11α,15α-Dihy­droxy­androst-4-ene-3,17-dione

Shen, Y.-B.; Wang, M.; Liang, Q.-K.; Luo, J.

doi:10.1107/S1600536811038608

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2752

https://doi.org/10.1107/S1600536811038608

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11α,15α-Dihydroxyandrost-4-ene-3,17-dione

Yan-Bing Shen,^a Min Wang,^a ^* Qi-Kun Liang ^a and Jian-Mei Luo ^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 22 July 2011; accepted 20 September 2011; online 30 September 2011)

The title compound, C₁₉H₂₆O₄, was biotransformed from androstenedione. In the crystal, intermolecular O—H⋯O hydrogen bonds link molecules into a corrugated sheet, which lies parallel to the ab plane. Ring A has a slightly distorted half-chair conformation, rings B and C adopt chair conformations, while the cyclopentane ring D adopts a 14α-envelope conformation.

Related literature

For related structures, see: Galdecki et al. (1990 ); Thamotharan et al. (2004 ); Vasuki et al. (2002 ). For details of biotransformation, see: Ahmad et al. (1992 ); Kollerov et al. (2008 ); Malaviya & Gomes (2008 ); Perez et al. (2006 ). For conformational analysis, see Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₉H₂₆O₄
M_r = 318.40
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.8716 (8) Å
b = 12.2725 (12) Å
c = 17.2100 (16) Å
V = 1662.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 113 K
0.22 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn 724CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.981, T_max = 0.990
17662 measured reflections
2275 independent reflections
2050 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.081
S = 1.03
2275 reflections
218 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.88 (3)	1.94 (3)	2.800 (2)	164 (3)
O2—H2⋯O1ⁱⁱ	0.81 (3)	1.95 (3)	2.7600 (19)	180 (3)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536811038608/lw2070sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038608/lw2070Isup2.hkl

checkCIF report

Comment top

Androst-4-ene-3,17-dione (AD) is the important intermediate in the pharmaceutical industry (Perez et al., 2006; Kollerov et al. 2008). The production of several high value steroid drugs is mostly derived from key compounds such as AD by chemical synthesis (Ahmad et al., 1992; Malaviya & Gomes, 2008).

The structure of the title compound is depicted in Fig. 1. The 11α,15α-dihydroxy-androstenedione has three six-membered rings (A/B/C) and one five-membered rings (D). Ring A has a slightly distorted half-chair conformation. Rings B and C adopt chair conformations, while the cyclopentane ring D adopts a 14α-envelope conformation. The torsion angle C8—C9—C11—O2 = 162.83 (13), indicates that the 11-hydroxy has an α configuration. The 15-hydroxy has an α configuration with the torsion angle C13—C14—C15—O3 = -160.83 (14)°. The bond lengths and angles are within normal ranges (Thamotharan et al., 2004; Vasuki, et al., 2002; Galdecki et al., 1990).

Two types of intermolecular hydrogen bonds contribute to the formation of a two-dimensional corrugated sheet lying parallel to the ab-plane, Figure 2. The O3 hydroxyl hydrogen forms a hydrogen bond to hydroxyl atom O2 at (1-x,y,z) by unit translation along the a-axis. Hydroxyl oxygen O2 forms a hydrogen bond to the screw-related carbonyl atom O1 at (1-x,-1/2+y,1/2-z), Table 1.

Related literature top

For related structures, see: Galdecki et al. (1990); Thamotharan et al. (2004); Vasuki et al. (2002). For details of biotransformation, see: Ahmad et al. (1992); Kollerov et al. (2008); Malaviya & Gomes (2008); Perez et al. (2006). For conformational analysis, see Cremer & Pople (1975).

Experimental top

Experimental

Reagents: Colletotrichum lini AS3. 4486 was obtained from Institute of Microbiology, Chinese Academy of Sciences and maintained on Potato Dextrose Agar at 4°C. Androst-4-en-3,17-dione was obtained from Tianjin Pharmaceutical Company.

