12β,14-Dihy­droxy-3-oxo-5β,20(22)-cardenolide monohydrate

He, C.-J.; Wang, M.; Sun, H.; Liu, Z.; Fu, Y.

doi:10.1107/S1600536810038031

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2704

https://doi.org/10.1107/S1600536810038031

Open

access

12β,14-Dihydroxy-3-oxo-5β,20(22)-cardenolide monohydrate

Chao-Jun He,^a Min Wang,^a ^* Hua Sun,^a Zeng-bing Liu ^a and Yu-wan Fu ^a

^aCollege of Biotechnology, Tianjin University of Science and Technology, Tianjin 300457, People's Republic of China
^*Correspondence e-mail: minw@tust.edu.cn

(Received 2 August 2010; accepted 23 September 2010; online 2 October 2010)

The title compound, digoxigenone, C₂₃H₃₀O₅·H₂O, was biotransformed from digoxigenin. In the crystal, intermolecular O—H⋯O hydrogen bonds contribute to the formation of a three-dimensional supramolecular structure. The title compound has three fused six-membered rings (A,B,C) and two non-fused five-membered rings (D,E). As in other structures, compound nucleus has a cis-trans-cis conformation for the A-B,B-C,C-D ring junctions with rings A, B and C exhibiting chair conformations.

Related literature

Digitoxin and digoxin, the typical clinically used forms (Kreis et al., 1998 ), are the drugs of choice for the treatment of congestive heart failure, acting as selective inhibitors of the Na+, K+ ATPase enzyme. For the biotransformation of digitoxigenin into digoxigenin and digoxigenone by Fusarium ciliatum and into 1 β-hydroxydigitoxigenin, 7-β-hydroxydigitoxigenin, 8-β-hydroxidigitoxigenin and digitoxigenone by Cochliobolus lunatus, see: Pádua et al. (2005 , 2007 ).

Experimental

Crystal data

C₂₃H₃₀O₅·H₂O
M_r = 404.49
Triclinic, P 1
a = 7.4017 (15) Å
b = 7.7450 (15) Å
c = 10.215 (2) Å
α = 99.51 (3)°
β = 94.70 (3)°
γ = 114.97 (3)°
V = 516.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.32 × 0.26 × 0.20 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.971, T_max = 0.982
5251 measured reflections
1809 independent reflections
1443 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.082
S = 1.00
1809 reflections
275 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6ⁱ	0.82	1.99	2.808 (3)	173
O3—H3⋯O2ⁱⁱ	0.82	2.10	2.900 (3)	164
O6—H1W⋯O1ⁱⁱⁱ	0.86 (1)	1.94 (1)	2.801 (3)	174 (4)
O6—H2W⋯O5^iv	0.86 (1)	1.91 (2)	2.741 (4)	162 (5)
Symmetry codes: (i) x-1, y, z-1; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) x, y-1, z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 global, I. DOI: https://doi.org/10.1107/S1600536810038031/hg2696sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038031/hg2696Isup2.hkl

checkCIF report

Comment top

Digitoxin and digoxin, the typical clinically used forms (Kreis et al., 1998), are the drugs of choice for the treatment of congestive heart failure, acting as selective inhibitors of the Na+, K+ ATPase enzyme. Digitoxigenin has been biotransformed into digoxigenin and digoxigenone by Fusarium ciliatum and into 1 beta-hydroxydigitoxigenin, 7 beta-hydroxydigitoxigenin, 8 beta-hydroxidigitoxigenin, and digitoxigenone by Cochliobolus lunatus (Pádua et al., 2005; Pádua et al., 2007). In this paper, we studied the biotransformation of digoxigenin by Arthrobacter simplex and reported crystal structure of the compound digoxigenone.

The crystal structure is shown in Fig. 1. The crystal structure consists of an digoxigenone molecule and one water molecule. Compound digoxigenone has three fused six-membered rings (A/B/C) and two non-fused five-membered rings (D/E). As in other structures the A, B and C rings have a chair conformation. The 12-hydroxy is beta configuration with the torsion angles C9—C11—C12—O2 = -179.6 (2)°. The 14-hydroxy is beta configuration with the torsion angles C7—C8—C14—O3 = -64.4 (3)°. The orientation of the lactone ring is determined by the torsion angle C(13)—C(17)—C(20)—C(22) = -113.1 (3)°.

