Carb-oxy-methyl ursolate monohydrate.

In the title compound, C(28)H(50)O(5)·H(2)O, all of the six-membered rings of the penta-cyclic triterpene skeleton adopt chair conformations. In the crystal, mol-ecules are linked by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For the synthesis, see: Wen et al. (2006 ▶). The crystal structure of ursolic acid is known from its ethanol solvate, see: Simon et al. (1992 ▶). For methyl uroslate-3-bromo­acetate, see: Stout & Stevens (1963 ▶). For methyl ursolate-3-p-bromo­benzoate, see: Paton & Paul (1979 ▶). For background to ursolic acid derivatives and their biological activity, see: Es-saady et al. (1996 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C32H50O5·H2O

M = 532.74

Monoclinic,

a = 13.338 (3) Å

b = 8.1010 (16) Å

c = 14.311 (3) Å

β = 106.26 (3)°

V = 1484.5 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.976, T max = 0.992

5692 measured reflections

5446 independent reflections

4536 reflections with I > 2σ(I)

R int = 0.025

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.134

S = 1.00

5446 reflections

350 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994) ▶; cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001619/hb5787sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001619/hb5787Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C32H50O5·H2O	F(000) = 584
Mr = 532.74	Dx = 1.192 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 13.338 (3) Å	θ = 9–13°
b = 8.1010 (16) Å	µ = 0.08 mm−1
c = 14.311 (3) Å	T = 293 K
β = 106.26 (3)°	Block, colorless
V = 1484.5 (5) Å3	0.30 × 0.20 × 0.10 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	4536 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
graphite	θmax = 25.4°, θmin = 1.5°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
Tmin = 0.976, Tmax = 0.992	l = −17→16
5692 measured reflections	3 standard reflections every 200 reflections
5446 independent reflections	intensity decay: 1%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.094P)2] where P = (Fo2 + 2Fc2)/3
5446 reflections	(Δ/σ)max < 0.001
350 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.85435 (16)	0.1230 (3)	0.65587 (19)	0.0785 (7)
H1A	0.8627	0.0229	0.6621	0.118*
C1	0.7706 (2)	0.1725 (3)	0.6936 (2)	0.0484 (6)
H1B	0.7911	0.1490	0.7636	0.058*
C2	0.6748 (2)	0.0714 (3)	0.64682 (19)	0.0456 (6)
H2A	0.6903	−0.0447	0.6601	0.055*
H2B	0.6557	0.0871	0.5769	0.055*
O2	0.16556 (16)	0.8730 (2)	0.72389 (16)	0.0640 (6)
O3	0.09919 (14)	0.6206 (2)	0.68621 (12)	0.0547 (5)
C3	0.58375 (18)	0.1207 (3)	0.68505 (18)	0.0401 (5)
H3A	0.6009	0.0951	0.7539	0.048*
H3B	0.5231	0.0557	0.6521	0.048*
C4	0.55611 (17)	0.3049 (3)	0.67043 (15)	0.0359 (5)
O4	−0.07654 (15)	0.8025 (2)	0.65381 (14)	0.0564 (5)
C5	0.65734 (17)	0.4056 (3)	0.71361 (16)	0.0343 (5)
H5A	0.6771	0.3794	0.7832	0.041*
O5	−0.10926 (14)	0.7942 (3)	0.49516 (14)	0.0579 (5)