Cultures Protocol: Colletotrichum lini AS3. 4486 was cultivated in shake flasks in two consecutive cultivation steps: 72 h for seed culture and 24 h for cell cultivation. Seed medium comprised glucose 30 g/L, corn steep liquor 10 g/L and tap water (pH 7.0). Cell cultivation medium comprised glucose 3 g/L, corn steep liquor 10 g/L, soy meal 10 g/L, NaNO₃ 2 g/L, KH₂PO₄, 1 g/L, K₂HPO₄, 2 g/L, MgSO₄.7H₂O 0.5g/L, KCl, 0.5g/L, FeSO₄.7H₂O, 0.02 g/L, (pH 7.0). Cells were grown in 250 ml shake flasks containing 50 ml culture medium on a rotary shaker (200 r/min) at 25°C using 10% (v/v) of the seed culture as inoculum.

Biotransformation: 50 mg of the androst-4-en-3,17-dione dissolved in 1 ml of ethanol was added to the culture after 24 h for growth and the reaction was allowed to proceed for 72 h. The mycelium was then removed by filtration.

Separation and purification: The biomass and the broth were extracted separately with EtOAc. All extracts were combined and dried (anhydr. MgSO₄). The solvents after filtration were evaporated under reduced pressure. The crude extracts were purified by Si gel column using dichloromethane/ether/methanol (25:2:1, v/v/v). The white powder was diffused with n-hexane/acetone at room temperature. Colorless prismatic crystals suitable for X-ray analysis were obtained.

Structure description top

For related structures, see: Galdecki et al. (1990); Thamotharan et al. (2004); Vasuki et al. (2002). For details of biotransformation, see: Ahmad et al. (1992); Kollerov et al. (2008); Malaviya & Gomes (2008); Perez et al. (2006). For conformational analysis, see Cremer & Pople (1975).

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. A view of (I) with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the packing of the title compound

11α,15α-Dihydroxyandrost-4-ene-3,17-dione top

Crystal data top

C₁₉H₂₆O₄	D_x = 1.272 Mg m⁻³
M_r = 318.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6101 reflections
a = 7.8716 (8) Å	θ = 2.0–28.0°
b = 12.2725 (12) Å	µ = 0.09 mm⁻¹
c = 17.2100 (16) Å	T = 113 K
V = 1662.6 (3) Å³	Prism, colourless
Z = 4	0.22 × 0.18 × 0.12 mm
F(000) = 688

Data collection top

Rigaku Saturn 724CCD diffractometer	2275 independent reflections
Radiation source: rotating anode	2050 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.047
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 2.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→16
T_min = 0.981, T_max = 0.990	l = −21→22
17662 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0478P)²] where P = (F_o² + 2F_c²)/3
2275 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₉H₂₆O₄	V = 1662.6 (3) Å³
M_r = 318.40	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.8716 (8) Å	µ = 0.09 mm⁻¹
b = 12.2725 (12) Å	T = 113 K
c = 17.2100 (16) Å	0.22 × 0.18 × 0.12 mm

Data collection top

Rigaku Saturn 724CCD diffractometer	2275 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2050 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.990	R_int = 0.047
17662 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.16 e Å⁻³
2275 reflections	Δρ_min = −0.20 e Å⁻³
218 parameters

