21-Hy-droxy-pregna-1,4-diene-3,20-dione.

The title compound, C(21)H(28)O(3), is a fungal transformed metabolite of decoxycorticosterone acetate, consisting of four fused rings A, B, C and D. Ring A is nearly planar, with a maximum deviation of 0.010 (3) Å from the least-squares plane, while the trans-fused rings B and C adopt chair conformations. The five-membered ring D is in an envelope conformation. The orientation of the side chain is stabilized by an intramolecular O-H⋯O hydrogen bond. In the crystal, adjecent mol-ecules are linked by C-H⋯O hydrogen bonds into extended zigzag chains along the a axis.

Related literature

The title compound was previously reported as the transformed metabolite of 11-de­oxy­corticosterone, see: Holland et al. (1995 ▶). For the crystal structure of the closely related compound corticosterone, see: Campsteyn et al. (1973 ▶) and for that of of 11-de­oxy­corticosterone, see: Dideberg et al. (1973 ▶); Dey et al. (1999 ▶).

Experimental

Crystal data

C21H28O3

M = 328.43

Monoclinic,

a = 7.5882 (9) Å

b = 11.3506 (13) Å

c = 10.5462 (12) Å

β = 102.258 (2)°

V = 887.64 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.36 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.972, T max = 0.990

5287 measured reflections

1739 independent reflections

1467 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 0.95

1739 reflections

219 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.13 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, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811028674/zb2014sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028674/zb2014Isup2.hkl

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

C21H28O3	F(000) = 356
Mr = 328.43	Dx = 1.229 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.5882 (9) Å	Cell parameters from 1378 reflections
b = 11.3506 (13) Å	θ = 2.0–25.5°
c = 10.5462 (12) Å	µ = 0.08 mm−1
β = 102.258 (2)°	T = 298 K
V = 887.64 (18) Å3	Block, colourless
Z = 2	0.36 × 0.13 × 0.12 mm

