Carb­oxy­methyl ursolate monohydrate

Zhong, Y.; Dai, Z.H.; Teng, Y.B.; Wu, B.; Zhou, J.P.

doi:10.1107/S1600536811001619

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o428

doi:10.1107/S1600536811001619

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Carboxymethyl ursolate monohydrate

Yan Zhong,^a,^b ZhaoHui Dai,^c YanBo Teng,^c Bin Wu ^c and JianPing Zhou ^a ^*

^aSchool of Pharmacy, China Pharmaceutical University, Tongjiaxiang No. 24 Nanjing, Nanjing 210009, People's Republic of China, ^bSchool of Chemistry and Chemical Engineering, Southeast University, Sipailou No. 2 Nanjing, Nanjing 210096, People's Republic of China, and ^cSchool of Pharmacy, Nanjing Medical University, Hanzhong Road No.140 Nanjing, Nanjing 210029, People's Republic of China
^*Correspondence e-mail: wjy090202@yahoo.com.cn

(Received 1 January 2011; accepted 11 January 2011; online 15 January 2011)

In the title compound, C₂₈H₅₀O₅·H₂O, all of the six-membered rings of the pentacyclic triterpene skeleton adopt chair conformations. In the crystal, molecules 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_r = 532.74
Monoclinic, P 2₁
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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.134
S = 1.00
5446 reflections
350 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y-1, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

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.

Supporting information

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

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

checkCIF report

Related literature top

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 top

To a solution of ursolic acid (5.0 g, 11 mmol) in DMF (125 ml) were added ethyl chloroacetate (1.17 ml, 11 mmol) and K2CO3 (4.5 g, 33 mmol). The reaction mixture was stirred at room temperature for 5 h, then filtered and concentrated to give ethoxycarbonylmethyl ursolate as a yellow oil, which is pure enough for the next step. The ester was dissolved in MeOH (50 ml), THF (75 ml) and 4 N NaOH (30 ml). The mixture was stirred at room temperature for 18 h. After solvent evaporation under reduced pressure, H2O (90 ml) was added. The mixture was acidified with 4 N HCl until the pH was adjusted to 3.0 and the product was extracted with CHCl₃ (75 ml). The organic layer was separated and dried in Na₂SO₄. Filtration and concentration under reduce pressure provided carboxymethyl ursolate as a white powder. The colorless block of the title compound used in x-ray diffraction studies were grown in a mixture of ethyl acetate and hexane by a slow evaporation at room temperature.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994; 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 70% probability level.
	Fig. 2. A packing diagram of (I).

Carboxymethyl ursolate monohydrate top

Crystal data top

C₃₂H₅₀O₅·H₂O	F(000) = 584
M_r = 532.74	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.094P)²] where P = (F_o² + 2F_c²)/3
5446 reflections	(Δ/σ)_max < 0.001
350 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃₂H₅₀O₅·H₂O	V = 1484.5 (5) Å³
M_r = 532.74	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 13.338 (3) Å	µ = 0.08 mm⁻¹
b = 8.1010 (16) Å	T = 293 K
c = 14.311 (3) Å	0.30 × 0.20 × 0.10 mm
β = 106.26 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	4536 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.025
T_min = 0.976, T_max = 0.992	3 standard reflections every 200 reflections
5692 measured reflections	intensity decay: 1%
5446 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.134	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
5446 reflections	Δρ_min = −0.23 e Å⁻³
350 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x, y−1/2, −z+1; (ii) x+1, y−1, z; (iii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₂H₅₀O₅·H₂O
M_r	532.74
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	13.338 (3), 8.1010 (16), 14.311 (3)
β (°)	106.26 (3)
V (Å³)	1484.5 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.976, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	5692, 5446, 4536
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.134, 1.00
No. of reflections	5446
No. of parameters	350
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS (Enraf–Nonius, 1994, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x, y−1/2, −z+1; (ii) x+1, y−1, z; (iii) −x+1, y+1/2, −z+1.

Acknowledgements

The authors acknowledge support from the Natural Science Fundation of Jiangsu Province (No. BK2010538). The authors also thank Professor Hua-Qin Wang of the Analysis Centre, Nanjing University, for collecting the crystallographic data.

References

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