Special details top

Experimental. Rigaku CrystalClear-SM Expert 2.0 r2

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	0.31267 (17)	0.53408 (9)	0.26929 (8)	0.0327 (3)
O2	0.51158 (16)	0.08691 (11)	0.09715 (8)	0.0284 (3)
H2	0.563 (3)	0.0711 (19)	0.1363 (15)	0.056 (8)*
O3	−0.27423 (18)	0.05176 (12)	−0.03028 (8)	0.0328 (3)
H3	−0.357 (4)	0.064 (2)	0.0029 (16)	0.071 (9)*
O4	0.16087 (19)	−0.21111 (10)	−0.06034 (7)	0.0349 (4)
C1	0.4080 (2)	0.26310 (14)	0.19535 (12)	0.0286 (4)
H1A	0.4888	0.2042	0.2087	0.034*
H1B	0.4428	0.2935	0.1445	0.034*
C2	0.4205 (2)	0.35273 (15)	0.25684 (12)	0.0309 (4)
H2A	0.4037	0.3203	0.3089	0.037*
H2B	0.5357	0.3850	0.2553	0.037*
C3	0.2921 (2)	0.44021 (14)	0.24442 (10)	0.0238 (4)
C4	0.1357 (2)	0.40863 (14)	0.20623 (10)	0.0232 (4)
H4	0.0535	0.4636	0.1964	0.028*
C5	0.1002 (2)	0.30692 (13)	0.18408 (10)	0.0214 (4)
C6	−0.0777 (2)	0.28022 (15)	0.15829 (11)	0.0299 (4)
H6A	−0.1398	0.3489	0.1482	0.036*
H6B	−0.1371	0.2415	0.2008	0.036*
C7	−0.0825 (2)	0.21006 (14)	0.08549 (11)	0.0267 (4)
H7A	−0.0385	0.2522	0.0408	0.032*
H7B	−0.2012	0.1890	0.0740	0.032*
C8	0.0253 (2)	0.10785 (13)	0.09697 (10)	0.0202 (4)
H8	−0.0158	0.0696	0.1447	0.024*
C9	0.2132 (2)	0.14340 (14)	0.11087 (9)	0.0185 (3)
H9	0.2434	0.1930	0.0669	0.022*
C10	0.2289 (2)	0.21395 (13)	0.18739 (10)	0.0205 (4)
C11	0.3406 (2)	0.04730 (14)	0.10728 (10)	0.0213 (4)
H11	0.3346	0.0064	0.1575	0.026*
C12	0.3116 (2)	−0.03257 (14)	0.04087 (10)	0.0236 (4)
H12A	0.3401	0.0030	−0.0091	0.028*
H12B	0.3875	−0.0963	0.0474	0.028*
C13	0.1278 (2)	−0.07058 (13)	0.03913 (9)	0.0212 (4)
C14	0.0122 (2)	0.02890 (13)	0.02873 (9)	0.0216 (4)
H14	0.0545	0.0688	−0.0181	0.026*
C15	−0.1598 (2)	−0.02117 (14)	0.00633 (10)	0.0257 (4)
H15	−0.2147	−0.0537	0.0533	0.031*
C16	−0.1069 (3)	−0.11229 (16)	−0.05010 (11)	0.0328 (5)
H16A	−0.1820	−0.1765	−0.0440	0.039*
H16B	−0.1139	−0.0866	−0.1045	0.039*
C17	0.0746 (2)	−0.14129 (15)	−0.02929 (10)	0.0262 (4)
C18	0.0840 (2)	−0.13973 (14)	0.11174 (9)	0.0256 (4)
H18A	−0.0316	−0.1685	0.1067	0.038*
H18B	0.0913	−0.0940	0.1583	0.038*
H18C	0.1645	−0.2003	0.1161	0.038*
C19	0.1869 (3)	0.14572 (15)	0.26033 (10)	0.0325 (5)
H19A	0.2029	0.1905	0.3069	0.049*
H19B	0.2625	0.0824	0.2627	0.049*
H19C	0.0686	0.1210	0.2577	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0360 (8)	0.0215 (6)	0.0407 (8)	−0.0023 (6)	−0.0052 (6)	−0.0074 (6)
O2	0.0162 (6)	0.0369 (7)	0.0322 (7)	0.0014 (6)	−0.0021 (6)	−0.0035 (6)
O3	0.0253 (7)	0.0453 (8)	0.0277 (7)	0.0002 (7)	−0.0082 (6)	0.0004 (6)
O4	0.0415 (9)	0.0337 (7)	0.0296 (7)	−0.0005 (7)	0.0077 (6)	−0.0113 (6)
C1	0.0193 (9)	0.0242 (10)	0.0422 (11)	0.0024 (8)	−0.0062 (8)	−0.0097 (8)
C2	0.0246 (9)	0.0266 (9)	0.0414 (11)	−0.0001 (8)	−0.0094 (9)	−0.0079 (9)
C3	0.0274 (9)	0.0224 (8)	0.0217 (8)	−0.0033 (8)	0.0029 (7)	−0.0018 (7)
C4	0.0235 (9)	0.0214 (9)	0.0246 (8)	0.0046 (7)	0.0005 (7)	−0.0006 (7)
C5	0.0210 (9)	0.0227 (9)	0.0206 (8)	−0.0002 (7)	0.0018 (7)	−0.0007 (7)
C6	0.0181 (9)	0.0265 (9)	0.0452 (11)	0.0025 (8)	−0.0018 (8)	−0.0105 (9)
C7	0.0187 (9)	0.0256 (9)	0.0357 (10)	0.0004 (8)	−0.0058 (8)	−0.0030 (8)
C8	0.0158 (8)	0.0217 (8)	0.0233 (8)	−0.0014 (7)	−0.0008 (7)	−0.0004 (7)
C9	0.0162 (8)	0.0193 (8)	0.0201 (8)	0.0001 (7)	−0.0008 (6)	0.0020 (7)
C10	0.0206 (9)	0.0189 (8)	0.0221 (8)	−0.0005 (7)	−0.0024 (7)	−0.0004 (7)
C11	0.0169 (8)	0.0233 (8)	0.0238 (8)	0.0007 (7)	−0.0006 (7)	0.0007 (7)
C12	0.0219 (9)	0.0248 (9)	0.0243 (8)	0.0023 (8)	0.0022 (7)	−0.0041 (7)
C13	0.0233 (9)	0.0219 (9)	0.0186 (8)	−0.0019 (7)	0.0027 (7)	−0.0048 (7)
C14	0.0184 (8)	0.0253 (9)	0.0212 (8)	−0.0024 (7)	0.0005 (7)	0.0001 (7)
C15	0.0223 (9)	0.0315 (10)	0.0234 (9)	−0.0038 (8)	−0.0026 (7)	−0.0024 (8)
C16	0.0302 (10)	0.0405 (11)	0.0275 (9)	−0.0075 (9)	0.0003 (8)	−0.0099 (9)
C17	0.0311 (10)	0.0269 (9)	0.0206 (8)	−0.0068 (9)	0.0063 (8)	−0.0026 (8)
C18	0.0323 (10)	0.0219 (8)	0.0225 (8)	0.0027 (8)	0.0041 (8)	−0.0014 (7)
C19	0.0553 (13)	0.0225 (8)	0.0197 (8)	−0.0005 (10)	−0.0029 (9)	−0.0007 (8)