H5B	−0.0879	0.7665	0.4467	0.069*
C6	0.75574 (19)	0.3587 (3)	0.68039 (18)	0.0425 (6)
C7	0.48023 (17)	0.3472 (3)	0.73329 (16)	0.0343 (5)
H7A	0.5160	0.3067	0.7987	0.041*
C9	0.56111 (19)	0.6301 (3)	0.77258 (17)	0.0404 (5)
H9A	0.5449	0.7470	0.7669	0.048*
H9B	0.5987	0.6085	0.8399	0.048*
C10	0.6324 (2)	0.5904 (3)	0.70921 (18)	0.0424 (6)
H10A	0.6968	0.6529	0.7316	0.051*
H10B	0.5987	0.6221	0.6425	0.051*
C11	0.3777 (2)	0.2509 (3)	0.7033 (2)	0.0544 (7)
H11A	0.3494	0.2572	0.6332	0.065*
H11B	0.3920	0.1357	0.7204	0.065*
C12	0.29722 (17)	0.3121 (3)	0.74972 (17)	0.0420 (5)
H12A	0.2350	0.2531	0.7364	0.050*
C13	0.30539 (16)	0.4407 (3)	0.80729 (15)	0.0330 (5)
C14	0.40501 (17)	0.5457 (3)	0.83295 (15)	0.0326 (5)
C15	0.45858 (18)	0.5331 (3)	0.74771 (16)	0.0353 (5)
C16	0.21627 (17)	0.4787 (3)	0.85160 (16)	0.0350 (5)
H16A	0.1534	0.4292	0.8080	0.042*
C17	0.19584 (18)	0.6672 (3)	0.85059 (17)	0.0373 (5)
C18	0.29810 (19)	0.7566 (3)	0.90141 (18)	0.0416 (5)
H18A	0.2845	0.8739	0.9037	0.050*
H18B	0.3234	0.7172	0.9679	0.050*
C19	0.38151 (19)	0.7295 (3)	0.84990 (17)	0.0390 (5)
H19A	0.4456	0.7814	0.8878	0.047*
H19B	0.3602	0.7847	0.7873	0.047*
C20	0.1086 (2)	0.7089 (3)	0.89839 (19)	0.0486 (6)
H20A	0.1045	0.8278	0.9044	0.058*
H20B	0.0423	0.6708	0.8564	0.058*
C21	0.1263 (2)	0.6317 (4)	0.99763 (19)	0.0533 (7)
H21A	0.0679	0.6580	1.0229	0.064*
H21B	0.1889	0.6780	1.0417	0.064*
C22	0.1377 (2)	0.4456 (3)	0.99400 (18)	0.0480 (6)
H22A	0.0736	0.4010	0.9498	0.058*
C23	0.22925 (19)	0.4004 (3)	0.95339 (17)	0.0411 (5)
H23A	0.2937	0.4431	0.9981	0.049*
C24	0.8518 (2)	0.4416 (4)	0.7495 (2)	0.0584 (7)
H24A	0.8526	0.4201	0.8157	0.088*
H24B	0.8486	0.5585	0.7381	0.088*
H24C	0.9141	0.3979	0.7378	0.088*
C25	0.7499 (3)	0.4133 (4)	0.5764 (2)	0.0605 (7)
H25A	0.8161	0.3942	0.5640	0.091*
H25B	0.7333	0.5288	0.5692	0.091*
H25C	0.6967	0.3512	0.5310	0.091*
C26	0.5071 (2)	0.3335 (4)	0.56091 (17)	0.0514 (7)
H26A	0.5437	0.2691	0.5247	0.077*
H26B	0.5120	0.4484	0.5463	0.077*
H26C	0.4350	0.3010	0.5434	0.077*
C27	0.3843 (2)	0.6049 (4)	0.65303 (17)	0.0512 (6)
H27A	0.4132	0.5853	0.5996	0.077*
H27B	0.3765	0.7215	0.6606	0.077*
H27C	0.3173	0.5522	0.6402	0.077*
C28	0.47549 (17)	0.4806 (3)	0.93108 (16)	0.0402 (5)
H28A	0.4440	0.5058	0.9821	0.060*
H28B	0.5428	0.5323	0.9449	0.060*
H28C	0.4833	0.3632	0.9272	0.060*
C29	0.2394 (3)	0.2128 (4)	0.9468 (2)	0.0610 (8)
H29A	0.2534	0.1656	1.0107	0.092*
H29B	0.2957	0.1871	0.9197	0.092*
H29C	0.1755	0.1681	0.9059	0.092*
C30	0.1508 (3)	0.3706 (4)	1.0951 (2)	0.0671 (8)
H30A	0.0986	0.4151	1.1225	0.101*
H30B	0.2189	0.3967	1.1365	0.101*
H30C	0.1429	0.2529	1.0894	0.101*
C31	0.15463 (19)	0.7326 (3)	0.74804 (19)	0.0441 (6)
C32	0.0496 (2)	0.6730 (4)	0.58938 (19)	0.0587 (8)
H32A	0.0359	0.5778	0.5466	0.070*
H32B	0.0960	0.7464	0.5676	0.070*
C33	−0.0518 (2)	0.7612 (3)	0.58279 (19)	0.0435 (6)
OW	−0.04995 (14)	0.6584 (3)	0.35682 (15)	0.0641 (6)
HWB	−0.0315	0.5578	0.3656	0.077*
HWA	0.0065	0.6702	0.3393	0.077*

