(7aR)-1-[(2R,5S,E)-6-Hy-droxy-5,6-dimethyl-hept-3-en-2-yl]-7a-methyl-hexa-hydro-1H-inden-4(2H)-one.

The chiral title compound, C(19)H(32)O(2), contains a [4.3.0]-bicyclic moiety in which the shared C-C bond presents a trans configuration and a side chain in which the C=C double bond shows an E conformation. The conformations of five- and six-membered rings are envelope (with the bridgehead atom bearing the methyl substituent as the flap) and chair, respectively, with a dihedral angle of 4.08 (17)° between the idealized planes of the rings. In the crystal, the mol-ecules are self-assembled via classical O-H⋯O hydrogen bonds, forming chains along [112]; these chains are linked by weak non-classical C-H⋯O hydrogen bonds, giving a two-dimensional supra-molecular structure parallel to (010). The absolute configuration was established according to the configuration of the starting material.

Related literature

The title compound is a precursor of the hormonally active form of vitamin D3. For general background to vitamin D3, see: Heaney (2008 ▶); Henry (2011 ▶). For related structures, see: Maehr & Uskokovic (2004 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C19H32O2

M = 292.45

Monoclinic,

a = 20.057 (4) Å

b = 7.3816 (15) Å

c = 13.700 (3) Å

β = 112.324 (4)°

V = 1876.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.07 mm−1

T = 293 K

0.45 × 0.36 × 0.18 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.602, T max = 0.745

4958 measured reflections

3254 independent reflections

2389 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.152

S = 1.02

3254 reflections

196 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.11 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051343/pv2614sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051343/pv2614Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812051343/pv2614Isup3.cml

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

C19H32O2	F(000) = 648
Mr = 292.45	Dx = 1.035 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 1729 reflections
a = 20.057 (4) Å	θ = 2.2–23.0°
b = 7.3816 (15) Å	µ = 0.07 mm−1
c = 13.700 (3) Å	T = 293 K
β = 112.324 (4)°	Prism, colourless
V = 1876.3 (6) Å3	0.45 × 0.36 × 0.18 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3254 independent reflections
Radiation source: fine-focus sealed tube	2389 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→14
Tmin = 0.602, Tmax = 0.745	k = −8→8
4958 measured reflections	l = −13→16

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0934P)2 + 0.0697P] where P = (Fo2 + 2Fc2)/3
3254 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.14 e Å−3
1 restraint	Δρmin = −0.11 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
C1	0.31315 (12)	−0.0108 (3)	0.83385 (16)	0.0467 (6)
H1	0.3524	0.0312	0.8135	0.056*
C2	0.32284 (17)	−0.2166 (4)	0.8512 (2)	0.0663 (8)
H2A	0.3046	−0.2556	0.9039	0.080*
H2B	0.3735	−0.2484	0.8752	0.080*
C3	0.28017 (17)	−0.3084 (4)	0.7442 (2)	0.0737 (8)
H3A	0.3107	−0.3896	0.7239	0.088*
H3B	0.2394	−0.3759	0.7469	0.088*
C3A	0.25554 (14)	−0.1495 (3)	0.66904 (18)	0.0554 (7)
H3A1	0.2968	−0.1140	0.6516	0.066*
C4	0.19282 (15)	−0.1736 (4)	0.5661 (2)	0.0619 (7)
O4	0.16051 (12)	−0.3154 (3)	0.53886 (15)	0.0849 (7)
C5	0.17509 (18)	−0.0054 (5)	0.4997 (2)	0.0807 (9)
H5A	0.1294	−0.0224	0.4411	0.097*
H5B	0.2118	0.0139	0.4708	0.097*
C6	0.17031 (19)	0.1620 (5)	0.5617 (2)	0.0827 (10)
H6A	0.1253	0.1584	0.5727	0.099*
H6B	0.1695	0.2690	0.5202	0.099*
C7	0.23275 (15)	0.1787 (4)	0.6691 (2)	0.0673 (8)
H7A	0.2769	0.2040	0.6582	0.081*
H7B	0.2236	0.2798	0.7075	0.081*
C7A	0.24264 (12)	0.0069 (3)	0.73468 (16)	0.0472 (6)
C8	0.17703 (13)	−0.0288 (5)	0.7620 (2)	0.0706 (8)
H8A	0.1349	−0.0386	0.6982	0.106*
H8B	0.1710	0.0694	0.8038	0.106*
H8C	0.1838	−0.1397	0.8012	0.106*
C1'	0.31086 (19)	0.2943 (4)	0.9234 (2)	0.0799 (10)
H1'1	0.3417	0.3421	0.8905	0.120*
H1'2	0.3227	0.3496	0.9914	0.120*
H1'3	0.2615	0.3200	0.8801	0.120*
C2'	0.32153 (14)	0.0889 (4)	0.93674 (19)	0.0552 (7)
H2'	0.2857	0.0405	0.9624	0.066*
C3'	0.39471 (14)	0.0496 (4)	1.01717 (17)	0.0554 (7)
H3'	0.4331	0.0888	1.0004	0.067*
C4'	0.41212 (13)	−0.0327 (4)	1.10809 (18)	0.0578 (7)
H4'	0.3744	−0.0706	1.1268	0.069*
C5'	0.48679 (13)	−0.0715 (4)	1.18480 (19)	0.0564 (7)
H5'	0.5196	−0.0367	1.1503	0.068*
C6'	0.4971 (2)	−0.2739 (5)	1.2070 (4)	0.1075 (14)
H6'1	0.4895	−0.3375	1.1425	0.161*
H6'2	0.4631	−0.3156	1.2359	0.161*
H6'3	0.5452	−0.2962	1.2566	0.161*
C7'	0.50827 (14)	0.0412 (5)	1.2868 (2)	0.0674 (8)
O7'	0.58126 (10)	−0.0077 (3)	1.34707 (14)	0.0824 (7)
H7'	0.5959	0.0494	1.4026	0.124*
C8'	0.5057 (2)	0.2410 (5)	1.2604 (3)	0.1151 (17)
H8'1	0.5409	0.2673	1.2307	0.173*
H8'2	0.5159	0.3110	1.3235	0.173*
H8'3	0.4585	0.2715	1.2104	0.173*
C9'	0.4620 (2)	0.0049 (11)	1.3478 (3)	0.145 (2)
H9'1	0.4765	0.0822	1.4086	0.218*
H9'2	0.4672	−0.1194	1.3699	0.218*
H9'3	0.4126	0.0287	1.3040	0.218*

