11α,15α-Dihy-droxy-androst-4-ene-3,17-dione.

The title compound, C(19)H(26)O(4), was biotransformed from androstenedione. In the crystal, inter-molecular 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 cyclo-pentane 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 = 318.40

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.081

S = 1.03

2275 reflections

218 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.20 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038608/lw2070sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038608/lw2070Isup2.hkl

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

C19H26O4	Dx = 1.272 Mg m−3
Mr = 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

Rigaku Saturn 724CCD diffractometer	2275 independent reflections
Radiation source: rotating anode	2050 reflections with I > 2σ(I)
multilayer	Rint = 0.047
Detector resolution: 14.22 pixels mm-1	θmax = 27.9°, θmin = 2.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→16
Tmin = 0.981, Tmax = 0.990	l = −21→22
17662 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)] = 0.037	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(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3
2275 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) ; (ii) .