B—C30—H30C	109.5
C15—C14—C8	110.77 (16)	O4—C31—H31A	109.5
C27—C14—C8	111.42 (17)	O4—C31—H31B	109.5
C13—C14—C8	107.97 (15)	H31A—C31—H31B	109.5
C16—C15—C14	115.59 (19)	O4—C31—H31C	109.5
C16—C15—H15A	108.4	H31A—C31—H31C	109.5
C14—C15—H15A	108.4	H31B—C31—H31C	109.5
C16—C15—H15B	108.4	C3—O1—H1	109.5
C14—C15—H15B	108.4	C28—O3—H3A	109.5
H15A—C15—H15B	107.4	C31—O4—H4	109.5
C10—C1—C2—C3	−55.7 (3)	C18—C13—C14—C27	−67.3 (2)
C1—C2—C3—O1	−177.2 (2)	C12—C13—C14—C8	−60.0 (2)
C1—C2—C3—C4	58.2 (3)	C18—C13—C14—C8	171.05 (17)
O1—C3—C4—C24	−51.5 (2)	C7—C8—C14—C15	−57.9 (2)
C2—C3—C4—C24	71.7 (3)	C26—C8—C14—C15	60.2 (2)
O1—C3—C4—C23	66.4 (2)	C9—C8—C14—C15	−177.70 (16)
C2—C3—C4—C23	−170.4 (2)	C7—C8—C14—C27	60.5 (2)
O1—C3—C4—C5	−177.52 (17)	C26—C8—C14—C27	178.54 (17)
C2—C3—C4—C5	−54.3 (2)	C9—C8—C14—C27	−59.3 (2)
C24—C4—C5—C6	60.3 (2)	C7—C8—C14—C13	−178.75 (16)
C3—C4—C5—C6	−175.89 (17)	C26—C8—C14—C13	−60.7 (2)
C23—C4—C5—C6	−60.9 (2)	C9—C8—C14—C13	61.41 (19)
C24—C4—C5—C10	−71.7 (2)	C27—C14—C15—C16	70.8 (2)
C3—C4—C5—C10	52.0 (2)	C13—C14—C15—C16	−48.4 (2)
C23—C4—C5—C10	166.98 (19)	C8—C14—C15—C16	−167.85 (18)
C4—C5—C6—C7	161.11 (17)	C14—C15—C16—C17	53.2 (3)
C10—C5—C6—C7	−63.7 (2)	C15—C16—C17—C28	68.7 (2)
C5—C6—C7—C8	56.8 (2)	C15—C16—C17—C18	−58.1 (2)
C6—C7—C8—C26	74.0 (2)	C15—C16—C17—C22	−171.1 (2)
C6—C7—C8—C9	−47.1 (2)	C12—C13—C18—C17	173.50 (19)
C6—C7—C8—C14	−165.83 (17)	C14—C13—C18—C17	−59.7 (2)
C7—C8—C9—C11	−179.51 (18)	C12—C13—C18—C19	47.0 (3)
C26—C8—C9—C11	62.2 (2)	C14—C13—C18—C19	173.75 (18)
C14—C8—C9—C11	−59.3 (2)	C16—C17—C18—C13	63.8 (2)
C7—C8—C9—C10	47.1 (2)	C28—C17—C18—C13	−59.2 (3)
C26—C8—C9—C10	−71.2 (2)	C22—C17—C18—C13	−173.45 (19)
C14—C8—C9—C10	167.28 (16)	C16—C17—C18—C19	−162.52 (18)
C2—C1—C10—C25	−73.5 (3)	C28—C17—C18—C19	74.4 (2)
C2—C1—C10—C5	50.1 (3)	C22—C17—C18—C19	−39.8 (2)
C2—C1—C10—C9	164.69 (19)	C13—C18—C19—C20	−85.4 (3)
C6—C5—C10—C1	175.72 (18)	C17—C18—C19—C20	145.8 (2)
C4—C5—C10—C1	−50.6 (2)	C13—C18—C19—C21	153.6 (2)
C6—C5—C10—C25	−64.9 (2)	C17—C18—C19—C21	24.8 (2)
C4—C5—C10—C25	68.8 (2)	C18—C19—C20—C29	128.0 (3)
C6—C5—C10—C9	59.7 (2)	C21—C19—C20—C29	−114.9 (3)
C4—C5—C10—C9	−166.61 (17)	C18—C19—C20—C30	−55.8 (4)
C11—C9—C10—C1	59.3 (2)	C21—C19—C20—C30	61.3 (4)
C8—C9—C10—C1	−169.06 (17)	C20—C19—C21—C22	−124.1 (2)
C11—C9—C10—C25	−59.3 (2)	C18—C19—C21—C22	0.2 (3)
C8—C9—C10—C25	72.4 (2)	C19—C21—C22—C17	−24.6 (3)
C11—C9—C10—C5	175.12 (18)	C16—C17—C22—C21	155.9 (2)
C8—C9—C10—C5	−53.2 (2)	C28—C17—C22—C21	−82.2 (2)
C8—C9—C11—C12	55.0 (3)	C18—C17—C22—C21	38.9 (3)
C10—C9—C11—C12	−170.47 (19)	C16—C17—C28—O2	28.9 (3)
C9—C11—C12—C13	−52.4 (3)	C18—C17—C28—O2	151.4 (3)
C11—C12—C13—C18	−178.50 (19)	C22—C17—C28—O2	−97.3 (3)
C11—C12—C13—C14	55.3 (3)	C16—C17—C28—O3	−154.5 (3)
C12—C13—C14—C15	178.84 (18)	C18—C17—C28—O3	−32.0 (4)
C18—C13—C14—C15	49.9 (2)	C22—C17—C28—O3	79.3 (3)
C12—C13—C14—C27	61.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4	0.82	1.76	2.571 (3)	170
O1—H1···O2i	0.82	1.95	2.753 (3)	165
O4—H4···O1ii	0.82	1.83	2.640 (3)	168

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O3H3AO4	0.82	1.76	2.571(3)	170
O1H1O2i	0.82	1.95	2.753(3)	165
O4H4O1ii	0.82	1.83	2.640(3)	168

Symmetry codes: (i) ; (ii) .