In the crystal packing (Fig. 2), X-ray analysis indicates that there were three types of intermolecular hydrogen bonds contributed to the formation of three-dimensional supramolecular structure: between solvent water molecule and carbonyl of adjacent digoxigenone molecule, hydroxyl of digoxigenone molecule and hydroxyl of adjacent digoxigenone molecule, and hydroxyl of digoxigenone molecule and solvent water molecule. The hydrogen bonding parameters are O(6)—H(6 A)···O(1)#3, 2.800 (3), 173.7; O(6)—H(6B)···O(5)#4, 2.742 (3), 160.3; O(2)—H(2)···O(6)#1 2.805 (2), 172.7; and O(3)—H(3)···O(2)#2, 2.901 (2), 163.7. (Symmetry code: #1 x - 1,y,z - 1; #2 x + 1,y,z; #3 x + 1,y + 1,z; #4 x,y - 1,z + 1).

Related literature top

Digitoxin and digoxin, the typical clinically used forms (Kreis et al., 1998), are the drugs of choice for the treatment of congestive heart failure, acting as selective inhibitors of the Na+, K+ ATPase enzyme. For the biotransformation of digitoxigenin into digoxigenin and digoxigenone by Fusarium ciliatum and into 1 beta-hydroxydigitoxigenin, 7-β-hydroxydigitoxigenin, 8-β-hydroxidigitoxigenin and digitoxigenone by Cochliobolus lunatus, see: Pádua et al. (2005, 2007).

Experimental top

The Arthrobacter simplex TCCC 11037 (stored in our laboratory) was maintained at 277 K on a slant containing glucose 10.0 g/L, yeast extract 10.0 g L-1 and agar 20.0 g L-1 (pH = 7.2). Seed media consists of glucose 10.0 g/L, corn slurry 10.0 g/L, peptone 5.0 g/L and KH₂PO₄ 2.5 g/L (pH = 7.2).

The Arthrobacter simplex (ASP) cells were prepared in two consecutive cultivation steps (18 h for seed culture and 24 h for cell incubation, respectively) in shake flasks. The whole ASP culture using 5% (v/v) of seed culture was grown in 250 ml shake flasks containing 30 ml culture media on a rotary shaker (160 rpm) at 305 K. Digoxigenin dissolved in ethanol (50 g L-1) and distributed among the flasks (0.34 g/L),and then the reaction was allowed to proceed for 7 days at 307 K. The biotransformation products were sequentially extracted with ethyl acetate (3 × 100 ml) in a separator funnel and the solvent was vacuum removed at 333 K, until a residue was produced. The crude extracts were purified by Si gel column using chloroform/methanol (25:1, v/v). The white power was diffused with petroleum ether/acetone (5:3, v/v) at room temperature. Colourless prism crystals were obtained.

Structure description top

Digitoxin and digoxin, the typical clinically used forms (Kreis et al., 1998), are the drugs of choice for the treatment of congestive heart failure, acting as selective inhibitors of the Na+, K+ ATPase enzyme. Digitoxigenin has been biotransformed into digoxigenin and digoxigenone by Fusarium ciliatum and into 1 beta-hydroxydigitoxigenin, 7 beta-hydroxydigitoxigenin, 8 beta-hydroxidigitoxigenin, and digitoxigenone by Cochliobolus lunatus (Pádua et al., 2005; Pádua et al., 2007). In this paper, we studied the biotransformation of digoxigenin by Arthrobacter simplex and reported crystal structure of the compound digoxigenone.