Geometric parameters (Å, º) top

O1—C3	1.240 (2)	C8—H8	1.0000
O2—C11	1.442 (2)	C9—C11	1.549 (2)
O2—H2	0.81 (3)	C9—C10	1.581 (2)
O3—C15	1.417 (2)	C9—H9	1.0000
O3—H3	0.88 (3)	C10—C19	1.545 (2)
O4—C17	1.217 (2)	C11—C12	1.523 (2)
C1—C2	1.530 (2)	C11—H11	1.0000
C1—C10	1.539 (2)	C12—C13	1.521 (2)
C1—H1A	0.9900	C12—H12A	0.9900
C1—H1B	0.9900	C12—H12B	0.9900
C2—C3	1.490 (2)	C13—C17	1.521 (2)
C2—H2A	0.9900	C13—C14	1.533 (2)
C2—H2B	0.9900	C13—C18	1.549 (2)
C3—C4	1.449 (2)	C14—C15	1.536 (2)
C4—C5	1.335 (2)	C14—H14	1.0000
C4—H4	0.9500	C15—C16	1.539 (2)
C5—C6	1.505 (2)	C15—H15	1.0000
C5—C10	1.527 (2)	C16—C17	1.515 (3)
C6—C7	1.521 (2)	C16—H16A	0.9900
C6—H6A	0.9900	C16—H16B	0.9900
C6—H6B	0.9900	C18—H18A	0.9800
C7—C8	1.527 (2)	C18—H18B	0.9800
C7—H7A	0.9900	C18—H18C	0.9800
C7—H7B	0.9900	C19—H19A	0.9800
C8—C14	1.526 (2)	C19—H19B	0.9800
C8—C9	1.561 (2)	C19—H19C	0.9800

