11β,17aα-Dihydr-oxy-17aβ-methyl-d-homoandrosta-1,4-diene-3,17-dione monohydrate.

In the title compound, C(21)H(28)O(4)·H(2)O, the cyclo-hexa-dienone ring is planar (r.m.s. deviation 0.0186 Å), whereas the two cyclo-hexane rings and the cyclo-hexa-none ring adopt chair conformations. The crystal structure is stabilized by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For general background, see: Conrow (1999 ▶). For details of the synthesis, see: Huo (2003 ▶).

Experimental

Crystal data

C21H28O4·H2O

M = 362.45

Monoclinic,

a = 6.641 (2) Å

b = 18.642 (6) Å

c = 8.017 (3) Å

β = 103.797 (4)°

V = 963.9 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.978, T max = 0.987

4866 measured reflections

2182 independent reflections

1778 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.104

S = 0.97

2182 reflections

254 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.15 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010770/gk2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010770/gk2193Isup2.hkl

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

C21H28O4·H2O	F(000) = 392
Mr = 362.45	Dx = 1.249 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1024 reflections
a = 6.641 (2) Å	θ = 2.8–27.1°
b = 18.642 (6) Å	µ = 0.09 mm−1
c = 8.017 (3) Å	T = 293 K
β = 103.797 (4)°	Plate, colorless
V = 963.9 (6) Å3	0.25 × 0.20 × 0.15 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	2182 independent reflections
Radiation source: fine-focus sealed tube	1778 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 27.1°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −8→8
Tmin = 0.978, Tmax = 0.987	k = −23→23
4866 measured reflections	l = −10→6

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3
2182 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 0.24 e Å−3
5 restraints	Δρmin = −0.15 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	0.1926 (4)	0.41488 (11)	0.9326 (3)	0.0555 (5)
O2	0.6229 (3)	0.61548 (11)	0.4180 (3)	0.0509 (5)
H2X	0.691 (4)	0.6524 (13)	0.440 (4)	0.055 (10)*
O3	0.1121 (4)	0.77632 (12)	−0.2435 (3)	0.0583 (6)
O4	−0.0063 (3)	0.78258 (11)	0.1395 (3)	0.0499 (5)
H4X	−0.050 (4)	0.8214 (11)	0.102 (4)	0.039 (8)*
O5	0.8509 (4)	0.74238 (15)	0.4291 (4)	0.0686 (7)
H5Y	0.936 (5)	0.756 (3)	0.523 (4)	0.089 (15)*
H5X	0.894 (6)	0.750 (2)	0.340 (4)	0.086 (14)*
C1	0.4634 (4)	0.52002 (13)	0.6909 (4)	0.0427 (6)
H1	0.5753	0.5514	0.7111	0.051*
C2	0.4114 (4)	0.49166 (14)	0.8260 (4)	0.0433 (6)
H2	0.4894	0.5028	0.9355	0.052*
C3	0.2351 (4)	0.44350 (13)	0.8073 (4)	0.0409 (6)
C4	0.1154 (4)	0.43065 (13)	0.6331 (4)	0.0403 (6)
H4	−0.0030	0.4023	0.6169	0.048*
C5	0.1682 (4)	0.45781 (13)	0.4951 (3)	0.0371 (6)
C6	0.0458 (4)	0.44352 (13)	0.3178 (4)	0.0437 (6)
H6A	−0.0788	0.4173	0.3230	0.052*
H6B	0.1265	0.4136	0.2591	0.052*
C7	−0.0148 (4)	0.51213 (14)	0.2155 (4)	0.0418 (6)
H7A	−0.1214	0.5364	0.2585	0.050*
H7B	−0.0738	0.4997	0.0964	0.050*
C8	0.1668 (4)	0.56397 (12)	0.2240 (3)	0.0328 (5)
H8	0.2664	0.5417	0.1673	0.039*
C9	0.2742 (4)	0.57722 (12)	0.4142 (3)	0.0332 (5)
H9	0.1632	0.5932	0.4671	0.040*
C10	0.3559 (4)	0.50534 (13)	0.5089 (3)	0.0366 (6)
C11	0.4311 (4)	0.63875 (13)	0.4440 (4)	0.0404 (6)
H11	0.4551	0.6519	0.5655	0.048*
C12	0.3482 (4)	0.70560 (12)	0.3407 (3)	0.0392 (6)
H12A	0.4596	0.7404	0.3542	0.047*
H12B	0.2406	0.7265	0.3886	0.047*
C13	0.2592 (4)	0.69250 (12)	0.1481 (3)	0.0337 (5)
C14	0.0878 (4)	0.63452 (12)	0.1298 (3)	0.0342 (5)
H14	−0.0177	0.6538	0.1847	0.041*
C15	−0.0196 (5)	0.62098 (16)	−0.0586 (4)	0.0485 (7)
H15A	0.0780	0.5987	−0.1153	0.058*
H15B	−0.1337	0.5879	−0.0644	0.058*
C16	−0.1023 (5)	0.68968 (17)	−0.1538 (4)	0.0535 (7)
H16A	−0.1490	0.6796	−0.2756	0.064*
H16B	−0.2203	0.7067	−0.1135	0.064*
C17	0.0599 (4)	0.74649 (14)	−0.1266 (4)	0.0415 (6)
C17A	0.1594 (4)	0.76373 (13)	0.0615 (3)	0.0396 (6)
C18	0.4297 (4)	0.67001 (16)	0.0598 (4)	0.0453 (6)
H18A	0.4766	0.6226	0.0963	0.068*
H18B	0.5437	0.7030	0.0901	0.068*
H18C	0.3758	0.6704	−0.0625	0.068*
C19	0.5131 (4)	0.46446 (16)	0.4290 (4)	0.0526 (7)
H19A	0.5383	0.4178	0.4805	0.079*
H19B	0.6408	0.4908	0.4493	0.079*
H19C	0.4575	0.4594	0.3075	0.079*
C20	0.3116 (5)	0.82621 (15)	0.0757 (4)	0.0559 (8)
H20A	0.3711	0.8364	0.1946	0.084*
H20B	0.2395	0.8678	0.0213	0.084*
H20C	0.4196	0.8136	0.0201	0.084*