Digitoxin and digoxin, the typical clinically used forms (Kreis et al., 1998), are the drugs of choice for the treatment of congestive heart failure, acting as selective inhibitors of the Na+, K+ ATPase enzyme. For the biotransformation of digitoxigenin into digoxigenin and digoxigenone by Fusarium ciliatum and into 1 beta-hydroxydigitoxigenin, 7-β-hydroxydigitoxigenin, 8-β-hydroxidigitoxigenin and digitoxigenone by Cochliobolus lunatus, see: Pádua et al. (2005, 2007).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. Perspective view of the title compound (noncoordinated water molecule was omitted for clarity)
	Fig. 2. View of the packing of the title compound

12β,14-Dihydroxy-3-oxo-5β,20 (22)-cardenolide monohydrate top

Crystal data top

C₂₃H₃₀O₅·H₂O	Z = 1
M_r = 404.49	F(000) = 218
Triclinic, P1	D_x = 1.302 Mg m⁻³
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4017 (15) Å	Cell parameters from 1642 reflections
b = 7.7450 (15) Å	θ = 2.1–27.8°
c = 10.215 (2) Å	µ = 0.09 mm⁻¹
α = 99.51 (3)°	T = 293 K
β = 94.70 (3)°	Prism, colourless
γ = 114.97 (3)°	0.32 × 0.26 × 0.20 mm
V = 516.0 (2) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1809 independent reflections
Radiation source: rotating anode	1443 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.035
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.1°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→8
T_min = 0.971, T_max = 0.982	l = −12→12
5251 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0504P)² + 0.010P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1809 reflections	Δρ_max = 0.15 e Å⁻³
275 parameters	Δρ_min = −0.14 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.43 (3)