C11—O2—H2	106.5 (18)	C19—C10—C9	111.30 (12)
C15—O3—H3	107.0 (18)	O2—C11—C12	105.43 (13)
C2—C1—C10	113.73 (15)	O2—C11—C9	110.63 (13)
C2—C1—H1A	108.8	C12—C11—C9	115.02 (13)
C10—C1—H1A	108.8	O2—C11—H11	108.5
C2—C1—H1B	108.8	C12—C11—H11	108.5
C10—C1—H1B	108.8	C9—C11—H11	108.5
H1A—C1—H1B	107.7	C13—C12—C11	110.77 (14)
C3—C2—C1	112.03 (15)	C13—C12—H12A	109.5
C3—C2—H2A	109.2	C11—C12—H12A	109.5
C1—C2—H2A	109.2	C13—C12—H12B	109.5
C3—C2—H2B	109.2	C11—C12—H12B	109.5
C1—C2—H2B	109.2	H12A—C12—H12B	108.1
H2A—C2—H2B	107.9	C12—C13—C17	116.88 (14)
O1—C3—C4	121.08 (17)	C12—C13—C14	108.82 (13)
O1—C3—C2	122.11 (16)	C17—C13—C14	101.58 (13)
C4—C3—C2	116.67 (14)	C12—C13—C18	111.33 (15)
C5—C4—C3	123.90 (17)	C17—C13—C18	104.51 (13)
C5—C4—H4	118.0	C14—C13—C18	113.48 (14)
C3—C4—H4	118.0	C8—C14—C13	112.07 (13)
C4—C5—C6	118.85 (16)	C8—C14—C15	120.43 (14)
C4—C5—C10	123.31 (16)	C13—C14—C15	103.52 (13)
C6—C5—C10	117.76 (14)	C8—C14—H14	106.7
C5—C6—C7	112.89 (15)	C13—C14—H14	106.7
C5—C6—H6A	109.0	C15—C14—H14	106.7
C7—C6—H6A	109.0	O3—C15—C14	114.78 (14)
C5—C6—H6B	109.0	O3—C15—C16	110.50 (15)
C7—C6—H6B	109.0	C14—C15—C16	102.16 (15)
H6A—C6—H6B	107.8	O3—C15—H15	109.7
C6—C7—C8	110.18 (14)	C14—C15—H15	109.7
C6—C7—H7A	109.6	C16—C15—H15	109.7
C8—C7—H7A	109.6	C17—C16—C15	106.06 (15)
C6—C7—H7B	109.6	C17—C16—H16A	110.5
C8—C7—H7B	109.6	C15—C16—H16A	110.5
H7A—C7—H7B	108.1	C17—C16—H16B	110.5
C14—C8—C7	112.61 (13)	C15—C16—H16B	110.5
C14—C8—C9	111.06 (13)	H16A—C16—H16B	108.7
C7—C8—C9	108.46 (13)	O4—C17—C16	126.00 (17)
C14—C8—H8	108.2	O4—C17—C13	126.01 (18)
C7—C8—H8	108.2	C16—C17—C13	107.96 (15)
C9—C8—H8	108.2	C13—C18—H18A	109.5
C11—C9—C8	113.24 (13)	C13—C18—H18B	109.5
C11—C9—C10	113.54 (12)	H18A—C18—H18B	109.5
C8—C9—C10	110.80 (13)	C13—C18—H18C	109.5
C11—C9—H9	106.2	H18A—C18—H18C	109.5
C8—C9—H9	106.2	H18B—C18—H18C	109.5
C10—C9—H9	106.2	C10—C19—H19A	109.5
C5—C10—C1	108.55 (13)	C10—C19—H19B	109.5
C5—C10—C19	107.05 (14)	H19A—C19—H19B	109.5
C1—C10—C19	109.65 (15)	C10—C19—H19C	109.5
C5—C10—C9	109.03 (13)	H19A—C19—H19C	109.5
C1—C10—C9	111.13 (14)	H19B—C19—H19C	109.5