	U11	U22	U33	U12	U13	U23
C1	0.0422 (12)	0.0519 (14)	0.0368 (10)	−0.0019 (12)	0.0048 (9)	−0.0014 (11)
C2	0.0731 (18)	0.0573 (17)	0.0500 (13)	0.0055 (14)	0.0027 (13)	−0.0010 (13)
C3	0.088 (2)	0.0542 (16)	0.0582 (15)	0.0030 (15)	0.0040 (14)	−0.0063 (14)
C3A	0.0536 (14)	0.0559 (16)	0.0444 (13)	−0.0055 (12)	0.0048 (11)	−0.0064 (11)
C4	0.0613 (16)	0.0701 (19)	0.0438 (13)	−0.0111 (15)	0.0079 (12)	−0.0117 (13)
O4	0.0868 (15)	0.0816 (15)	0.0583 (11)	−0.0232 (13)	−0.0039 (10)	−0.0162 (11)
C5	0.086 (2)	0.090 (2)	0.0425 (13)	−0.0127 (18)	−0.0011 (13)	0.0046 (16)
C6	0.093 (2)	0.077 (2)	0.0523 (16)	0.0033 (18)	−0.0011 (16)	0.0166 (15)
C7	0.0736 (19)	0.0615 (18)	0.0467 (14)	−0.0021 (16)	0.0002 (13)	0.0083 (13)
C7A	0.0444 (13)	0.0503 (14)	0.0385 (10)	−0.0030 (12)	0.0061 (9)	0.0007 (11)
C8	0.0474 (14)	0.101 (2)	0.0565 (14)	−0.0084 (15)	0.0117 (11)	−0.0040 (16)
C1'	0.095 (2)	0.072 (2)	0.0541 (15)	0.0132 (17)	0.0068 (15)	−0.0143 (14)
C2'	0.0507 (14)	0.0651 (18)	0.0419 (13)	−0.0001 (12)	0.0086 (11)	−0.0079 (11)
C3'	0.0508 (15)	0.0722 (19)	0.0359 (12)	−0.0071 (12)	0.0081 (11)	−0.0076 (11)
C4'	0.0484 (14)	0.0715 (19)	0.0470 (13)	−0.0112 (13)	0.0108 (11)	−0.0020 (13)
C5'	0.0483 (15)	0.0643 (18)	0.0478 (13)	−0.0007 (12)	0.0081 (11)	−0.0007 (12)
C6'	0.086 (3)	0.066 (2)	0.136 (3)	0.0032 (18)	0.003 (2)	0.007 (2)
C7'	0.0483 (15)	0.096 (3)	0.0433 (12)	0.0113 (14)	0.0012 (11)	−0.0076 (13)
O7'	0.0566 (12)	0.1072 (18)	0.0569 (10)	0.0184 (12)	−0.0083 (9)	−0.0136 (12)
C8'	0.097 (3)	0.082 (3)	0.112 (3)	0.018 (2)	−0.022 (2)	−0.034 (2)
C9'	0.094 (3)	0.287 (7)	0.0559 (17)	0.032 (4)	0.0299 (19)	0.005 (3)