Crystal data top

C₂₃H₃₀O₅·H₂O	γ = 114.97 (3)°
M_r = 404.49	V = 516.0 (2) Å³
Triclinic, P1	Z = 1
a = 7.4017 (15) Å	Mo Kα radiation
b = 7.7450 (15) Å	µ = 0.09 mm⁻¹
c = 10.215 (2) Å	T = 293 K
α = 99.51 (3)°	0.32 × 0.26 × 0.20 mm
β = 94.70 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1809 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1443 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.982	R_int = 0.035
5251 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.15 e Å⁻³
1809 reflections	Δρ_min = −0.14 e Å⁻³
275 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
C1	−0.0073 (4)	0.3043 (5)	0.5686 (3)	0.0474 (8)
H1A	−0.1000	0.3610	0.5551	0.057*
H1B	−0.0281	0.2103	0.4864	0.057*
C2	−0.0581 (5)	0.1979 (5)	0.6826 (3)	0.0566 (9)
H2A	−0.0574	0.2868	0.7618	0.068*
H2B	−0.1931	0.0907	0.6569	0.068*
C3	0.0884 (5)	0.1203 (5)	0.7161 (3)	0.0562 (9)
C4	0.2931 (5)	0.2275 (5)	0.6930 (3)	0.0548 (8)
H4	0.3868	0.1813	0.7137	0.066*
C5	0.3553 (4)	0.3895 (4)	0.6435 (3)	0.0394 (7)
C6	0.5751 (4)	0.5096 (5)	0.6423 (3)	0.0510 (8)
H6A	0.6496	0.4382	0.6646	0.061*
H6B	0.6252	0.6295	0.7107	0.061*
C7	0.6133 (4)	0.5598 (5)	0.5056 (3)	0.0426 (7)
H7A	0.5823	0.4415	0.4395	0.051*
H7B	0.7552	0.6476	0.5118	0.051*
C8	0.4846 (4)	0.6561 (4)	0.4589 (3)	0.0302 (6)
H8	0.5236	0.7780	0.5253	0.036*
C9	0.2593 (3)	0.5255 (4)	0.4572 (3)	0.0299 (6)
H9	0.2219	0.4043	0.3906	0.036*
C10	0.2105 (4)	0.4666 (3)	0.5934 (2)	0.0321 (6)
C11	0.1312 (4)	0.6216 (4)	0.4064 (3)	0.0380 (7)
H11A	−0.0108	0.5345	0.4005	0.046*
H11B	0.1622	0.7411	0.4712	0.046*
C12	0.1679 (4)	0.6685 (4)	0.2704 (3)	0.0333 (6)
H12	0.1254	0.5461	0.2038	0.040*
C13	0.3939 (4)	0.8041 (3)	0.2682 (2)	0.0302 (6)
C14	0.5248 (4)	0.7098 (4)	0.3221 (3)	0.0311 (6)
C15	0.4892 (4)	0.5418 (4)	0.2060 (3)	0.0364 (6)
H15A	0.3658	0.4274	0.2068	0.044*
H15B	0.6013	0.5080	0.2116	0.044*
C16	0.4720 (4)	0.6179 (4)	0.0779 (3)	0.0441 (7)
H16A	0.3672	0.5153	0.0083	0.053*
H16B	0.5991	0.6614	0.0442	0.053*
C17	0.4186 (4)	0.7903 (4)	0.1164 (3)	0.0350 (6)
H17	0.2852	0.7522	0.0644	0.042*
C18	0.2350 (5)	0.6415 (5)	0.7033 (3)	0.0507 (8)
H18A	0.2182	0.6027	0.7878	0.076*
H18B	0.1346	0.6836	0.6789	0.076*
H18C	0.3674	0.7469	0.7116	0.076*
C19	0.4521 (4)	1.0101 (4)	0.3480 (3)	0.0418 (7)
H19A	0.5941	1.0896	0.3529	0.063*
H19B	0.4220	1.0049	0.4373	0.063*
H19C	0.3767	1.0654	0.3039	0.063*
C20	0.5633 (4)	0.9736 (4)	0.0803 (3)	0.0380 (6)
C21	0.7889 (4)	1.0689 (4)	0.1180 (4)	0.0567 (9)
H21A	0.8296	1.1136	0.2150	0.068*
H21B	0.8434	0.9787	0.0863	0.068*
C22	0.5139 (5)	1.0757 (4)	0.0035 (3)	0.0488 (8)
H22	0.3828	1.0478	−0.0331	0.059*
C23	0.6953 (5)	1.2364 (4)	−0.0143 (3)	0.0523 (8)