C10—C1—C2—C3	−53.7 (2)	C10—C9—C11—O2	−69.69 (17)
C1—C2—C3—O1	−155.82 (17)	C8—C9—C11—C12	43.52 (19)
C1—C2—C3—C4	28.3 (2)	C10—C9—C11—C12	171.00 (14)
O1—C3—C4—C5	−174.15 (17)	O2—C11—C12—C13	−173.29 (13)
C2—C3—C4—C5	1.8 (3)	C9—C11—C12—C13	−51.13 (19)
C3—C4—C5—C6	169.05 (16)	C11—C12—C13—C17	173.62 (14)
C3—C4—C5—C10	−7.7 (3)	C11—C12—C13—C14	59.39 (18)
C4—C5—C6—C7	136.19 (17)	C11—C12—C13—C18	−66.41 (17)
C10—C5—C6—C7	−46.9 (2)	C7—C8—C14—C13	177.14 (14)
C5—C6—C7—C8	53.8 (2)	C9—C8—C14—C13	55.28 (18)
C6—C7—C8—C14	174.60 (14)	C7—C8—C14—C15	−60.8 (2)
C6—C7—C8—C9	−62.07 (19)	C9—C8—C14—C15	177.33 (15)
C14—C8—C9—C11	−44.45 (18)	C12—C13—C14—C8	−63.21 (17)
C7—C8—C9—C11	−168.71 (14)	C17—C13—C14—C8	172.92 (14)
C14—C8—C9—C10	−173.35 (13)	C18—C13—C14—C8	61.33 (18)
C7—C8—C9—C10	62.39 (17)	C12—C13—C14—C15	165.52 (14)
C4—C5—C10—C1	−16.8 (2)	C17—C13—C14—C15	41.65 (16)
C6—C5—C10—C1	166.38 (16)	C18—C13—C14—C15	−69.93 (17)
C4—C5—C10—C19	101.45 (19)	C8—C14—C15—O3	73.1 (2)
C6—C5—C10—C19	−75.32 (18)	C13—C14—C15—O3	−160.83 (14)
C4—C5—C10—C9	−138.03 (16)	C8—C14—C15—C16	−167.34 (15)
C6—C5—C10—C9	45.2 (2)	C13—C14—C15—C16	−41.22 (17)
C2—C1—C10—C5	46.6 (2)	O3—C15—C16—C17	147.08 (15)
C2—C1—C10—C19	−70.07 (19)	C14—C15—C16—C17	24.51 (18)
C2—C1—C10—C9	166.46 (14)	C15—C16—C17—O4	179.09 (17)
C11—C9—C10—C5	179.05 (13)	C15—C16—C17—C13	1.08 (18)
C8—C9—C10—C5	−52.21 (17)	C12—C13—C17—O4	37.5 (2)
C11—C9—C10—C1	59.44 (18)	C14—C13—C17—O4	155.76 (17)
C8—C9—C10—C1	−171.82 (14)	C18—C13—C17—O4	−86.0 (2)
C11—C9—C10—C19	−63.08 (18)	C12—C13—C17—C16	−144.46 (16)
C8—C9—C10—C19	65.66 (18)	C14—C13—C17—C16	−26.23 (17)
C8—C9—C11—O2	162.83 (13)	C18—C13—C17—C16	92.00 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.88 (3)	1.94 (3)	2.800 (2)	164 (3)
O2—H2···O1ⁱⁱ	0.81 (3)	1.95 (3)	2.7600 (19)	180 (3)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₆O₄
M_r	318.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	113
a, b, c (Å)	7.8716 (8), 12.2725 (12), 17.2100 (16)
V (Å³)	1662.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn 724CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.981, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	17662, 2275, 2050
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.081, 1.03
No. of reflections	2275
No. of parameters	218
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

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
O3—H3···O2ⁱ	0.88 (3)	1.94 (3)	2.800 (2)	164 (3)
O2—H2···O1ⁱⁱ	0.81 (3)	1.95 (3)	2.7600 (19)	180 (3)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21076158), the Program for New Century Excellent Talents in Universities (No. NCET-08–0911) and the Foundation for Excellent Doctoral Dissertations of Tianjin University of Science and Technology in 2010 (No. B201001).

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