	U11	U22	U33	U12	U13	U23
O1	0.0566 (12)	0.0473 (12)	0.149 (2)	0.0031 (10)	0.0575 (14)	−0.0128 (13)
C1	0.0439 (14)	0.0373 (13)	0.0673 (16)	0.0051 (11)	0.0211 (13)	−0.0026 (12)
C2	0.0506 (15)	0.0300 (12)	0.0590 (15)	0.0019 (11)	0.0198 (12)	−0.0073 (11)
O2	0.0589 (12)	0.0472 (11)	0.0797 (14)	0.0059 (9)	0.0092 (10)	0.0249 (10)
O3	0.0641 (12)	0.0464 (10)	0.0434 (9)	0.0193 (9)	−0.0018 (8)	0.0006 (8)
C3	0.0411 (12)	0.0271 (11)	0.0542 (13)	−0.0019 (10)	0.0168 (11)	−0.0084 (10)
C4	0.0370 (11)	0.0288 (11)	0.0405 (12)	0.0031 (10)	0.0084 (9)	−0.0033 (10)
O4	0.0618 (12)	0.0465 (10)	0.0634 (12)	0.0084 (10)	0.0216 (9)	−0.0023 (9)
C5	0.0372 (12)	0.0294 (11)	0.0362 (11)	−0.0002 (9)	0.0101 (9)	0.0005 (9)
O5	0.0508 (10)	0.0576 (12)	0.0575 (11)	0.0168 (10)	0.0024 (8)	0.0007 (9)
C6	0.0440 (13)	0.0324 (12)	0.0562 (15)	−0.0022 (10)	0.0222 (12)	−0.0042 (11)
C7	0.0353 (12)	0.0282 (12)	0.0380 (11)	−0.0007 (9)	0.0077 (9)	−0.0044 (9)
C9	0.0486 (13)	0.0246 (11)	0.0507 (13)	−0.0019 (10)	0.0183 (11)	−0.0061 (10)
C10	0.0492 (14)	0.0270 (12)	0.0527 (14)	−0.0007 (10)	0.0169 (11)	0.0021 (10)
C11	0.0432 (14)	0.0457 (15)	0.0740 (19)	−0.0102 (12)	0.0158 (13)	−0.0316 (14)
C12	0.0306 (11)	0.0400 (12)	0.0520 (13)	−0.0038 (10)	0.0056 (10)	−0.0125 (11)
C13	0.0327 (11)	0.0267 (10)	0.0354 (11)	0.0058 (9)	0.0026 (9)	0.0019 (9)
C14	0.0335 (11)	0.0267 (11)	0.0344 (11)	0.0019 (9)	0.0041 (9)	−0.0036 (9)
C15	0.0386 (12)	0.0287 (11)	0.0354 (11)	0.0042 (9)	0.0051 (10)	−0.0009 (9)
C16	0.0325 (11)	0.0284 (11)	0.0397 (12)	0.0027 (9)	0.0027 (9)	−0.0004 (9)
C17	0.0379 (12)	0.0262 (11)	0.0471 (13)	0.0069 (9)	0.0110 (10)	0.0008 (9)
C18	0.0464 (13)	0.0275 (11)	0.0488 (13)	0.0016 (10)	0.0101 (11)	−0.0074 (10)
C19	0.0429 (13)	0.0281 (12)	0.0448 (13)	−0.0030 (10)	0.0102 (10)	−0.0089 (10)
C20	0.0476 (15)	0.0393 (14)	0.0612 (16)	0.0113 (11)	0.0191 (12)	−0.0049 (12)
C21	0.0541 (15)	0.0531 (16)	0.0594 (16)	0.0007 (13)	0.0268 (13)	−0.0073 (13)
C22	0.0497 (14)	0.0460 (15)	0.0488 (14)	−0.0057 (12)	0.0144 (11)	−0.0037 (12)
C23	0.0424 (13)	0.0363 (13)	0.0416 (13)	−0.0011 (10)	0.0068 (10)	−0.0003 (10)
C24	0.0451 (14)	0.0475 (15)	0.084 (2)	−0.0076 (12)	0.0208 (14)	−0.0105 (15)
C25	0.0755 (19)	0.0542 (17)	0.0652 (18)	−0.0055 (15)	0.0418 (16)	−0.0010 (14)
C26	0.0559 (16)	0.0558 (17)	0.0403 (13)	0.0059 (13)	0.0101 (11)	−0.0091 (12)
C27	0.0602 (16)	0.0487 (15)	0.0409 (13)	0.0173 (13)	0.0080 (11)	0.0033 (11)
C28	0.0357 (11)	0.0447 (14)	0.0363 (12)	0.0013 (10)	0.0036 (9)	−0.0010 (10)
C29	0.074 (2)	0.0428 (16)	0.0670 (18)	0.0079 (14)	0.0207 (16)	0.0121 (13)
C30	0.078 (2)	0.068 (2)	0.0618 (18)	−0.0087 (16)	0.0303 (16)	0.0056 (14)
C31	0.0369 (13)	0.0399 (14)	0.0553 (14)	0.0104 (11)	0.0127 (11)	0.0045 (12)
C32	0.0658 (18)	0.0592 (18)	0.0459 (14)	0.0277 (15)	0.0073 (13)	0.0019 (12)
C33	0.0465 (13)	0.0279 (12)	0.0528 (15)	0.0019 (10)	0.0086 (12)	0.0017 (10)
OW	0.0455 (10)	0.0595 (13)	0.0849 (14)	0.0056 (9)	0.0141 (10)	−0.0206 (11)