O1	0.0400 (5)	−0.0230 (4)	0.7666 (3)	0.0905 (10)
O2	0.0392 (3)	0.7578 (3)	0.2377 (2)	0.0497 (6)
H2	0.0251	0.7534	0.1566	0.075*
O3	0.7324 (2)	0.8562 (2)	0.33978 (19)	0.0392 (5)
H3	0.8017	0.8051	0.3095	0.059*
O4	0.8586 (3)	1.2327 (3)	0.0526 (2)	0.0610 (6)
O5	0.7166 (4)	1.3617 (4)	−0.0773 (3)	0.0797 (8)
O6	0.9639 (4)	0.7538 (4)	0.9630 (3)	0.0661 (7)
H1W	0.979 (7)	0.816 (5)	0.899 (3)	0.105 (15)*
H2W	0.901 (7)	0.6285 (16)	0.937 (4)	0.13 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0383 (16)	0.0560 (19)	0.0500 (19)	0.0171 (14)	0.0123 (14)	0.0255 (16)
C2	0.0578 (19)	0.053 (2)	0.061 (2)	0.0180 (16)	0.0204 (16)	0.0302 (16)
C3	0.076 (2)	0.0477 (19)	0.049 (2)	0.0266 (17)	0.0187 (17)	0.0210 (16)
C4	0.070 (2)	0.063 (2)	0.056 (2)	0.0440 (18)	0.0204 (16)	0.0306 (17)
C5	0.0454 (16)	0.0485 (17)	0.0328 (16)	0.0267 (14)	0.0062 (12)	0.0149 (13)
C6	0.0421 (17)	0.075 (2)	0.0494 (19)	0.0327 (16)	0.0062 (14)	0.0296 (17)
C7	0.0332 (16)	0.0563 (18)	0.0503 (18)	0.0265 (14)	0.0103 (13)	0.0232 (15)
C8	0.0299 (13)	0.0342 (14)	0.0291 (14)	0.0165 (11)	0.0042 (10)	0.0076 (11)
C9	0.0297 (13)	0.0332 (14)	0.0311 (14)	0.0168 (11)	0.0066 (10)	0.0099 (11)
C10	0.0342 (15)	0.0356 (16)	0.0300 (15)	0.0179 (12)	0.0057 (11)	0.0089 (12)
C11	0.0336 (15)	0.0534 (17)	0.0390 (16)	0.0261 (13)	0.0104 (12)	0.0205 (14)
C12	0.0263 (13)	0.0449 (16)	0.0383 (16)	0.0213 (12)	0.0098 (11)	0.0166 (13)
C13	0.0309 (13)	0.0318 (14)	0.0306 (15)	0.0156 (11)	0.0074 (11)	0.0083 (11)
C14	0.0234 (13)	0.0334 (14)	0.0380 (15)	0.0127 (11)	0.0087 (11)	0.0096 (12)
C15	0.0371 (14)	0.0359 (15)	0.0399 (16)	0.0179 (12)	0.0138 (12)	0.0093 (13)
C16	0.0528 (17)	0.0400 (15)	0.0382 (17)	0.0183 (13)	0.0133 (13)	0.0083 (13)
C17	0.0322 (13)	0.0384 (15)	0.0311 (14)	0.0117 (12)	0.0056 (11)	0.0096 (12)
C18	0.075 (2)	0.0529 (19)	0.0376 (17)	0.0377 (18)	0.0189 (15)	0.0126 (15)
C19	0.0480 (16)	0.0357 (15)	0.0439 (16)	0.0210 (13)	0.0088 (13)	0.0076 (13)
C20	0.0429 (15)	0.0383 (15)	0.0328 (15)	0.0169 (12)	0.0113 (12)	0.0088 (12)
C21	0.0425 (18)	0.049 (2)	0.074 (2)	0.0101 (15)	0.0141 (15)	0.0295 (17)
C22	0.055 (2)	0.0499 (18)	0.0475 (18)	0.0235 (16)	0.0153 (14)	0.0210 (15)
C23	0.071 (2)	0.0427 (18)	0.0470 (19)	0.0238 (16)	0.0232 (17)	0.0179 (15)
O1	0.119 (2)	0.0708 (17)	0.107 (2)	0.0453 (16)	0.0475 (19)	0.0631 (18)
O2	0.0421 (11)	0.0820 (15)	0.0485 (12)	0.0417 (11)	0.0136 (10)	0.0331 (12)
O3	0.0267 (9)	0.0401 (11)	0.0502 (12)	0.0131 (8)	0.0086 (8)	0.0119 (9)
O4	0.0545 (14)	0.0495 (13)	0.0670 (16)	0.0068 (10)	0.0171 (11)	0.0236 (11)
O5	0.108 (2)	0.0596 (15)	0.083 (2)	0.0347 (15)	0.0367 (15)	0.0438 (14)
O6	0.0627 (15)	0.0775 (19)	0.0564 (15)	0.0232 (15)	0.0116 (12)	0.0316 (14)

