(1R,3aR,5aS,6S,8aR,8bR,9aS)-1-Hydr-oxy-6-isopropyl-1,3a,5a-trimethyl-perhydro-cyclo-penta-[a]cyclo-propa[i]naphthalen-4-one.

The title compound (also know as azorellanone), C(20)H(32)O(2), is built up from three fused carbocycles, one five-membered ring and two six-membered rings. The five membered-ring has an envelope conformation, whereas the six-membered rings have a distorted half-chair and a twist-boat conformation. In the crystal, mol-ecules are linked by O-H⋯O inter-actions into zigzag chains with graph-set notation C(8) along [010]. The absolute configuration was assigned on the basis of earlier chemical studies.

Related literature

For related structures, see: Loyola et al. (1998 ▶, 2000 ▶, 2001 ▶, 2004 ▶); Borquez et al. (2007 ▶). For the biological properties of diterpenoids with azorellane and mulinane skeletons, see: Chiaramello et al. (2003 ▶); Fuentes et al. (2005 ▶); Delporte et al. (2003 ▶); Morales et al. (2003 ▶); Neira et al. (1998 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C20H32O2

M = 304.46

Monoclinic,

a = 6.0073 (5) Å

b = 13.3348 (11) Å

c = 11.2743 (8) Å

β = 99.271 (6)°

V = 891.34 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 173 K

0.37 × 0.36 × 0.36 mm

Data collection

Stoe IPDSII two-circle diffractometer

6336 measured reflections

2107 independent reflections

1876 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.100

S = 1.00

2107 reflections

204 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.2 e Å−3

Δρmin = −0.16 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810001169/fl2288sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001169/fl2288Isup2.hkl

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

C20H32O2	F(000) = 336
Mr = 304.46	Dx = 1.134 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6216 reflections
a = 6.0073 (5) Å	θ = 3.5–27.8°
b = 13.3348 (11) Å	µ = 0.07 mm−1
c = 11.2743 (8) Å	T = 173 K
β = 99.271 (6)°	Block, colourless
V = 891.34 (12) Å3	0.37 × 0.36 × 0.36 mm
Z = 2

Stoe IPDSII two-circle diffractometer	Rint = 0.066
graphite	θmax = 27.5°, θmin = 3.4°
ω scans	h = −7→7
6336 measured reflections	k = −17→17
2107 independent reflections	l = −13→14
1876 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.065P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2107 reflections	Δρmax = 0.2 e Å−3
204 parameters	Δρmin = −0.16 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (6)