O1—C1	1.427 (3)	C16—H16A	0.9800
O1—H1A	0.8200	C17—C31	1.512 (3)
C1—C2	1.508 (4)	C17—C18	1.536 (3)
C1—C6	1.526 (3)	C17—C20	1.543 (3)
C1—H1B	0.9800	C18—C19	1.513 (3)
C2—C3	1.518 (3)	C18—H18A	0.9700
C2—H2A	0.9700	C18—H18B	0.9700
C2—H2B	0.9700	C19—H19A	0.9700
O2—C31	1.209 (3)	C19—H19B	0.9700
O3—C31	1.337 (3)	C20—C21	1.509 (4)
O3—C32	1.423 (3)	C20—H20A	0.9700
C3—C4	1.537 (3)	C20—H20B	0.9700
C3—H3A	0.9700	C21—C22	1.517 (4)
C3—H3B	0.9700	C21—H21A	0.9700
C4—C26	1.538 (3)	C21—H21B	0.9700
C4—C5	1.551 (3)	C22—C30	1.533 (4)
C4—C7	1.569 (3)	C22—C23	1.536 (3)
O4—C33	1.201 (3)	C22—H22A	0.9800
C5—C10	1.531 (3)	C23—C29	1.531 (4)
C5—C6	1.563 (3)	C23—H23A	0.9800
C5—H5A	0.9800	C24—H24A	0.9600
O5—C33	1.301 (3)	C24—H24B	0.9600
O5—H5B	0.8500	C24—H24C	0.9600
C6—C25	1.533 (4)	C25—H25A	0.9600
C6—C24	1.536 (4)	C25—H25B	0.9600
C7—C11	1.528 (3)	C25—H25C	0.9600
C7—C15	1.558 (3)	C26—H26A	0.9600
C7—H7A	0.9800	C26—H26B	0.9600
C9—C10	1.521 (3)	C26—H26C	0.9600
C9—C15	1.530 (3)	C27—H27A	0.9600
C9—H9A	0.9700	C27—H27B	0.9600
C9—H9B	0.9700	C27—H27C	0.9600
C10—H10A	0.9700	C28—H28A	0.9600
C10—H10B	0.9700	C28—H28B	0.9600
C11—C12	1.496 (4)	C28—H28C	0.9600
C11—H11A	0.9700	C29—H29A	0.9600
C11—H11B	0.9700	C29—H29B	0.9600
C12—C13	1.314 (3)	C29—H29C	0.9600
C12—H12A	0.9300	C30—H30A	0.9600
C13—C16	1.527 (3)	C30—H30B	0.9600
C13—C14	1.533 (3)	C30—H30C	0.9600
C14—C28	1.548 (3)	C32—C33	1.508 (4)
C14—C19	1.555 (3)	C32—H32A	0.9700
C14—C15	1.580 (3)	C32—H32B	0.9700
C15—C27	1.550 (3)	OW—HWB	0.8500
C16—C17	1.550 (3)	OW—HWA	0.8634
C16—C23	1.553 (3)
C1—O1—H1A	109.5	C20—C17—C16	111.3 (2)
O1—C1—C2	109.6 (2)	C19—C18—C17	112.19 (18)
O1—C1—C6	108.6 (2)	C19—C18—H18A	109.2
C2—C1—C6	114.7 (2)	C17—C18—H18A	109.2
O1—C1—H1B	107.9	C19—C18—H18B	109.2
C2—C1—H1B	107.9	C17—C18—H18B	109.2
C6—C1—H1B	107.9	H18A—C18—H18B	107.9
C1—C2—C3	111.17 (19)	C18—C19—C14	115.02 (19)
C1—C2—H2A	109.4	C18—C19—H19A	108.5
C3—C2—H2A	109.4	C14—C19—H19A	108.5
C1—C2—H2B	109.4	C18—C19—H19B	108.5
C3—C2—H2B	109.4	C14—C19—H19B	108.5
H2A—C2—H2B	108.0	H19A—C19—H19B	107.5
C31—O3—C32	117.5 (2)	C21—C20—C17	112.9 (2)
C2—C3—C4	113.07 (19)	C21—C20—H20A	109.0
C2—C3—H3A	109.0	C17—C20—H20A	109.0
C4—C3—H3A	109.0	C21—C20—H20B	109.0
C2—C3—H3B	109.0	C17—C20—H20B	109.0
C4—C3—H3B	109.0	H20A—C20—H20B	107.8
H3A—C3—H3B	107.8	C20—C21—C22	111.7 (2)
C3—C4—C26	107.61 (19)	C20—C21—H21A	109.3
C3—C4—C5	107.93 (18)	C22—C21—H21A	109.3
C26—C4—C5	113.6 (2)	C20—C21—H21B	109.3
C3—C4—C7	107.62 (18)	C22—C21—H21B	109.3
C26—C4—C7	113.15 (18)	H21A—C21—H21B	107.9
C5—C4—C7	106.63 (17)	C21—C22—C30	110.3 (2)
C10—C5—C4	110.11 (19)	C21—C22—C23	110.4 (2)
C10—C5—C6	114.61 (19)	C30—C22—C23	111.7 (2)
C4—C5—C6	117.54 (18)	C21—C22—H22A	108.1
C10—C5—H5A	104.3	C30—C22—H22A	108.1
C4—C5—H5A	104.3	C23—C22—H22A	108.1
C6—C5—H5A	104.3	C29—C23—C22	110.7 (2)
C33—O5—H5B	119.3	C29—C23—C16	109.6 (2)
C1—C6—C25	112.0 (2)	C22—C23—C16	111.4 (2)
C1—C6—C24	107.2 (2)	C29—C23—H23A	108.3
C25—C6—C24	107.8 (2)	C22—C23—H23A	108.3
C1—C6—C5	107.09 (19)	C16—C23—H23A	108.3
C25—C6—C5	114.0 (2)	C6—C24—H24A	109.5
C24—C6—C5	108.5 (2)	C6—C24—H24B	109.5
C11—C7—C15	110.25 (19)	H24A—C24—H24B	109.5
C11—C7—C4	113.45 (18)	C6—C24—H24C	109.5
C15—C7—C4	117.41 (18)	H24A—C24—H24C	109.5
C11—C7—H7A	104.8	H24B—C24—H24C	109.5
C15—C7—H7A	104.8	C6—C25—H25A	109.5
C4—C7—H7A	104.8	C6—C25—H25B	109.5
C10—C9—C15	114.85 (19)	H25A—C25—H25B	109.5
C10—C9—H9A	108.6	C6—C25—H25C	109.5
C15—C9—H9A	108.6	H25A—C25—H25C	109.5
C10—C9—H9B	108.6	H25B—C25—H25C	109.5
C15—C9—H9B	108.6	C4—C26—H26A	109.5
H9A—C9—H9B	107.5	C4—C26—H26B	109.5
C9—C10—C5	110.30 (19)	H26A—C26—H26B	109.5
C9—C10—H10A	109.6	C4—C26—H26C	109.5
C5—C10—H10A	109.6	H26A—C26—H26C	109.5
C9—C10—H10B	109.6	H26B—C26—H26C	109.5
C5—C10—H10B	109.6	C15—C27—H27A	109.5
H10A—C10—H10B	108.1	C15—C27—H27B	109.5
C12—C11—C7	113.78 (19)	H27A—C27—H27B	109.5
C12—C11—H11A	108.8	C15—C27—H27C	109.5
C7—C11—H11A	108.8	H27A—C27—H27C	109.5
C12—C11—H11B	108.8	H27B—C27—H27C	109.5
C7—C11—H11B	108.8	C14—C28—H28A	109.5
H11A—C11—H11B	107.7	C14—C28—H28B	109.5
C13—C12—C11	126.7 (2)	H28A—C28—H28B	109.5
C13—C12—H12A	116.7	C14—C28—H28C	109.5
C11—C12—H12A	116.7	H28A—C28—H28C	109.5
C12—C13—C16	118.9 (2)	H28B—C28—H28C	109.5
C12—C13—C14	120.3 (2)	C23—C29—H29A	109.5
C16—C13—C14	120.80 (18)	C23—C29—H29B	109.5
C13—C14—C28	107.08 (18)	H29A—C29—H29B	109.5
C13—C14—C19	111.68 (18)	C23—C29—H29C	109.5
C28—C14—C19	106.42 (18)	H29A—C29—H29C	109.5
C13—C14—C15	109.16 (17)	H29B—C29—H29C	109.5
C28—C14—C15	112.80 (17)	C22—C30—H30A	109.5
C19—C14—C15	109.69 (17)	C22—C30—H30B	109.5
C9—C15—C27	108.7 (2)	H30A—C30—H30B	109.5
C9—C15—C7	109.91 (18)	C22—C30—H30C	109.5
C27—C15—C7	110.09 (19)	H30A—C30—H30C	109.5
C9—C15—C14	110.80 (18)	H30B—C30—H30C	109.5
C27—C15—C14	109.52 (18)	O2—C31—O3	122.5 (2)
C7—C15—C14	107.78 (17)	O2—C31—C17	124.6 (3)
C13—C16—C17	110.48 (19)	O3—C31—C17	112.8 (2)
C13—C16—C23	114.31 (18)	O3—C32—C33	111.5 (2)
C17—C16—C23	112.59 (19)	O3—C32—H32A	109.3
C13—C16—H16A	106.3	C33—C32—H32A	109.3
C17—C16—H16A	106.3	O3—C32—H32B	109.3
C23—C16—H16A	106.3	C33—C32—H32B	109.3
C31—C17—C18	109.12 (19)	H32A—C32—H32B	108.0
C31—C17—C20	103.84 (19)	O4—C33—O5	122.0 (2)
C18—C17—C20	111.50 (19)	O4—C33—C32	122.2 (2)
C31—C17—C16	111.69 (19)	O5—C33—C32	115.7 (2)
C18—C17—C16	109.25 (18)	HWB—OW—HWA	84.8
O1—C1—C2—C3	−179.9 (2)	C4—C7—C15—C14	−165.94 (16)
C6—C1—C2—C3	−57.5 (3)	C13—C14—C15—C9	−177.45 (18)
C1—C2—C3—C4	57.0 (3)	C28—C14—C15—C9	−58.5 (2)
C2—C3—C4—C26	70.6 (3)	C19—C14—C15—C9	59.9 (2)
C2—C3—C4—C5	−52.4 (2)	C13—C14—C15—C27	62.6 (2)
C2—C3—C4—C7	−167.17 (19)	C28—C14—C15—C27	−178.5 (2)
C3—C4—C5—C10	−174.95 (18)	C19—C14—C15—C27	−60.1 (2)
C26—C4—C5—C10	65.8 (2)	C13—C14—C15—C7	−57.2 (2)
C7—C4—C5—C10	−59.6 (2)	C28—C14—C15—C7	61.7 (2)
C3—C4—C5—C6	51.3 (3)	C19—C14—C15—C7	−179.83 (18)
C26—C4—C5—C6	−67.9 (3)	C12—C13—C16—C17	−139.4 (2)
C7—C4—C5—C6	166.72 (18)	C14—C13—C16—C17	43.4 (3)
O1—C1—C6—C25	49.3 (3)	C12—C13—C16—C23	92.4 (3)
C2—C1—C6—C25	−73.7 (3)	C14—C13—C16—C23	−84.8 (2)
O1—C1—C6—C24	−68.8 (3)	C13—C16—C17—C31	66.4 (2)
C2—C1—C6—C24	168.3 (2)	C23—C16—C17—C31	−164.42 (19)
O1—C1—C6—C5	174.9 (2)	C13—C16—C17—C18	−54.4 (2)
C2—C1—C6—C5	52.0 (3)	C23—C16—C17—C18	74.8 (2)
C10—C5—C6—C1	177.7 (2)	C13—C16—C17—C20	−177.98 (18)
C4—C5—C6—C1	−50.6 (3)	C23—C16—C17—C20	−48.8 (3)
C10—C5—C6—C25	−57.8 (3)	C31—C17—C18—C19	−60.7 (2)
C4—C5—C6—C25	73.9 (3)	C20—C17—C18—C19	−174.8 (2)
C10—C5—C6—C24	62.3 (3)	C16—C17—C18—C19	61.7 (2)
C4—C5—C6—C24	−166.0 (2)	C17—C18—C19—C14	−53.9 (3)
C3—C4—C7—C11	−61.6 (2)	C13—C14—C19—C18	37.8 (3)
C26—C4—C7—C11	57.2 (3)	C28—C14—C19—C18	−78.7 (2)
C5—C4—C7—C11	−177.2 (2)	C15—C14—C19—C18	158.94 (18)
C3—C4—C7—C15	167.87 (19)	C31—C17—C20—C21	171.4 (2)
C26—C4—C7—C15	−73.4 (3)	C18—C17—C20—C21	−71.2 (3)
C5—C4—C7—C15	52.3 (2)	C16—C17—C20—C21	51.1 (3)
C15—C9—C10—C5	−56.6 (3)	C17—C20—C21—C22	−56.5 (3)
C4—C5—C10—C9	63.7 (2)	C20—C21—C22—C30	−177.6 (2)
C6—C5—C10—C9	−161.1 (2)	C20—C21—C22—C23	58.5 (3)
C15—C7—C11—C12	−35.2 (3)	C21—C22—C23—C29	−178.4 (2)
C4—C7—C11—C12	−169.2 (2)	C30—C22—C23—C29	58.4 (3)
C7—C11—C12—C13	3.6 (4)	C21—C22—C23—C16	−56.1 (3)
C11—C12—C13—C16	−177.1 (2)	C30—C22—C23—C16	−179.3 (2)
C11—C12—C13—C14	0.2 (4)	C13—C16—C23—C29	−57.9 (3)
C12—C13—C14—C28	−95.1 (2)	C17—C16—C23—C29	175.0 (2)
C16—C13—C14—C28	82.1 (2)	C13—C16—C23—C22	179.22 (19)
C12—C13—C14—C19	148.8 (2)	C17—C16—C23—C22	52.1 (3)
C16—C13—C14—C19	−34.0 (3)	C32—O3—C31—O2	−1.8 (4)
C12—C13—C14—C15	27.3 (3)	C32—O3—C31—C17	175.0 (2)
C16—C13—C14—C15	−155.50 (18)	C18—C17—C31—O2	−32.5 (3)
C10—C9—C15—C27	−74.9 (2)	C20—C17—C31—O2	86.5 (3)
C10—C9—C15—C7	45.6 (3)	C16—C17—C31—O2	−153.4 (2)
C10—C9—C15—C14	164.66 (18)	C18—C17—C31—O3	150.77 (19)
C11—C7—C15—C9	−177.09 (19)	C20—C17—C31—O3	−90.2 (2)
C4—C7—C15—C9	−45.1 (3)	C16—C17—C31—O3	29.9 (3)
C11—C7—C15—C27	−57.3 (3)	C31—O3—C32—C33	−81.0 (3)
C4—C7—C15—C27	74.7 (2)	O3—C32—C33—O4	10.7 (4)
C11—C7—C15—C14	62.1 (2)	O3—C32—C33—O5	−171.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
OW—HWB···O2i	0.85	2.41	2.839 (3)	112
OW—HWB···O4i	0.85	2.58	3.365 (3)	154
O1—H1A···O4ii	0.82	1.98	2.758 (3)	159
OW—HWA···O1iii	0.86	1.88	2.681 (3)	154
O5—H5B···OW	0.85	1.74	2.575 (3)	165
C12—H12A···OWi	0.93	2.57	3.455 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW—HWB⋯O2i	0.85	2.41	2.839 (3)	112
OW—HWB⋯O4i	0.85	2.58	3.365 (3)	154
O1—H1A⋯O4ii	0.82	1.98	2.758 (3)	159
OW—HWA⋯O1iii	0.86	1.88	2.681 (3)	154
O5—H5B⋯OW	0.85	1.74	2.575 (3)	165
C12—H12A⋯OWi	0.93	2.57	3.455 (3)	159

Symmetry codes: (i) ; (ii) ; (iii) .