Geometric parameters (Å, º) top

C1—C2	1.518 (4)	C13—C19	1.526 (4)
C1—C10	1.536 (4)	C13—C14	1.555 (3)
C1—H1A	0.9700	C13—C17	1.567 (3)
C1—H1B	0.9700	C14—O3	1.448 (3)
C2—C3	1.487 (4)	C14—C15	1.523 (4)
C2—H2A	0.9700	C15—C16	1.538 (4)
C2—H2B	0.9700	C15—H15A	0.9700
C3—O1	1.229 (4)	C15—H15B	0.9700
C3—C4	1.450 (5)	C16—C17	1.547 (4)
C4—C5	1.342 (4)	C16—H16A	0.9700
C4—H4	0.9300	C16—H16B	0.9700
C5—C6	1.497 (4)	C17—C20	1.501 (4)
C5—C10	1.523 (3)	C17—H17	0.9800
C6—C7	1.527 (4)	C18—H18A	0.9600
C6—H6A	0.9700	C18—H18B	0.9600
C6—H6B	0.9700	C18—H18C	0.9600
C7—C8	1.528 (4)	C19—H19A	0.9600
C7—H7A	0.9700	C19—H19B	0.9600
C7—H7B	0.9700	C19—H19C	0.9600
C8—C14	1.539 (3)	C20—C22	1.333 (4)
C8—C9	1.540 (3)	C20—C21	1.497 (4)
C8—H8	0.9800	C21—O4	1.451 (3)
C9—C11	1.537 (3)	C21—H21A	0.9700
C9—C10	1.558 (3)	C21—H21B	0.9700
C9—H9	0.9800	C22—C23	1.445 (4)
C10—C18	1.544 (4)	C22—H22	0.9300
C11—C12	1.510 (4)	C23—O5	1.215 (4)
C11—H11A	0.9700	C23—O4	1.352 (4)
C11—H11B	0.9700	O2—H2	0.8200
C12—O2	1.442 (3)	O3—H3	0.8200
C12—C13	1.560 (3)	O6—H1W	0.861 (11)
C12—H12	0.9800	O6—H2W	0.862 (11)

C2—C1—C10	113.8 (2)	C13—C12—H12	108.7
C2—C1—H1A	108.8	C19—C13—C14	113.6 (2)
C10—C1—H1A	108.8	C19—C13—C12	110.0 (2)
C2—C1—H1B	108.8	C14—C13—C12	108.13 (19)
C10—C1—H1B	108.8	C19—C13—C17	114.5 (2)
H1A—C1—H1B	107.7	C14—C13—C17	103.33 (19)
C3—C2—C1	111.8 (3)	C12—C13—C17	106.8 (2)
C3—C2—H2A	109.3	O3—C14—C15	108.79 (19)
C1—C2—H2A	109.3	O3—C14—C8	107.92 (19)
C3—C2—H2B	109.3	C15—C14—C8	116.0 (2)
C1—C2—H2B	109.3	O3—C14—C13	105.59 (19)
H2A—C2—H2B	107.9	C15—C14—C13	104.0 (2)
O1—C3—C4	121.6 (3)	C8—C14—C13	113.95 (19)
O1—C3—C2	121.4 (3)	C14—C15—C16	105.1 (2)
C4—C3—C2	116.9 (3)	C14—C15—H15A	110.7
C5—C4—C3	123.9 (3)	C16—C15—H15A	110.7
C5—C4—H4	118.1	C14—C15—H15B	110.7
C3—C4—H4	118.1	C16—C15—H15B	110.7
C4—C5—C6	120.8 (3)	H15A—C15—H15B	108.8
C4—C5—C10	122.4 (3)	C15—C16—C17	107.2 (2)
C6—C5—C10	116.7 (2)	C15—C16—H16A	110.3
C5—C6—C7	112.2 (2)	C17—C16—H16A	110.3
C5—C6—H6A	109.2	C15—C16—H16B	110.3
C7—C6—H6A	109.2	C17—C16—H16B	110.3
C5—C6—H6B	109.2	H16A—C16—H16B	108.5
C7—C6—H6B	109.2	C20—C17—C16	112.9 (2)
H6A—C6—H6B	107.9	C20—C17—C13	116.6 (2)
C6—C7—C8	111.6 (2)	C16—C17—C13	105.62 (19)
C6—C7—H7A	109.3	C20—C17—H17	107.1
C8—C7—H7A	109.3	C16—C17—H17	107.1
C6—C7—H7B	109.3	C13—C17—H17	107.1
C8—C7—H7B	109.3	C10—C18—H18A	109.5
H7A—C7—H7B	108.0	C10—C18—H18B	109.5
C7—C8—C14	111.8 (2)	H18A—C18—H18B	109.5
C7—C8—C9	110.3 (2)	C10—C18—H18C	109.5
C14—C8—C9	112.24 (18)	H18A—C18—H18C	109.5
C7—C8—H8	107.4	H18B—C18—H18C	109.5
C14—C8—H8	107.4	C13—C19—H19A	109.5
C9—C8—H8	107.4	C13—C19—H19B	109.5
C11—C9—C8	109.72 (19)	H19A—C19—H19B	109.5
C11—C9—C10	112.22 (19)	C13—C19—H19C	109.5
C8—C9—C10	114.26 (19)	H19A—C19—H19C	109.5
C11—C9—H9	106.7	H19B—C19—H19C	109.5
C8—C9—H9	106.7	C22—C20—C21	107.7 (2)
C10—C9—H9	106.7	C22—C20—C17	125.9 (3)
C5—C10—C1	109.3 (2)	C21—C20—C17	126.4 (2)
C5—C10—C18	107.8 (2)	O4—C21—C20	105.0 (2)
C1—C10—C18	110.2 (2)	O4—C21—H21A	110.7
C5—C10—C9	109.2 (2)	C20—C21—H21A	110.7
C1—C10—C9	108.2 (2)	O4—C21—H21B	110.7
C18—C10—C9	112.1 (2)	C20—C21—H21B	110.7
C12—C11—C9	112.8 (2)	H21A—C21—H21B	108.8
C12—C11—H11A	109.0	C20—C22—C23	109.6 (3)
C9—C11—H11A	109.0	C20—C22—H22	125.2
C12—C11—H11B	109.0	C23—C22—H22	125.2
C9—C11—H11B	109.0	O5—C23—O4	120.3 (3)
H11A—C11—H11B	107.8	O5—C23—C22	130.4 (3)
O2—C12—C11	106.0 (2)	O4—C23—C22	109.3 (2)
O2—C12—C13	111.4 (2)	C12—O2—H2	109.5
C11—C12—C13	113.1 (2)	C14—O3—H3	109.5
O2—C12—H12	108.7	C23—O4—C21	108.4 (2)
C11—C12—H12	108.7	H1W—O6—H2W	114.3 (19)