C1—C2	1.538 (4)	C8—H8C	0.9600
C1—C2'	1.541 (3)	C1'—C2'	1.533 (4)
C1—C7A	1.550 (3)	C1'—H1'1	0.9600
C1—H1	0.9800	C1'—H1'2	0.9600
C2—C3	1.545 (4)	C1'—H1'3	0.9600
C2—H2A	0.9700	C2'—C3'	1.491 (4)
C2—H2B	0.9700	C2'—H2'	0.9800
C3—C3A	1.515 (4)	C3'—C4'	1.308 (3)
C3—H3A	0.9700	C3'—H3'	0.9300
C3—H3B	0.9700	C4'—C5'	1.495 (3)
C3A—C4	1.501 (3)	C4'—H4'	0.9300
C3A—C7A	1.545 (3)	C5'—C6'	1.523 (5)
C3A—H3A1	0.9800	C5'—C7'	1.540 (4)
C4—O4	1.213 (3)	C5'—H5'	0.9800
C4—C5	1.500 (4)	C6'—H6'1	0.9600
C5—C6	1.524 (5)	C6'—H6'2	0.9600
C5—H5A	0.9700	C6'—H6'3	0.9600
C5—H5B	0.9700	C7'—O7'	1.427 (3)
C6—C7	1.532 (4)	C7'—C9'	1.490 (5)
C6—H6A	0.9700	C7'—C8'	1.515 (6)
C6—H6B	0.9700	O7'—H7'	0.8200
C7—C7A	1.524 (4)	C8'—H8'1	0.9600
C7—H7A	0.9700	C8'—H8'2	0.9600
C7—H7B	0.9700	C8'—H8'3	0.9600
C7A—C8	1.522 (3)	C9'—H9'1	0.9600
C8—H8A	0.9600	C9'—H9'2	0.9600
C8—H8B	0.9600	C9'—H9'3	0.9600
C2—C1—C2'	111.5 (2)	H8A—C8—H8B	109.5
C2—C1—C7A	103.77 (19)	C7A—C8—H8C	109.5
C2'—C1—C7A	120.50 (19)	H8A—C8—H8C	109.5
C2—C1—H1	106.8	H8B—C8—H8C	109.5
C2'—C1—H1	106.8	C2'—C1'—H1'1	109.5
C7A—C1—H1	106.8	C2'—C1'—H1'2	109.5
C1—C2—C3	107.2 (2)	H1'1—C1'—H1'2	109.5
C1—C2—H2A	110.3	C2'—C1'—H1'3	109.5
C3—C2—H2A	110.3	H1'1—C1'—H1'3	109.5
C1—C2—H2B	110.3	H1'2—C1'—H1'3	109.5
C3—C2—H2B	110.3	C3'—C2'—C1'	109.5 (2)
H2A—C2—H2B	108.5	C3'—C2'—C1	108.5 (2)
C3A—C3—C2	103.0 (2)	C1'—C2'—C1	113.7 (2)
C3A—C3—H3A	111.2	C3'—C2'—H2'	108.3
C2—C3—H3A	111.2	C1'—C2'—H2'	108.3
C3A—C3—H3B	111.2	C1—C2'—H2'	108.3
C2—C3—H3B	111.2	C4'—C3'—C2'	128.7 (3)
H3A—C3—H3B	109.1	C4'—C3'—H3'	115.6
C4—C3A—C3	119.2 (2)	C2'—C3'—H3'	115.6
C4—C3A—C7A	111.7 (2)	C3'—C4'—C5'	126.3 (2)
C3—C3A—C7A	105.5 (2)	C3'—C4'—H4'	116.8
C4—C3A—H3A1	106.6	C5'—C4'—H4'	116.8
C3—C3A—H3A1	106.6	C4'—C5'—C6'	110.6 (2)
C7A—C3A—H3A1	106.6	C4'—C5'—C7'	113.2 (2)
O4—C4—C5	123.5 (2)	C6'—C5'—C7'	112.2 (3)
O4—C4—C3A	123.4 (3)	C4'—C5'—H5'	106.8
C5—C4—C3A	113.1 (2)	C6'—C5'—H5'	106.8
C4—C5—C6	112.5 (2)	C7'—C5'—H5'	106.8
C4—C5—H5A	109.1	C5'—C6'—H6'1	109.5
C6—C5—H5A	109.1	C5'—C6'—H6'2	109.5
C4—C5—H5B	109.1	H6'1—C6'—H6'2	109.5
C6—C5—H5B	109.1	C5'—C6'—H6'3	109.5
H5A—C5—H5B	107.8	H6'1—C6'—H6'3	109.5
C5—C6—C7	113.5 (3)	H6'2—C6'—H6'3	109.5
C5—C6—H6A	108.9	O7'—C7'—C9'	110.5 (3)
C7—C6—H6A	108.9	O7'—C7'—C8'	108.6 (3)
C5—C6—H6B	108.9	C9'—C7'—C8'	109.6 (4)
C7—C6—H6B	108.9	O7'—C7'—C5'	105.1 (2)
H6A—C6—H6B	107.7	C9'—C7'—C5'	113.1 (3)
C7A—C7—C6	112.0 (2)	C8'—C7'—C5'	109.7 (3)
C7A—C7—H7A	109.2	C7'—O7'—H7'	109.5
C6—C7—H7A	109.2	C7'—C8'—H8'1	109.5
C7A—C7—H7B	109.2	C7'—C8'—H8'2	109.5
C6—C7—H7B	109.2	H8'1—C8'—H8'2	109.5
H7A—C7—H7B	107.9	C7'—C8'—H8'3	109.5
C8—C7A—C7	111.0 (2)	H8'1—C8'—H8'3	109.5
C8—C7A—C3A	111.4 (2)	H8'2—C8'—H8'3	109.5
C7—C7A—C3A	106.98 (19)	C7'—C9'—H9'1	109.5
C8—C7A—C1	110.87 (18)	C7'—C9'—H9'2	109.5
C7—C7A—C1	117.3 (2)	H9'1—C9'—H9'2	109.5
C3A—C7A—C1	98.54 (18)	C7'—C9'—H9'3	109.5
C7A—C8—H8A	109.5	H9'1—C9'—H9'3	109.5
C7A—C8—H8B	109.5	H9'2—C9'—H9'3	109.5
C2'—C1—C2—C3	153.7 (2)	C2—C1—C7A—C8	75.8 (3)
C7A—C1—C2—C3	22.6 (3)	C2'—C1—C7A—C8	−49.9 (3)
C1—C2—C3—C3A	6.2 (3)	C2—C1—C7A—C7	−155.3 (2)
C2—C3—C3A—C4	−159.6 (3)	C2'—C1—C7A—C7	79.0 (3)
C2—C3—C3A—C7A	−33.2 (3)	C2—C1—C7A—C3A	−41.2 (2)
C3—C3A—C4—O4	−0.6 (5)	C2'—C1—C7A—C3A	−166.8 (2)
C7A—C3A—C4—O4	−124.0 (3)	C2—C1—C2'—C3'	59.0 (3)
C3—C3A—C4—C5	−179.5 (3)	C7A—C1—C2'—C3'	−179.0 (2)
C7A—C3A—C4—C5	57.1 (3)	C2—C1—C2'—C1'	−178.8 (3)
O4—C4—C5—C6	132.6 (3)	C7A—C1—C2'—C1'	−56.9 (3)
C3A—C4—C5—C6	−48.5 (4)	C1'—C2'—C3'—C4'	117.4 (3)
C4—C5—C6—C7	46.1 (4)	C1—C2'—C3'—C4'	−118.0 (3)
C5—C6—C7—C7A	−52.5 (4)	C2'—C3'—C4'—C5'	178.7 (3)
C6—C7—C7A—C8	−63.9 (3)	C3'—C4'—C5'—C6'	−122.4 (4)
C6—C7—C7A—C3A	57.8 (3)	C3'—C4'—C5'—C7'	110.6 (3)
C6—C7—C7A—C1	167.2 (2)	C4'—C5'—C7'—O7'	−177.4 (2)
C4—C3A—C7A—C8	61.0 (3)	C6'—C5'—C7'—O7'	56.5 (3)
C3—C3A—C7A—C8	−69.8 (3)	C4'—C5'—C7'—C9'	62.0 (4)
C4—C3A—C7A—C7	−60.5 (3)	C6'—C5'—C7'—C9'	−64.2 (4)
C3—C3A—C7A—C7	168.7 (2)	C4'—C5'—C7'—C8'	−60.8 (3)
C4—C3A—C7A—C1	177.5 (2)	C6'—C5'—C7'—C8'	173.1 (3)
C3—C3A—C7A—C1	46.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O7′—H7′···O4i	0.82	2.08	2.876 (3)	164
C3A—H3A1···O7′ii	0.98	2.56	3.523 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7′—H7′⋯O4i	0.82	2.08	2.876 (3)	164
C3A—H3A1⋯O7′ii	0.98	2.56	3.523 (3)	166

Symmetry codes: (i) ; (ii) .