	U11	U22	U33	U12	U13	U23
O1	0.0786 (14)	0.0499 (11)	0.0436 (12)	−0.0146 (10)	0.0255 (10)	0.0001 (9)
O2	0.0356 (9)	0.0403 (11)	0.0753 (15)	−0.0050 (8)	0.0104 (10)	0.0063 (10)
O3	0.0817 (14)	0.0535 (12)	0.0414 (12)	−0.0120 (11)	0.0181 (10)	0.0069 (10)
O4	0.0664 (12)	0.0407 (10)	0.0477 (12)	0.0179 (9)	0.0239 (10)	0.0110 (9)
O5	0.0723 (15)	0.0808 (17)	0.0542 (15)	−0.0300 (13)	0.0177 (13)	0.0031 (13)
C1	0.0380 (13)	0.0372 (13)	0.0484 (16)	−0.0063 (11)	0.0014 (12)	0.0077 (12)
C2	0.0526 (15)	0.0356 (13)	0.0384 (15)	−0.0026 (11)	0.0040 (12)	0.0039 (11)
C3	0.0528 (14)	0.0294 (12)	0.0445 (16)	0.0016 (11)	0.0195 (12)	0.0001 (11)
C4	0.0419 (13)	0.0328 (12)	0.0482 (16)	−0.0065 (10)	0.0147 (12)	0.0030 (11)
C5	0.0410 (12)	0.0267 (11)	0.0430 (15)	−0.0010 (10)	0.0091 (11)	−0.0008 (10)
C6	0.0512 (14)	0.0335 (13)	0.0460 (15)	−0.0118 (11)	0.0111 (13)	−0.0026 (12)
C7	0.0439 (14)	0.0387 (13)	0.0404 (15)	−0.0111 (11)	0.0053 (12)	−0.0011 (12)
C8	0.0346 (12)	0.0295 (11)	0.0329 (13)	−0.0045 (9)	0.0055 (10)	−0.0011 (9)
C9	0.0339 (11)	0.0309 (11)	0.0345 (13)	−0.0027 (9)	0.0079 (10)	0.0011 (9)
C10	0.0339 (12)	0.0348 (13)	0.0414 (14)	−0.0007 (10)	0.0098 (10)	0.0072 (11)
C11	0.0410 (13)	0.0378 (13)	0.0385 (15)	−0.0083 (10)	0.0017 (11)	0.0030 (11)
C12	0.0460 (13)	0.0309 (12)	0.0385 (14)	−0.0086 (10)	0.0056 (11)	−0.0009 (10)
C13	0.0377 (12)	0.0283 (11)	0.0344 (13)	−0.0044 (9)	0.0073 (10)	−0.0003 (9)
C14	0.0350 (12)	0.0332 (12)	0.0337 (14)	−0.0032 (9)	0.0069 (10)	−0.0012 (10)
C15	0.0567 (16)	0.0434 (14)	0.0386 (15)	−0.0154 (13)	−0.0024 (13)	0.0006 (12)
C16	0.0551 (15)	0.0609 (18)	0.0382 (16)	−0.0120 (14)	−0.0014 (13)	0.0072 (13)
C17	0.0504 (14)	0.0373 (13)	0.0357 (15)	0.0037 (11)	0.0082 (12)	0.0060 (11)
C17A	0.0497 (14)	0.0338 (13)	0.0365 (14)	0.0013 (11)	0.0129 (12)	0.0019 (10)
C18	0.0452 (13)	0.0444 (14)	0.0498 (17)	−0.0029 (12)	0.0180 (12)	−0.0005 (12)
C19	0.0520 (16)	0.0423 (15)	0.068 (2)	0.0121 (13)	0.0239 (15)	0.0125 (14)
C20	0.075 (2)	0.0386 (15)	0.0492 (18)	−0.0124 (14)	0.0058 (15)	0.0027 (13)