C10—C1—C2—C3	−54.0 (4)	C7—C8—C14—O3	−64.4 (3)
C1—C2—C3—O1	−153.4 (3)	C9—C8—C14—O3	171.01 (18)
C1—C2—C3—C4	29.7 (4)	C7—C8—C14—C15	57.9 (3)
O1—C3—C4—C5	−177.1 (3)	C9—C8—C14—C15	−66.7 (3)
C2—C3—C4—C5	−0.2 (5)	C7—C8—C14—C13	178.7 (2)
C3—C4—C5—C6	170.4 (3)	C9—C8—C14—C13	54.1 (3)
C3—C4—C5—C10	−6.1 (5)	C19—C13—C14—O3	−48.0 (3)
C4—C5—C6—C7	131.9 (3)	C12—C13—C14—O3	−170.35 (19)
C10—C5—C6—C7	−51.3 (4)	C17—C13—C14—O3	76.7 (2)
C5—C6—C7—C8	53.6 (4)	C19—C13—C14—C15	−162.5 (2)
C6—C7—C8—C14	179.2 (2)	C12—C13—C14—C15	75.2 (2)
C6—C7—C8—C9	−55.2 (3)	C17—C13—C14—C15	−37.8 (2)
C7—C8—C9—C11	−178.5 (3)	C19—C13—C14—C8	70.3 (3)
C14—C8—C9—C11	−53.1 (3)	C12—C13—C14—C8	−52.1 (3)
C7—C8—C9—C10	54.5 (3)	C17—C13—C14—C8	−165.0 (2)
C14—C8—C9—C10	179.9 (2)	O3—C14—C15—C16	−75.9 (2)
C4—C5—C10—C1	−17.3 (4)	C8—C14—C15—C16	162.2 (2)
C6—C5—C10—C1	166.1 (3)	C13—C14—C15—C16	36.3 (2)
C4—C5—C10—C18	102.6 (3)	C14—C15—C16—C17	−20.6 (3)
C6—C5—C10—C18	−74.1 (3)	C15—C16—C17—C20	125.5 (2)
C4—C5—C10—C9	−135.4 (3)	C15—C16—C17—C13	−3.0 (3)
C6—C5—C10—C9	47.9 (3)	C19—C13—C17—C20	22.6 (3)
C2—C1—C10—C5	46.7 (3)	C14—C13—C17—C20	−101.5 (2)
C2—C1—C10—C18	−71.5 (3)	C12—C13—C17—C20	144.6 (2)
C2—C1—C10—C9	165.6 (2)	C19—C13—C17—C16	148.9 (2)
C11—C9—C10—C5	−175.0 (2)	C14—C13—C17—C16	24.8 (2)
C8—C9—C10—C5	−49.3 (3)	C12—C13—C17—C16	−89.1 (2)
C11—C9—C10—C1	66.1 (3)	C16—C17—C20—C22	124.3 (3)
C8—C9—C10—C1	−168.16 (19)	C13—C17—C20—C22	−113.1 (3)
C11—C9—C10—C18	−55.6 (3)	C16—C17—C20—C21	−52.4 (4)
C8—C9—C10—C18	70.1 (3)	C13—C17—C20—C21	70.1 (4)
C8—C9—C11—C12	55.3 (3)	C22—C20—C21—O4	−0.7 (3)
C10—C9—C11—C12	−176.6 (2)	C17—C20—C21—O4	176.6 (2)
C9—C11—C12—O2	−179.6 (2)	C21—C20—C22—C23	0.4 (3)
C9—C11—C12—C13	−57.3 (3)	C17—C20—C22—C23	−176.9 (2)
O2—C12—C13—C19	48.2 (3)	C20—C22—C23—O5	179.4 (3)
C11—C12—C13—C19	−71.1 (3)	C20—C22—C23—O4	0.1 (3)
O2—C12—C13—C14	172.8 (2)	O5—C23—O4—C21	−179.9 (3)
C11—C12—C13—C14	53.5 (3)	C22—C23—O4—C21	−0.5 (3)
O2—C12—C13—C17	−76.6 (2)	C20—C21—O4—C23	0.7 (3)
C11—C12—C13—C17	164.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6ⁱ	0.82	1.99	2.808 (3)	173
O3—H3···O2ⁱⁱ	0.82	2.10	2.900 (3)	164
O6—H1W···O1ⁱⁱⁱ	0.86 (1)	1.94 (1)	2.801 (3)	174 (4)
O6—H2W···O5^iv	0.86 (1)	1.91 (2)	2.741 (4)	162 (5)