Bruker SMART APEX CCD area-detector diffractometer	1739 independent reflections
Radiation source: fine-focus sealed tube	1467 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 8.33 pixels mm-1	θmax = 25.5°, θmin = 2.0°
ω scan	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→13
Tmin = 0.972, Tmax = 0.990	l = −8→12
5287 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0661P)2 + 0.090P] where P = (Fo2 + 2Fc2)/3
1739 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.14 e Å−3
1 restraint	Δρmin = −0.13 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	0.5573 (4)	0.6466 (3)	0.9017 (2)	0.0945 (9)
O2	0.2867 (4)	0.3644 (3)	−0.2454 (2)	0.0913 (9)
H1O2	0.1895	0.4096	−0.2788	0.110*
O3	0.0016 (3)	0.4543 (3)	−0.1825 (2)	0.0826 (9)
C1	0.5718 (4)	0.6862 (3)	0.5714 (3)	0.0618 (9)
H1A	0.6579	0.6870	0.5203	0.074*
C2	0.6286 (4)	0.6644 (4)	0.6965 (3)	0.0685 (10)
H2A	0.7504	0.6497	0.7289	0.082*
C3	0.5054 (4)	0.6630 (3)	0.7843 (3)	0.0629 (8)
C4	0.3171 (4)	0.6834 (3)	0.7260 (3)	0.0567 (8)
H4A	0.2338	0.6820	0.7791	0.068*
C5	0.2577 (4)	0.7042 (3)	0.5998 (3)	0.0454 (7)
C6	0.0594 (4)	0.7164 (3)	0.5427 (3)	0.0587 (8)
H6A	0.0351	0.7927	0.5011	0.070*
H6B	−0.0086	0.7106	0.6107	0.070*
C7	0.0023 (4)	0.6184 (3)	0.4432 (3)	0.0543 (8)
H7A	0.0165	0.5428	0.4870	0.065*
H7B	−0.1241	0.6279	0.4027	0.065*
C8	0.1135 (3)	0.6197 (2)	0.3392 (2)	0.0374 (6)
H8A	0.0915	0.6947	0.2924	0.045*
C9	0.3169 (3)	0.6114 (2)	0.4003 (2)	0.0391 (6)
H9A	0.3345	0.5360	0.4465	0.047*
C10	0.3807 (3)	0.7096 (3)	0.5053 (2)	0.0441 (7)
C11	0.4304 (4)	0.6053 (3)	0.2956 (3)	0.0520 (8)
H11A	0.4262	0.6814	0.2532	0.062*
H11B	0.5549	0.5898	0.3373	0.062*
C12	0.3677 (3)	0.5108 (3)	0.1926 (3)	0.0496 (7)
H12A	0.4374	0.5169	0.1257	0.059*
H12B	0.3889	0.4335	0.2320	0.059*
C13	0.1683 (3)	0.5243 (2)	0.1315 (2)	0.0374 (6)
C14	0.0637 (3)	0.5206 (2)	0.2418 (2)	0.0371 (6)
H14A	0.0989	0.4472	0.2894	0.045*
C15	−0.1335 (4)	0.5052 (3)	0.1719 (3)	0.0515 (7)
H15A	−0.2019	0.4657	0.2273	0.062*
H15B	−0.1889	0.5809	0.1460	0.062*
C16	−0.1246 (4)	0.4299 (3)	0.0534 (3)	0.0572 (8)
H16A	−0.1928	0.4667	−0.0248	0.069*
H16B	−0.1748	0.3524	0.0617	0.069*
C17	0.0763 (3)	0.4196 (3)	0.0464 (2)	0.0442 (6)
H17A	0.1233	0.3460	0.0893	0.053*
C18	0.1330 (5)	0.6381 (3)	0.0533 (3)	0.0561 (8)
H18A	0.1603	0.7044	0.1106	0.084*
H18B	0.0086	0.6412	0.0094	0.084*
H18C	0.2080	0.6403	−0.0094	0.084*
C19	0.3717 (5)	0.8342 (3)	0.4439 (3)	0.0665 (9)
H19A	0.3905	0.8925	0.5113	0.100*
H19B	0.2554	0.8457	0.3881	0.100*
H19C	0.4635	0.8415	0.3943	0.100*
C20	0.1086 (4)	0.4173 (3)	−0.0904 (3)	0.0487 (7)
C21	0.2832 (5)	0.3690 (4)	−0.1131 (3)	0.0672 (9)
H22A	0.3817	0.4181	−0.0685	0.081*
H22B	0.3013	0.2903	−0.0767	0.081*

	U11	U22	U33	U12	U13	U23
O1	0.104 (2)	0.128 (2)	0.0422 (12)	0.0043 (19)	−0.0030 (12)	0.0045 (16)
O2	0.1074 (19)	0.113 (2)	0.0626 (15)	0.0171 (18)	0.0394 (14)	−0.0185 (16)
O3	0.0769 (16)	0.123 (2)	0.0423 (11)	0.0197 (15)	0.0010 (11)	−0.0080 (13)
C1	0.0358 (13)	0.100 (3)	0.0503 (17)	−0.0076 (16)	0.0113 (13)	−0.0282 (18)
C2	0.0459 (16)	0.100 (3)	0.0544 (18)	0.0067 (18)	−0.0006 (15)	−0.022 (2)
C3	0.072 (2)	0.072 (2)	0.0398 (15)	−0.0014 (18)	0.0019 (15)	−0.0067 (16)
C4	0.0578 (16)	0.079 (2)	0.0381 (14)	−0.0107 (16)	0.0206 (13)	−0.0129 (15)
C5	0.0430 (13)	0.0529 (17)	0.0418 (14)	−0.0062 (12)	0.0127 (12)	−0.0123 (13)
C6	0.0418 (14)	0.086 (2)	0.0511 (17)	0.0021 (15)	0.0167 (13)	−0.0210 (17)
C7	0.0346 (13)	0.079 (2)	0.0510 (16)	−0.0073 (14)	0.0138 (12)	−0.0163 (16)
C8	0.0332 (12)	0.0424 (14)	0.0374 (12)	0.0011 (11)	0.0091 (10)	−0.0030 (11)
C9	0.0343 (12)	0.0466 (14)	0.0378 (13)	−0.0019 (11)	0.0111 (11)	−0.0039 (12)
C10	0.0390 (13)	0.0617 (18)	0.0338 (13)	−0.0067 (12)	0.0130 (11)	−0.0076 (13)
C11	0.0353 (13)	0.081 (2)	0.0430 (14)	−0.0117 (13)	0.0161 (12)	−0.0176 (15)
C12	0.0365 (14)	0.072 (2)	0.0435 (14)	0.0019 (13)	0.0164 (12)	−0.0132 (15)
C13	0.0384 (13)	0.0406 (14)	0.0347 (12)	0.0018 (11)	0.0115 (11)	−0.0028 (12)
C14	0.0350 (13)	0.0384 (13)	0.0383 (13)	−0.0001 (10)	0.0086 (11)	0.0010 (11)
C15	0.0371 (14)	0.0630 (19)	0.0541 (16)	−0.0042 (13)	0.0093 (12)	−0.0162 (15)
C16	0.0489 (15)	0.0660 (19)	0.0572 (17)	−0.0109 (15)	0.0126 (14)	−0.0192 (16)
C17	0.0481 (14)	0.0418 (14)	0.0423 (14)	−0.0010 (13)	0.0089 (12)	−0.0069 (13)
C18	0.083 (2)	0.0443 (16)	0.0436 (15)	−0.0050 (15)	0.0185 (14)	−0.0006 (13)
C19	0.085 (2)	0.061 (2)	0.0556 (19)	−0.0246 (18)	0.0177 (17)	−0.0115 (16)
C20	0.0550 (15)	0.0485 (16)	0.0416 (14)	−0.0026 (14)	0.0079 (13)	−0.0127 (13)
C21	0.075 (2)	0.074 (2)	0.0573 (19)	0.0070 (18)	0.0232 (16)	−0.0122 (17)

O1—C3	1.231 (4)	C11—H11A	0.9700
O2—C21	1.402 (4)	C11—H11B	0.9700
O2—H1O2	0.9067	C12—C13	1.522 (4)
O3—C20	1.202 (3)	C12—H12A	0.9700
C1—C2	1.321 (4)	C12—H12B	0.9700
C1—C10	1.493 (4)	C13—C18	1.525 (4)
C1—H1A	0.9300	C13—C14	1.542 (3)
C2—C3	1.450 (5)	C13—C17	1.562 (4)
C2—H2A	0.9300	C14—C15	1.531 (3)
C3—C4	1.450 (4)	C14—H14A	0.9800
C4—C5	1.332 (4)	C15—C16	1.528 (4)
C4—H4A	0.9300	C15—H15A	0.9700
C5—C6	1.504 (4)	C15—H15B	0.9700
C5—C10	1.505 (4)	C16—C17	1.546 (4)
C6—C7	1.527 (4)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700
C6—H6B	0.9700	C17—C20	1.514 (4)
C7—C8	1.519 (4)	C17—H17A	0.9800
C7—H7A	0.9700	C18—H18A	0.9600
C7—H7B	0.9700	C18—H18B	0.9600
C8—C14	1.517 (3)	C18—H18C	0.9600
C8—C9	1.544 (3)	C19—H19A	0.9600
C8—H8A	0.9800	C19—H19B	0.9600
C9—C11	1.539 (3)	C19—H19C	0.9600
C9—C10	1.574 (4)	C20—C21	1.500 (4)
C9—H9A	0.9800	C21—H22A	0.9700
C10—C19	1.551 (5)	C21—H22B	0.9700
C11—C12	1.528 (4)
C21—O2—H1O2	100.3	C13—C12—H12B	109.4
C2—C1—C10	125.3 (3)	C11—C12—H12B	109.4
C2—C1—H1A	117.4	H12A—C12—H12B	108.0
C10—C1—H1A	117.4	C12—C13—C18	111.0 (2)
C1—C2—C3	121.5 (3)	C12—C13—C14	107.63 (19)
C1—C2—H2A	119.2	C18—C13—C14	111.8 (2)
C3—C2—H2A	119.2	C12—C13—C17	116.7 (2)
O1—C3—C2	122.2 (3)	C18—C13—C17	109.15 (19)
O1—C3—C4	121.8 (3)	C14—C13—C17	100.0 (2)
C2—C3—C4	116.0 (2)	C8—C14—C15	119.2 (2)
C5—C4—C3	123.1 (3)	C8—C14—C13	113.4 (2)
C5—C4—H4A	118.4	C15—C14—C13	104.29 (19)
C3—C4—H4A	118.4	C8—C14—H14A	106.4
C4—C5—C6	120.9 (3)	C15—C14—H14A	106.4
C4—C5—C10	122.9 (2)	C13—C14—H14A	106.4
C6—C5—C10	116.1 (2)	C16—C15—C14	104.4 (2)
C5—C6—C7	108.8 (2)	C16—C15—H15A	110.9
C5—C6—H6A	109.9	C14—C15—H15A	110.9
C7—C6—H6A	109.9	C16—C15—H15B	110.9
C5—C6—H6B	109.9	C14—C15—H15B	110.9
C7—C6—H6B	109.9	H15A—C15—H15B	108.9
H6A—C6—H6B	108.3	C15—C16—C17	107.3 (2)
C8—C7—C6	111.6 (2)	C15—C16—H16A	110.3
C8—C7—H7A	109.3	C17—C16—H16A	110.3
C6—C7—H7A	109.3	C15—C16—H16B	110.3
C8—C7—H7B	109.3	C17—C16—H16B	110.3
C6—C7—H7B	109.3	H16A—C16—H16B	108.5
H7A—C7—H7B	108.0	C20—C17—C16	114.0 (2)
C14—C8—C7	112.6 (2)	C20—C17—C13	114.7 (2)
C14—C8—C9	108.66 (19)	C16—C17—C13	103.9 (2)
C7—C8—C9	111.0 (2)	C20—C17—H17A	108.0
C14—C8—H8A	108.1	C16—C17—H17A	108.0
C7—C8—H8A	108.1	C13—C17—H17A	108.0
C9—C8—H8A	108.1	C13—C18—H18A	109.5
C11—C9—C8	111.5 (2)	C13—C18—H18B	109.5
C11—C9—C10	113.7 (2)	H18A—C18—H18B	109.5
C8—C9—C10	112.4 (2)	C13—C18—H18C	109.5
C11—C9—H9A	106.2	H18A—C18—H18C	109.5
C8—C9—H9A	106.2	H18B—C18—H18C	109.5
C10—C9—H9A	106.2	C10—C19—H19A	109.5
C1—C10—C5	111.2 (2)	C10—C19—H19B	109.5
C1—C10—C19	108.0 (3)	H19A—C19—H19B	109.5
C5—C10—C19	109.6 (2)	C10—C19—H19C	109.5
C1—C10—C9	109.0 (2)	H19A—C19—H19C	109.5
C5—C10—C9	107.2 (2)	H19B—C19—H19C	109.5
C19—C10—C9	111.9 (2)	O3—C20—C21	117.8 (3)
C12—C11—C9	113.8 (2)	O3—C20—C17	123.1 (3)
C12—C11—H11A	108.8	C21—C20—C17	119.1 (3)
C9—C11—H11A	108.8	O2—C21—C20	112.2 (3)
C12—C11—H11B	108.8	O2—C21—H22A	109.2
C9—C11—H11B	108.8	C20—C21—H22A	109.2
H11A—C11—H11B	107.7	O2—C21—H22B	109.2
C13—C12—C11	111.2 (2)	C20—C21—H22B	109.2
C13—C12—H12A	109.4	H22A—C21—H22B	107.9
C11—C12—H12A	109.4
C10—C1—C2—C3	−0.9 (6)	C10—C9—C11—C12	−179.4 (2)
C1—C2—C3—O1	−177.6 (4)	C9—C11—C12—C13	53.7 (3)
C1—C2—C3—C4	1.6 (6)	C11—C12—C13—C18	66.5 (3)
O1—C3—C4—C5	178.4 (4)	C11—C12—C13—C14	−56.2 (3)
C2—C3—C4—C5	−0.9 (5)	C11—C12—C13—C17	−167.6 (2)
C3—C4—C5—C6	175.7 (3)	C7—C8—C14—C15	53.7 (3)
C3—C4—C5—C10	−0.6 (5)	C9—C8—C14—C15	177.0 (2)
C4—C5—C6—C7	−117.8 (3)	C7—C8—C14—C13	177.0 (2)
C10—C5—C6—C7	58.7 (4)	C9—C8—C14—C13	−59.6 (3)
C5—C6—C7—C8	−56.2 (3)	C12—C13—C14—C8	61.7 (3)
C6—C7—C8—C14	178.0 (2)	C18—C13—C14—C8	−60.5 (3)
C6—C7—C8—C9	56.0 (3)	C17—C13—C14—C8	−175.93 (19)
C14—C8—C9—C11	52.3 (3)	C12—C13—C14—C15	−167.1 (2)
C7—C8—C9—C11	176.6 (2)	C18—C13—C14—C15	70.7 (3)
C14—C8—C9—C10	−178.8 (2)	C17—C13—C14—C15	−44.7 (2)
C7—C8—C9—C10	−54.4 (3)	C8—C14—C15—C16	161.2 (3)
C2—C1—C10—C5	−0.5 (5)	C13—C14—C15—C16	33.4 (3)
C2—C1—C10—C19	119.7 (4)	C14—C15—C16—C17	−8.4 (3)
C2—C1—C10—C9	−118.5 (4)	C15—C16—C17—C20	−144.8 (3)
C4—C5—C10—C1	1.3 (4)	C15—C16—C17—C13	−19.3 (3)
C6—C5—C10—C1	−175.1 (3)	C12—C13—C17—C20	−80.5 (3)
C4—C5—C10—C19	−118.0 (3)	C18—C13—C17—C20	46.4 (3)
C6—C5—C10—C19	65.5 (3)	C14—C13—C17—C20	163.8 (2)
C4—C5—C10—C9	120.4 (3)	C12—C13—C17—C16	154.4 (2)
C6—C5—C10—C9	−56.1 (3)	C18—C13—C17—C16	−78.8 (3)
C11—C9—C10—C1	−59.5 (3)	C14—C13—C17—C16	38.7 (3)
C8—C9—C10—C1	172.8 (2)	C16—C17—C20—O3	21.1 (4)
C11—C9—C10—C5	−179.9 (2)	C13—C17—C20—O3	−98.5 (3)
C8—C9—C10—C5	52.3 (3)	C16—C17—C20—C21	−160.2 (3)
C11—C9—C10—C19	59.9 (3)	C13—C17—C20—C21	80.2 (3)
C8—C9—C10—C19	−67.8 (3)	O3—C20—C21—O2	−5.9 (5)
C8—C9—C11—C12	−51.2 (3)	C17—C20—C21—O2	175.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O3	0.91	1.98	2.602 (4)	124
C21—H22B···O1i	0.97	2.53	3.415 (5)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O3	0.91	1.98	2.602 (4)	124
C21—H22B⋯O1i	0.97	2.53	3.415 (5)	152

Symmetry code: (i) .