O1—C3	1.228 (3)	C9—H9	0.9800
O2—C11	1.407 (3)	C10—C19	1.549 (4)
O2—H2X	0.821 (19)	C11—C12	1.525 (3)
O3—C17	1.209 (4)	C11—H11	0.9800
O4—C17A	1.433 (3)	C12—C13	1.535 (4)
O4—H4X	0.810 (18)	C12—H12A	0.9700
O5—H5Y	0.86 (2)	C12—H12B	0.9700
O5—H5X	0.85 (2)	C13—C18	1.531 (4)
C1—C2	1.323 (4)	C13—C14	1.551 (3)
C1—C10	1.489 (4)	C13—C17A	1.570 (3)
C1—H1	0.9300	C14—C15	1.530 (4)
C2—C3	1.454 (4)	C14—H14	0.9800
C2—H2	0.9300	C15—C16	1.524 (4)
C3—C4	1.452 (4)	C15—H15A	0.9700
C4—C5	1.337 (4)	C15—H15B	0.9700
C4—H4	0.9300	C16—C17	1.489 (4)
C5—C6	1.483 (4)	C16—H16A	0.9700
C5—C10	1.512 (3)	C16—H16B	0.9700
C6—C7	1.521 (4)	C17—C17A	1.529 (4)
C6—H6A	0.9700	C17A—C20	1.528 (4)
C6—H6B	0.9700	C18—H18A	0.9599
C7—C8	1.535 (3)	C18—H18B	0.9599
C7—H7A	0.9700	C18—H18C	0.9599
C7—H7B	0.9700	C19—H19A	0.9599
C8—C9	1.541 (3)	C19—H19B	0.9599
C8—C14	1.545 (3)	C19—H19C	0.9599
C8—H8	0.9800	C20—H20A	0.9599
C9—C11	1.530 (3)	C20—H20B	0.9599
C9—C10	1.571 (3)	C20—H20C	0.9599
C11—O2—H2X	101 (2)	C13—C12—H12A	108.6
C17A—O4—H4X	108 (2)	C11—C12—H12B	108.6
H5Y—O5—H5X	114 (4)	C13—C12—H12B	108.6
C2—C1—C10	124.8 (2)	H12A—C12—H12B	107.6
C2—C1—H1	117.6	C18—C13—C12	111.0 (2)
C10—C1—H1	117.6	C18—C13—C14	111.9 (2)
C1—C2—C3	121.5 (3)	C12—C13—C14	107.69 (19)
C1—C2—H2	119.2	C18—C13—C17A	107.9 (2)
C3—C2—H2	119.2	C12—C13—C17A	109.33 (19)
O1—C3—C4	122.3 (2)	C14—C13—C17A	108.94 (19)
O1—C3—C2	121.3 (3)	C15—C14—C8	111.5 (2)
C4—C3—C2	116.3 (2)	C15—C14—C13	111.5 (2)
C5—C4—C3	122.8 (2)	C8—C14—C13	113.00 (19)
C5—C4—H4	118.6	C15—C14—H14	106.8
C3—C4—H4	118.6	C8—C14—H14	106.8
C4—C5—C6	122.2 (2)	C13—C14—H14	106.8
C4—C5—C10	122.4 (2)	C16—C15—C14	112.5 (2)
C6—C5—C10	115.4 (2)	C16—C15—H15A	109.1
C5—C6—C7	112.3 (2)	C14—C15—H15A	109.1
C5—C6—H6A	109.1	C16—C15—H15B	109.1
C7—C6—H6A	109.1	C14—C15—H15B	109.1
C5—C6—H6B	109.1	H15A—C15—H15B	107.8
C7—C6—H6B	109.1	C17—C16—C15	111.3 (2)
H6A—C6—H6B	107.9	C17—C16—H16A	109.4