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

Experimental details

Crystal data
Chemical formula	C₂₃H₃₀O₅·H₂O
M_r	404.49
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4017 (15), 7.7450 (15), 10.215 (2)
α, β, γ (°)	99.51 (3), 94.70 (3), 114.97 (3)
V (Å³)	516.0 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.26 × 0.20

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.971, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5251, 1809, 1443
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.082, 1.00
No. of reflections	1809
No. of parameters	275
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: CrystalClear (Rigaku, 2005), 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
O2—H2···O6ⁱ	0.82	1.99	2.808 (3)	172.7
O3—H3···O2ⁱⁱ	0.82	2.10	2.900 (3)	163.6
O6—H1W···O1ⁱⁱⁱ	0.861 (11)	1.943 (11)	2.801 (3)	174 (4)
O6—H2W···O5^iv	0.862 (11)	1.908 (18)	2.741 (4)	162 (5)

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

Acknowledgements

This work was supported by the Natural Science Foundation of Tianjin (No. 08JCZDJC15200)

References

Kreis, W., Hensel, A. & Stuhlemmer, U. (1998). Planta Med. 64, 491–499. Web of Science CrossRef CAS Google Scholar
Pádua, R. M., Oliveira, A. B., Souza Filho, J. D., Takahashi, J. A., Silva, M. A. & Braga, F. C. (2007). J. Braz. Chem. Soc. 18, 1303–1310. Google Scholar
Pádua, R. M., Oliveira, A. B., Souza Filho, J. D., Vieira, G. J., Takahashi, J. A. & Braga, F. C. (2005). J. Braz. Chem. Soc. 16, 614–619. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar