3β-Acet-oxy-19-hy-droxy-Δ(5)-pregnen-20-one.

In the title compound, C(23)H(34)O(4), the C/D and D/E rings are trans fused and the A/B ring possesses an anti fusion. The two cyclo-hexane rings adopt a chair conformation while the cyclo-hexene ring exhibits a half-chair conformation. The cyclo-pentane ring displays an envelope conformation with the C atom bearing the methyl group as the flap. In the crystal, the mol-ecules are linked by O-H⋯O hydrogen bonds, forming chains along the b axis.

Related literature

For an overview of steroids as biologically important mol­ecules, see: Fieser & Fieser (1961) ▶; Hanson (2010 ▶). For examples of steroids possessing a rearranged A/B-ring system, see: Du et al. (2008 ▶); Aoki et al. (2006 ▶); Flyer et al. (2010 ▶). For related C-19-functionalized steroids, see: El Sheikh et al. (2007 ▶); Shenvi et al. (2008 ▶). For an overview of remote functionalization, see: Reese (2001 ▶); Heusler & Kalvoda (1964 ▶). For the first synthesis of the title compound, see: Halpern et al. (1963 ▶). For examples of the title compound as an inter­mediate for rearranged A/B-ring systems, see: Knox et al. (1965 ▶); Kranz et al. (2011 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C23H34O4

M = 374.50

Orthorhombic,

a = 8.6960 (6) Å

b = 12.3708 (4) Å

c = 18.3303 (10) Å

V = 1971.91 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.3 × 0.3 × 0.3 mm

Data collection

Nonius KappaCCD diffractometer

9889 measured reflections

2457 independent reflections

1943 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.079

S = 0.99

2457 reflections

247 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Hooft 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SCHAKAL99 (Keller, 1999 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813002493/lr2076sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002493/lr2076Isup2.hkl

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

C23H34O4	F(000) = 816
Mr = 374.50	Dx = 1.261 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9889 reflections
a = 8.6960 (6) Å	θ = 2.0–27.0°
b = 12.3708 (4) Å	µ = 0.08 mm−1
c = 18.3303 (10) Å	T = 100 K
V = 1971.91 (18) Å3	Prism, colourless
Z = 4	0.3 × 0.3 × 0.3 mm

Nonius KappaCCD diffractometer	1943 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 27.0°, θmin = 2.0°
Phi/ω–Scans scans	h = −6→11
9889 measured reflections	k = −12→15
2457 independent reflections	l = −21→23

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) = 0.079	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3
2457 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.23 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	−0.03545 (17)	0.54114 (10)	0.67613 (8)	0.0195 (3)
O2	−0.13591 (19)	0.70584 (11)	0.65410 (8)	0.0267 (4)
O3	0.20344 (19)	0.38623 (10)	0.94444 (8)	0.0246 (4)
H3A	0.1481	0.3467	0.9180	0.037*
O4	−0.0183 (2)	0.54920 (11)	1.30301 (9)	0.0360 (5)
C1	−0.0748 (2)	0.47261 (15)	0.87606 (11)	0.0170 (5)
H1A	−0.0708	0.4021	0.9016	0.020*
H1B	−0.1789	0.5030	0.8836	0.020*
C2	−0.0516 (3)	0.45275 (14)	0.79398 (11)	0.0182 (5)
H2A	0.0481	0.4161	0.7856	0.022*
H2B	−0.1345	0.4055	0.7752	0.022*
C3	−0.0541 (3)	0.55950 (14)	0.75430 (11)	0.0180 (5)
H3	−0.1547	0.5964	0.7634	0.022*
C4	0.0760 (3)	0.63061 (15)	0.78170 (11)	0.0188 (5)
H4A	0.1758	0.5953	0.7713	0.023*
H4B	0.0738	0.7007	0.7557	0.023*
C5	0.0611 (2)	0.64986 (15)	0.86293 (11)	0.0165 (5)
C6	0.0610 (3)	0.75048 (15)	0.88802 (11)	0.0172 (5)
H6	0.0682	0.8072	0.8532	0.021*
C7	0.0504 (3)	0.78158 (14)	0.96614 (11)	0.0172 (5)
H7A	−0.0510	0.8155	0.9751	0.021*
H7B	0.1306	0.8360	0.9769	0.021*
C8	0.0700 (3)	0.68595 (14)	1.01773 (11)	0.0160 (5)
H8	0.1819	0.6683	1.0216	0.019*
C9	−0.0163 (2)	0.58588 (14)	0.98836 (11)	0.0165 (5)
H9	−0.1252	0.6093	0.9807	0.020*
C10	0.0442 (2)	0.54967 (14)	0.91196 (11)	0.0161 (5)
C11	−0.0222 (3)	0.49458 (14)	1.04593 (11)	0.0193 (5)
H20A	−0.0894	0.4359	1.0277	0.023*
H20B	0.0825	0.4644	1.0522	0.023*
C12	−0.0822 (3)	0.53265 (15)	1.12077 (11)	0.0185 (5)
H12A	−0.1904	0.5564	1.1159	0.022*
H12B	−0.0793	0.4716	1.1556	0.022*
C13	0.0157 (2)	0.62660 (15)	1.15054 (11)	0.0158 (5)
C14	0.0106 (3)	0.71672 (14)	1.09252 (11)	0.0154 (5)
H14	−0.1005	0.7351	1.0859	0.018*
C15	0.0832 (3)	0.81413 (15)	1.13106 (11)	0.0191 (5)
H15A	0.0457	0.8828	1.1098	0.023*
H15B	0.1967	0.8119	1.1274	0.023*
C16	0.0306 (3)	0.80233 (14)	1.21114 (11)	0.0216 (5)
H16A	−0.0408	0.8614	1.2246	0.026*
H16B	0.1201	0.8042	1.2445	0.026*
C17	−0.0521 (3)	0.69056 (14)	1.21538 (11)	0.0173 (5)
H17	−0.1627	0.7040	1.2035	0.021*
C18	0.1795 (3)	0.58958 (16)	1.16724 (12)	0.0232 (5)
H18A	0.1764	0.5277	1.2006	0.035*
H18B	0.2366	0.6489	1.1900	0.035*
H18C	0.2306	0.5683	1.1218	0.035*
C19	0.2043 (2)	0.49419 (15)	0.91585 (12)	0.0199 (5)
H19A	0.2488	0.4924	0.8661	0.024*
H19B	0.2728	0.5391	0.9466	0.024*
C20	−0.0486 (3)	0.64326 (16)	1.29112 (11)	0.0219 (5)
C21	−0.0887 (3)	0.71767 (17)	1.35354 (11)	0.0293 (6)
H21A	0.0035	0.7569	1.3691	0.044*
H21B	−0.1286	0.6750	1.3944	0.044*
H21C	−0.1672	0.7694	1.3376	0.044*
C22	−0.0763 (3)	0.62330 (17)	0.63230 (12)	0.0221 (5)
C23	−0.0378 (3)	0.60069 (18)	0.55382 (12)	0.0315 (6)
H23A	0.0720	0.6136	0.5456	0.047*
H23B	−0.0981	0.6485	0.5223	0.047*
H23C	−0.0622	0.5252	0.5424	0.047*

	U11	U22	U33	U12	U13	U23
O1	0.0238 (9)	0.0196 (7)	0.0151 (8)	0.0004 (7)	0.0002 (7)	−0.0013 (6)
O2	0.0370 (10)	0.0199 (8)	0.0232 (9)	0.0036 (7)	−0.0009 (8)	0.0023 (7)
O3	0.0298 (10)	0.0191 (7)	0.0248 (9)	0.0059 (7)	−0.0058 (8)	−0.0034 (6)
O4	0.0604 (13)	0.0203 (8)	0.0274 (10)	0.0038 (9)	0.0007 (9)	0.0066 (6)
C1	0.0157 (11)	0.0153 (10)	0.0200 (11)	−0.0005 (9)	−0.0012 (9)	0.0014 (8)
C2	0.0176 (12)	0.0158 (10)	0.0213 (12)	0.0008 (9)	−0.0014 (10)	−0.0024 (8)
C3	0.0208 (12)	0.0187 (10)	0.0145 (11)	0.0006 (10)	0.0020 (10)	−0.0025 (8)
C4	0.0200 (12)	0.0184 (10)	0.0180 (11)	−0.0006 (9)	0.0025 (10)	0.0005 (9)
C5	0.0117 (11)	0.0207 (11)	0.0171 (12)	−0.0011 (9)	0.0000 (9)	0.0013 (8)
C6	0.0175 (12)	0.0184 (10)	0.0156 (11)	−0.0014 (9)	−0.0013 (10)	0.0030 (8)
C7	0.0180 (12)	0.0136 (10)	0.0199 (11)	−0.0022 (9)	0.0004 (10)	−0.0003 (8)
C8	0.0148 (11)	0.0144 (10)	0.0188 (12)	−0.0007 (9)	0.0010 (10)	0.0018 (8)
C9	0.0179 (12)	0.0151 (10)	0.0166 (11)	−0.0003 (9)	−0.0002 (9)	0.0008 (8)
C10	0.0151 (11)	0.0149 (10)	0.0185 (11)	−0.0005 (9)	−0.0008 (9)	−0.0007 (8)
C11	0.0239 (13)	0.0165 (10)	0.0174 (12)	−0.0011 (9)	−0.0008 (9)	−0.0001 (8)
C12	0.0221 (12)	0.0153 (10)	0.0183 (11)	−0.0025 (9)	−0.0002 (10)	0.0018 (9)
C13	0.0172 (11)	0.0162 (10)	0.0139 (11)	0.0002 (9)	−0.0005 (9)	0.0022 (8)
C14	0.0147 (11)	0.0138 (10)	0.0177 (11)	0.0004 (9)	−0.0003 (9)	0.0011 (8)
C15	0.0226 (12)	0.0167 (10)	0.0179 (12)	−0.0032 (9)	−0.0010 (10)	−0.0011 (8)
C16	0.0283 (14)	0.0161 (10)	0.0204 (12)	−0.0047 (10)	0.0007 (11)	−0.0028 (8)
C17	0.0190 (12)	0.0162 (10)	0.0166 (11)	−0.0017 (9)	−0.0023 (10)	0.0011 (8)
C18	0.0236 (13)	0.0228 (11)	0.0232 (13)	0.0034 (10)	−0.0024 (10)	0.0022 (10)
C19	0.0164 (12)	0.0185 (11)	0.0250 (12)	0.0001 (9)	−0.0017 (10)	−0.0007 (9)
C20	0.0219 (13)	0.0230 (11)	0.0208 (12)	−0.0033 (10)	−0.0033 (11)	0.0022 (9)
C21	0.0440 (17)	0.0237 (12)	0.0203 (13)	−0.0065 (11)	0.0002 (12)	−0.0009 (9)
C22	0.0225 (12)	0.0230 (12)	0.0208 (12)	−0.0050 (10)	−0.0024 (11)	0.0019 (9)
C23	0.0393 (17)	0.0329 (12)	0.0223 (13)	−0.0003 (12)	0.0019 (12)	−0.0001 (10)

O1—C22	1.344 (2)	C11—C12	1.542 (3)
O1—C3	1.460 (2)	C11—H20A	0.9900
O2—C22	1.213 (2)	C11—H20B	0.9900
O3—C19	1.435 (2)	C12—C13	1.541 (3)
O3—H3A	0.8400	C12—H12A	0.9900
O4—C20	1.213 (2)	C12—H12B	0.9900
C1—C2	1.538 (3)	C13—C18	1.527 (3)
C1—C10	1.553 (3)	C13—C14	1.541 (3)
C1—H1A	0.9900	C13—C17	1.545 (3)
C1—H1B	0.9900	C14—C15	1.533 (3)
C2—C3	1.508 (3)	C14—H14	1.0000
C2—H2A	0.9900	C15—C16	1.545 (3)
C2—H2B	0.9900	C15—H15A	0.9900
C3—C4	1.519 (3)	C15—H15B	0.9900
C3—H3	1.0000	C16—C17	1.561 (3)
C4—C5	1.513 (3)	C16—H16A	0.9900
C4—H4A	0.9900	C16—H16B	0.9900
C4—H4B	0.9900	C17—C20	1.507 (3)
C5—C6	1.327 (3)	C17—H17	1.0000
C5—C10	1.538 (3)	C18—H18A	0.9800
C6—C7	1.486 (3)	C18—H18B	0.9800
C6—H6	0.9500	C18—H18C	0.9800
C7—C8	1.524 (2)	C19—H19A	0.9900
C7—H7A	0.9900	C19—H19B	0.9900
C7—H7B	0.9900	C20—C21	1.509 (3)
C8—C14	1.514 (3)	C21—H21A	0.9800
C8—C9	1.544 (3)	C21—H21B	0.9800
C8—H8	1.0000	C21—H21C	0.9800
C9—C11	1.547 (3)	C22—C23	1.503 (3)
C9—C10	1.562 (3)	C23—H23A	0.9800
C9—H9	1.0000	C23—H23B	0.9800
C10—C19	1.554 (3)	C23—H23C	0.9800
C22—O1—C3	116.09 (15)	C11—C12—H12A	109.4
C19—O3—H3A	109.5	C13—C12—H12B	109.4
C2—C1—C10	115.17 (17)	C11—C12—H12B	109.4
C2—C1—H1A	108.5	H12A—C12—H12B	108.0
C10—C1—H1A	108.5	C18—C13—C12	111.11 (16)
C2—C1—H1B	108.5	C18—C13—C14	112.45 (17)
C10—C1—H1B	108.5	C12—C13—C14	106.58 (16)
H1A—C1—H1B	107.5	C18—C13—C17	110.81 (18)
C3—C2—C1	109.27 (15)	C12—C13—C17	116.62 (17)
C3—C2—H2A	109.8	C14—C13—C17	98.59 (14)
C1—C2—H2A	109.8	C8—C14—C15	118.33 (17)
C3—C2—H2B	109.8	C8—C14—C13	115.67 (15)
C1—C2—H2B	109.8	C15—C14—C13	103.82 (16)
H2A—C2—H2B	108.3	C8—C14—H14	106.0
O1—C3—C2	109.60 (14)	C15—C14—H14	106.0
O1—C3—C4	109.38 (16)	C13—C14—H14	106.0
C2—C3—C4	109.69 (17)	C14—C15—C16	103.98 (16)
O1—C3—H3	109.4	C14—C15—H15A	111.0
C2—C3—H3	109.4	C16—C15—H15A	111.0
C4—C3—H3	109.4	C14—C15—H15B	111.0
C5—C4—C3	110.67 (17)	C16—C15—H15B	111.0
C5—C4—H4A	109.5	H15A—C15—H15B	109.0
C3—C4—H4A	109.5	C15—C16—C17	105.52 (15)
C5—C4—H4B	109.5	C15—C16—H16A	110.6
C3—C4—H4B	109.5	C17—C16—H16A	110.6
H4A—C4—H4B	108.1	C15—C16—H16B	110.6
C6—C5—C4	119.25 (17)	C17—C16—H16B	110.6
C6—C5—C10	123.59 (18)	H16A—C16—H16B	108.8
C4—C5—C10	117.15 (16)	C20—C17—C13	120.13 (16)
C5—C6—C7	125.24 (18)	C20—C17—C16	112.36 (17)
C5—C6—H6	117.4	C13—C17—C16	103.86 (16)
C7—C6—H6	117.4	C20—C17—H17	106.6
C6—C7—C8	112.96 (16)	C13—C17—H17	106.6
C6—C7—H7A	109.0	C16—C17—H17	106.6
C8—C7—H7A	109.0	C13—C18—H18A	109.5
C6—C7—H7B	109.0	C13—C18—H18B	109.5
C8—C7—H7B	109.0	H18A—C18—H18B	109.5
H7A—C7—H7B	107.8	C13—C18—H18C	109.5
C14—C8—C7	109.19 (15)	H18A—C18—H18C	109.5
C14—C8—C9	110.59 (17)	H18B—C18—H18C	109.5
C7—C8—C9	110.59 (16)	O3—C19—C10	115.04 (17)
C14—C8—H8	108.8	O3—C19—H19A	108.5
C7—C8—H8	108.8	C10—C19—H19A	108.5
C9—C8—H8	108.8	O3—C19—H19B	108.5
C8—C9—C11	111.31 (16)	C10—C19—H19B	108.5
C8—C9—C10	112.25 (16)	H19A—C19—H19B	107.5
C11—C9—C10	114.42 (15)	O4—C20—C17	122.86 (19)
C8—C9—H9	106.1	O4—C20—C21	119.94 (19)
C11—C9—H9	106.1	C17—C20—C21	117.18 (17)
C10—C9—H9	106.1	C20—C21—H21A	109.5
C5—C10—C1	108.10 (16)	C20—C21—H21B	109.5
C5—C10—C19	107.29 (16)	H21A—C21—H21B	109.5
C1—C10—C19	110.20 (15)	C20—C21—H21C	109.5
C5—C10—C9	108.97 (15)	H21A—C21—H21C	109.5
C1—C10—C9	109.34 (17)	H21B—C21—H21C	109.5
C19—C10—C9	112.81 (17)	O2—C22—O1	123.6 (2)
C12—C11—C9	113.28 (15)	O2—C22—C23	124.6 (2)
C12—C11—H20A	108.9	O1—C22—C23	111.88 (18)
C9—C11—H20A	108.9	C22—C23—H23A	109.5
C12—C11—H20B	108.9	C22—C23—H23B	109.5
C9—C11—H20B	108.9	H23A—C23—H23B	109.5
H20A—C11—H20B	107.7	C22—C23—H23C	109.5
C13—C12—C11	111.00 (17)	H23A—C23—H23C	109.5
C13—C12—H12A	109.4	H23B—C23—H23C	109.5
C10—C1—C2—C3	−57.1 (2)	C9—C11—C12—C13	−56.8 (2)
C22—O1—C3—C2	162.62 (17)	C11—C12—C13—C18	−65.7 (2)
C22—O1—C3—C4	−77.1 (2)	C11—C12—C13—C14	57.1 (2)
C1—C2—C3—O1	−178.82 (16)	C11—C12—C13—C17	166.01 (16)
C1—C2—C3—C4	61.1 (2)	C7—C8—C14—C15	−58.5 (2)
O1—C3—C4—C5	−179.18 (15)	C9—C8—C14—C15	179.59 (17)
C2—C3—C4—C5	−58.9 (2)	C7—C8—C14—C13	177.42 (17)
C3—C4—C5—C6	−126.4 (2)	C9—C8—C14—C13	55.5 (2)
C3—C4—C5—C10	52.6 (2)	C18—C13—C14—C8	63.1 (2)
C4—C5—C6—C7	−178.7 (2)	C12—C13—C14—C8	−58.9 (2)
C10—C5—C6—C7	2.3 (4)	C17—C13—C14—C8	179.88 (18)
C5—C6—C7—C8	10.9 (3)	C18—C13—C14—C15	−68.3 (2)
C6—C7—C8—C14	−162.88 (18)	C12—C13—C14—C15	169.74 (17)
C6—C7—C8—C9	−41.0 (3)	C17—C13—C14—C15	48.5 (2)
C14—C8—C9—C11	−48.9 (2)	C8—C14—C15—C16	−164.60 (18)
C7—C8—C9—C11	−169.97 (18)	C13—C14—C15—C16	−34.9 (2)
C14—C8—C9—C10	−178.62 (16)	C14—C15—C16—C17	6.9 (2)
C7—C8—C9—C10	60.3 (2)	C18—C13—C17—C20	−51.9 (2)
C6—C5—C10—C1	134.0 (2)	C12—C13—C17—C20	76.5 (2)
C4—C5—C10—C1	−45.0 (2)	C14—C13—C17—C20	−169.98 (19)
C6—C5—C10—C19	−107.2 (2)	C18—C13—C17—C16	74.70 (19)
C4—C5—C10—C19	73.8 (2)	C12—C13—C17—C16	−156.87 (17)
C6—C5—C10—C9	15.2 (3)	C14—C13—C17—C16	−43.38 (19)
C4—C5—C10—C9	−163.72 (18)	C15—C16—C17—C20	154.51 (18)
C2—C1—C10—C5	46.9 (2)	C15—C16—C17—C13	23.2 (2)
C2—C1—C10—C19	−70.0 (2)	C5—C10—C19—O3	−165.71 (16)
C2—C1—C10—C9	165.42 (16)	C1—C10—C19—O3	−48.2 (2)
C8—C9—C10—C5	−45.7 (2)	C9—C10—C19—O3	74.3 (2)
C11—C9—C10—C5	−173.76 (17)	C13—C17—C20—O4	−12.8 (3)
C8—C9—C10—C1	−163.62 (15)	C16—C17—C20—O4	−135.4 (2)
C11—C9—C10—C1	68.3 (2)	C13—C17—C20—C21	168.8 (2)
C8—C9—C10—C19	73.38 (19)	C16—C17—C20—C21	46.2 (3)
C11—C9—C10—C19	−54.7 (2)	C3—O1—C22—O2	−5.2 (3)
C8—C9—C11—C12	51.4 (2)	C3—O1—C22—C23	174.20 (17)
C10—C9—C11—C12	179.96 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2i	0.84	2.19	2.9305 (19)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2i	0.84	2.19	2.9305 (19)	147

Symmetry code: (i) .