C6—C7—C8	113.7 (2)	C15—C16—H16A	109.4
C6—C7—H7A	108.8	C17—C16—H16B	109.4
C8—C7—H7A	108.8	C15—C16—H16B	109.4
C6—C7—H7B	108.8	H16A—C16—H16B	108.0
C8—C7—H7B	108.8	O3—C17—C16	123.0 (3)
H7A—C7—H7B	107.7	O3—C17—C17A	122.1 (3)
C7—C8—C9	108.5 (2)	C16—C17—C17A	114.9 (2)
C7—C8—C14	110.02 (19)	O4—C17A—C20	110.1 (2)
C9—C8—C14	111.72 (19)	O4—C17A—C17	106.6 (2)
C7—C8—H8	108.8	C20—C17A—C17	110.9 (2)
C9—C8—H8	108.8	O4—C17A—C13	107.5 (2)
C14—C8—H8	108.8	C20—C17A—C13	114.2 (2)
C11—C9—C8	114.3 (2)	C17—C17A—C13	107.2 (2)
C11—C9—C10	114.83 (19)	C13—C18—H18A	109.5
C8—C9—C10	111.49 (19)	C13—C18—H18B	109.5
C11—C9—H9	105.0	H18A—C18—H18B	109.5
C8—C9—H9	105.0	C13—C18—H18C	109.5
C10—C9—H9	105.0	H18A—C18—H18C	109.5
C1—C10—C5	111.9 (2)	H18B—C18—H18C	109.5
C1—C10—C19	106.4 (2)	C10—C19—H19A	109.5
C5—C10—C19	107.8 (2)	C10—C19—H19B	109.5
C1—C10—C9	110.3 (2)	H19A—C19—H19B	109.5
C5—C10—C9	106.31 (19)	C10—C19—H19C	109.5
C19—C10—C9	114.1 (2)	H19A—C19—H19C	109.5
O2—C11—C12	113.2 (2)	H19B—C19—H19C	109.5
O2—C11—C9	110.6 (2)	C17A—C20—H20A	109.5
C12—C11—C9	112.6 (2)	C17A—C20—H20B	109.5
O2—C11—H11	106.7	H20A—C20—H20B	109.5
C12—C11—H11	106.7	C17A—C20—H20C	109.5
C9—C11—H11	106.7	H20A—C20—H20C	109.5
C11—C12—C13	114.8 (2)	H20B—C20—H20C	109.5
C11—C12—H12A	108.6
C10—C1—C2—C3	−1.7 (4)	O2—C11—C12—C13	74.9 (3)
C1—C2—C3—O1	176.9 (3)	C9—C11—C12—C13	−51.5 (3)
C1—C2—C3—C4	−2.3 (4)	C11—C12—C13—C18	−66.8 (3)
O1—C3—C4—C5	−175.5 (3)	C11—C12—C13—C14	56.0 (3)
C2—C3—C4—C5	3.7 (4)	C11—C12—C13—C17A	174.3 (2)
C3—C4—C5—C6	179.3 (2)	C7—C8—C14—C15	−59.1 (3)
C3—C4—C5—C10	−1.0 (4)	C9—C8—C14—C15	−179.7 (2)
C4—C5—C6—C7	127.3 (3)	C7—C8—C14—C13	174.4 (2)
C10—C5—C6—C7	−52.5 (3)	C9—C8—C14—C13	53.8 (3)
C5—C6—C7—C8	49.2 (3)	C18—C13—C14—C15	−61.1 (3)
C6—C7—C8—C9	−52.6 (3)	C12—C13—C14—C15	176.6 (2)
C6—C7—C8—C14	−175.2 (2)	C17A—C13—C14—C15	58.1 (3)
C7—C8—C9—C11	−168.7 (2)	C18—C13—C14—C8	65.4 (3)
C14—C8—C9—C11	−47.2 (3)	C12—C13—C14—C8	−56.9 (3)
C7—C8—C9—C10	59.0 (2)	C17A—C13—C14—C8	−175.36 (19)
C14—C8—C9—C10	−179.54 (19)	C8—C14—C15—C16	179.1 (2)
C2—C1—C10—C5	4.1 (4)	C13—C14—C15—C16	−53.6 (3)
C2—C1—C10—C19	−113.5 (3)	C14—C15—C16—C17	50.2 (4)
C2—C1—C10—C9	122.3 (3)	C15—C16—C17—O3	124.4 (3)
C4—C5—C10—C1	−2.7 (3)	C15—C16—C17—C17A	−54.6 (4)
C6—C5—C10—C1	177.0 (2)	O3—C17—C17A—O4	125.0 (3)
C4—C5—C10—C19	114.0 (3)	C16—C17—C17A—O4	−56.0 (3)
C6—C5—C10—C19	−66.2 (3)	O3—C17—C17A—C20	5.2 (4)
C4—C5—C10—C9	−123.2 (3)	C16—C17—C17A—C20	−175.8 (3)
C6—C5—C10—C9	56.6 (3)	O3—C17—C17A—C13	−120.1 (3)
C11—C9—C10—C1	46.5 (3)	C16—C17—C17A—C13	58.9 (3)
C8—C9—C10—C1	178.55 (19)	C18—C13—C17A—O4	177.4 (2)
C11—C9—C10—C5	168.0 (2)	C12—C13—C17A—O4	−61.7 (2)
C8—C9—C10—C5	−59.9 (3)	C14—C13—C17A—O4	55.7 (3)
C11—C9—C10—C19	−73.2 (3)	C18—C13—C17A—C20	−60.2 (3)
C8—C9—C10—C19	58.8 (3)	C12—C13—C17A—C20	60.7 (3)
C8—C9—C11—O2	−81.9 (3)	C14—C13—C17A—C20	178.2 (2)
C10—C9—C11—O2	48.8 (3)	C18—C13—C17A—C17	63.1 (3)
C8—C9—C11—C12	45.8 (3)	C12—C13—C17A—C17	−176.0 (2)
C10—C9—C11—C12	176.5 (2)	C14—C13—C17A—C17	−58.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2X···O5	0.82 (2)	2.00 (2)	2.799 (3)	166 (3)
C1—H1···O2	0.93	2.72	3.191 (3)	112
C12—H12A···O5	0.97	2.52	3.315 (4)	139
C18—H18A···O2	0.96	2.53	3.028 (4)	112
C19—H19B···O2	0.96	2.34	2.915 (4)	118
O4—H4X···O1i	0.81 (2)	1.97 (2)	2.758 (3)	164 (3)
O5—H5Y···O3ii	0.86 (2)	1.99 (2)	2.851 (4)	171 (4)
O5—H5X···O4iii	0.85 (2)	1.97 (2)	2.811 (3)	172 (4)
C16—H16A···O5iv	0.97	2.64	3.427 (4)	138
C6—H6A···O3v	0.97	2.70	3.297 (3)	120

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2X⋯O5	0.821 (19)	2.00 (2)	2.799 (3)	166 (3)
O4—H4X⋯O1i	0.810 (18)	1.97 (2)	2.758 (3)	164 (3)
O5—H5Y⋯O3ii	0.86 (2)	1.99 (2)	2.851 (4)	171 (4)
O5—H5X⋯O4iii	0.85 (2)	1.97 (2)	2.811 (3)	172 (4)

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