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	1.0462 (3)	0.74056 (12)	0.32053 (17)	0.0400 (4)
H1	1.088 (5)	0.801 (2)	0.369 (3)	0.053 (8)*
O2	0.8592 (3)	0.42953 (12)	0.55110 (15)	0.0470 (5)
C1	0.8182 (4)	0.44374 (16)	0.0885 (2)	0.0340 (4)
H1A	0.9569	0.4797	0.0761	0.041*
H1B	0.688	0.4727	0.0344	0.041*
C2	0.8394 (3)	0.33017 (15)	0.06515 (19)	0.0313 (4)
H2A	0.9912	0.3144	0.0467	0.038*
H2B	0.7253	0.3089	−0.0036	0.038*
C3	0.8004 (3)	0.27562 (15)	0.18129 (18)	0.0261 (4)
H3	0.9506	0.2684	0.2336	0.031*
C4	0.7041 (3)	0.16952 (15)	0.1557 (2)	0.0311 (4)
H4	0.5664	0.1751	0.0931	0.037*
C5	0.6621 (3)	0.35294 (14)	0.24246 (18)	0.0246 (4)
C6	0.6819 (4)	0.34028 (15)	0.38011 (19)	0.0308 (4)
H6A	0.5353	0.3164	0.3987	0.037*
H6B	0.7956	0.2878	0.4068	0.037*
C7	0.7475 (3)	0.43507 (15)	0.45144 (19)	0.0302 (4)
C8	0.6549 (3)	0.53588 (15)	0.40016 (18)	0.0271 (4)
C9	0.6806 (3)	0.54398 (14)	0.26617 (18)	0.0272 (4)
C10	0.7838 (3)	0.45080 (14)	0.21941 (18)	0.0254 (4)
H10	0.938	0.4451	0.2679	0.03*
C11	0.5111 (4)	0.60649 (17)	0.1836 (2)	0.0364 (5)
H11A	0.4639	0.5823	0.1003	0.044*
H11B	0.3916	0.6409	0.2192	0.044*
C12	0.7496 (4)	0.64378 (15)	0.2178 (2)	0.0340 (5)
H12	0.8433	0.6374	0.1525	0.041*
C13	0.8031 (4)	0.73557 (15)	0.2965 (2)	0.0356 (5)
C14	0.7134 (4)	0.72394 (15)	0.4149 (2)	0.0357 (5)
H14A	0.7752	0.7782	0.4706	0.043*
H14B	0.5471	0.7305	0.4	0.043*
C15	0.7781 (3)	0.62273 (15)	0.47304 (19)	0.0307 (4)
H15A	0.7402	0.6221	0.5553	0.037*
H15B	0.943	0.613	0.4795	0.037*
C16	0.7113 (5)	0.83020 (18)	0.2302 (3)	0.0524 (7)
H16A	0.7472	0.8885	0.2827	0.079*
H16B	0.5473	0.8245	0.2075	0.079*
H16C	0.7803	0.8384	0.1577	0.079*
C17	0.4059 (4)	0.53345 (18)	0.4215 (2)	0.0370 (5)
H17A	0.3306	0.5959	0.3921	0.055*
H17B	0.402	0.5264	0.5077	0.055*
H17C	0.3281	0.4765	0.3782	0.055*
C18	0.8759 (4)	0.10463 (17)	0.1047 (2)	0.0425 (5)
H18A	0.9196	0.1379	0.0344	0.064*
H18B	0.8087	0.0392	0.0809	0.064*
H18C	1.0095	0.0951	0.1661	0.064*
C19	0.6366 (5)	0.11760 (17)	0.2651 (2)	0.0429 (5)
H19A	0.5275	0.1594	0.2985	0.064*
H19B	0.7706	0.1076	0.3261	0.064*
H19C	0.5682	0.0525	0.2411	0.064*
C20	0.4160 (3)	0.35344 (16)	0.1790 (2)	0.0338 (4)
H20A	0.4119	0.361	0.0922	0.051*
H20B	0.3356	0.4095	0.2092	0.051*
H20C	0.3435	0.2902	0.1952	0.051*

	U11	U22	U33	U12	U13	U23
O1	0.0403 (8)	0.0284 (7)	0.0521 (10)	−0.0029 (6)	0.0101 (7)	−0.0037 (7)
O2	0.0642 (10)	0.0364 (8)	0.0347 (9)	0.0084 (8)	−0.0096 (8)	0.0001 (7)
C1	0.0422 (10)	0.0317 (10)	0.0303 (11)	−0.0025 (8)	0.0127 (8)	0.0006 (8)
C2	0.0327 (9)	0.0345 (10)	0.0287 (10)	−0.0030 (7)	0.0109 (8)	−0.0038 (8)
C3	0.0235 (8)	0.0298 (9)	0.0251 (9)	0.0000 (7)	0.0041 (7)	−0.0019 (7)
C4	0.0317 (10)	0.0282 (9)	0.0325 (11)	−0.0004 (7)	0.0028 (8)	−0.0044 (8)
C5	0.0214 (8)	0.0275 (8)	0.0253 (10)	−0.0013 (6)	0.0055 (6)	−0.0015 (7)
C6	0.0375 (10)	0.0303 (9)	0.0261 (10)	−0.0009 (8)	0.0099 (8)	0.0006 (8)
C7	0.0330 (9)	0.0331 (10)	0.0257 (10)	0.0025 (8)	0.0084 (7)	0.0008 (8)
C8	0.0255 (9)	0.0299 (9)	0.0261 (10)	0.0024 (7)	0.0048 (7)	−0.0035 (7)
C9	0.0271 (9)	0.0286 (9)	0.0251 (10)	0.0010 (7)	0.0020 (7)	−0.0001 (7)
C10	0.0230 (7)	0.0274 (8)	0.0261 (10)	−0.0010 (7)	0.0054 (6)	0.0006 (7)
C11	0.0400 (11)	0.0332 (10)	0.0326 (11)	0.0057 (9)	−0.0041 (8)	0.0012 (8)
C12	0.0414 (11)	0.0271 (9)	0.0328 (11)	0.0005 (8)	0.0041 (9)	0.0021 (8)
C13	0.0393 (11)	0.0255 (9)	0.0406 (12)	0.0021 (8)	0.0020 (9)	−0.0017 (9)
C14	0.0347 (10)	0.0319 (11)	0.0397 (12)	0.0048 (8)	0.0034 (9)	−0.0086 (8)
C15	0.0312 (9)	0.0332 (10)	0.0278 (10)	0.0008 (8)	0.0047 (7)	−0.0048 (8)
C16	0.0708 (17)	0.0302 (11)	0.0520 (16)	0.0069 (11)	−0.0024 (13)	0.0029 (11)
C17	0.0303 (10)	0.0403 (11)	0.0425 (13)	0.0010 (8)	0.0126 (8)	−0.0066 (10)
C18	0.0462 (12)	0.0343 (11)	0.0475 (15)	0.0059 (9)	0.0095 (10)	−0.0106 (10)
C19	0.0560 (14)	0.0314 (10)	0.0429 (14)	−0.0048 (10)	0.0130 (11)	−0.0010 (10)
C20	0.0227 (8)	0.0373 (10)	0.0413 (12)	−0.0006 (8)	0.0046 (8)	−0.0054 (9)

O1—C13	1.443 (3)	C10—H10	1.00
O1—H1	0.99 (3)	C11—C12	1.507 (3)
O2—C7	1.215 (3)	C11—H11A	0.99
C1—C10	1.525 (3)	C11—H11B	0.99
C1—C2	1.546 (3)	C12—C13	1.516 (3)
C1—H1A	0.99	C12—H12	1.00
C1—H1B	0.99	C13—C16	1.524 (3)
C2—C3	1.548 (3)	C13—C14	1.525 (4)
C2—H2A	0.99	C14—C15	1.523 (3)
C2—H2B	0.99	C14—H14A	0.99
C3—C4	1.538 (3)	C14—H14B	0.99
C3—C5	1.553 (3)	C15—H15A	0.99
C3—H3	1.00	C15—H15B	0.99
C4—C19	1.525 (3)	C16—H16A	0.98
C4—C18	1.529 (3)	C16—H16B	0.98
C4—H4	1.00	C16—H16C	0.98
C5—C20	1.535 (2)	C17—H17A	0.98
C5—C10	1.538 (3)	C17—H17B	0.98
C5—C6	1.547 (3)	C17—H17C	0.98
C6—C7	1.516 (3)	C18—H18A	0.98
C6—H6A	0.99	C18—H18B	0.98
C6—H6B	0.99	C18—H18C	0.98
C7—C8	1.532 (3)	C19—H19A	0.98
C8—C15	1.539 (3)	C19—H19B	0.98
C8—C9	1.547 (3)	C19—H19C	0.98
C8—C17	1.553 (3)	C20—H20A	0.98
C9—C11	1.514 (3)	C20—H20B	0.98
C9—C10	1.520 (3)	C20—H20C	0.98
C9—C12	1.521 (3)
C13—O1—H1	107.5 (18)	C12—C11—H11A	117.7
C10—C1—C2	104.67 (16)	C9—C11—H11A	117.7
C10—C1—H1A	110.8	C12—C11—H11B	117.7
C2—C1—H1A	110.8	C9—C11—H11B	117.7
C10—C1—H1B	110.8	H11A—C11—H11B	114.8
C2—C1—H1B	110.8	C11—C12—C13	121.3 (2)
H1A—C1—H1B	108.9	C11—C12—C9	60.01 (14)
C1—C2—C3	106.74 (17)	C13—C12—C9	122.7 (2)
C1—C2—H2A	110.4	C11—C12—H12	114.1
C3—C2—H2A	110.4	C13—C12—H12	114.1
C1—C2—H2B	110.4	C9—C12—H12	114.1
C3—C2—H2B	110.4	O1—C13—C12	105.05 (18)
H2A—C2—H2B	108.6	O1—C13—C16	109.21 (19)
C4—C3—C2	112.18 (16)	C12—C13—C16	110.81 (19)
C4—C3—C5	118.79 (15)	O1—C13—C14	109.27 (18)
C2—C3—C5	103.20 (15)	C12—C13—C14	111.03 (18)
C4—C3—H3	107.4	C16—C13—C14	111.26 (19)
C2—C3—H3	107.4	C15—C14—C13	111.42 (17)
C5—C3—H3	107.4	C15—C14—H14A	109.3
C19—C4—C18	109.33 (18)	C13—C14—H14A	109.3
C19—C4—C3	114.03 (18)	C15—C14—H14B	109.3
C18—C4—C3	109.55 (17)	C13—C14—H14B	109.3
C19—C4—H4	107.9	H14A—C14—H14B	108
C18—C4—H4	107.9	C14—C15—C8	111.71 (16)
C3—C4—H4	107.9	C14—C15—H15A	109.3
C20—C5—C10	111.46 (15)	C8—C15—H15A	109.3
C20—C5—C6	112.37 (17)	C14—C15—H15B	109.3
C10—C5—C6	107.48 (15)	C8—C15—H15B	109.3
C20—C5—C3	109.86 (16)	H15A—C15—H15B	107.9
C10—C5—C3	100.68 (14)	C13—C16—H16A	109.5
C6—C5—C3	114.39 (16)	C13—C16—H16B	109.5
C7—C6—C5	114.38 (16)	H16A—C16—H16B	109.5
C7—C6—H6A	108.7	C13—C16—H16C	109.5
C5—C6—H6A	108.7	H16A—C16—H16C	109.5
C7—C6—H6B	108.7	H16B—C16—H16C	109.5
C5—C6—H6B	108.7	C8—C17—H17A	109.5
H6A—C6—H6B	107.6	C8—C17—H17B	109.5
O2—C7—C6	119.85 (18)	H17A—C17—H17B	109.5
O2—C7—C8	121.02 (18)	C8—C17—H17C	109.5
C6—C7—C8	118.94 (17)	H17A—C17—H17C	109.5
C7—C8—C15	110.17 (16)	H17B—C17—H17C	109.5
C7—C8—C9	110.04 (15)	C4—C18—H18A	109.5
C15—C8—C9	110.73 (16)	C4—C18—H18B	109.5
C7—C8—C17	102.90 (17)	H18A—C18—H18B	109.5
C15—C8—C17	108.97 (16)	C4—C18—H18C	109.5
C9—C8—C17	113.75 (17)	H18A—C18—H18C	109.5
C11—C9—C10	120.53 (17)	H18B—C18—H18C	109.5
C11—C9—C12	59.54 (14)	C4—C19—H19A	109.5
C10—C9—C12	116.15 (17)	C4—C19—H19B	109.5
C11—C9—C8	118.43 (17)	H19A—C19—H19B	109.5
C10—C9—C8	113.08 (16)	C4—C19—H19C	109.5
C12—C9—C8	119.15 (17)	H19A—C19—H19C	109.5
C9—C10—C1	120.82 (17)	H19B—C19—H19C	109.5
C9—C10—C5	113.78 (16)	C5—C20—H20A	109.5
C1—C10—C5	104.67 (15)	C5—C20—H20B	109.5
C9—C10—H10	105.4	H20A—C20—H20B	109.5
C1—C10—H10	105.4	C5—C20—H20C	109.5
C5—C10—H10	105.4	H20A—C20—H20C	109.5
C12—C11—C9	60.45 (13)	H20B—C20—H20C	109.5
C10—C1—C2—C3	3.7 (2)	C12—C9—C10—C1	−38.2 (2)
C1—C2—C3—C4	152.34 (17)	C8—C9—C10—C1	178.76 (16)
C1—C2—C3—C5	23.3 (2)	C11—C9—C10—C5	−95.5 (2)
C2—C3—C4—C19	−173.09 (18)	C12—C9—C10—C5	−164.01 (16)
C5—C3—C4—C19	−52.7 (2)	C8—C9—C10—C5	53.0 (2)
C2—C3—C4—C18	64.0 (2)	C2—C1—C10—C9	−159.73 (17)
C5—C3—C4—C18	−175.61 (18)	C2—C1—C10—C5	−29.8 (2)
C4—C3—C5—C20	−48.0 (2)	C20—C5—C10—C9	61.6 (2)
C2—C3—C5—C20	76.87 (19)	C6—C5—C10—C9	−62.0 (2)
C4—C3—C5—C10	−165.61 (16)	C3—C5—C10—C9	178.04 (16)
C2—C3—C5—C10	−40.77 (17)	C20—C5—C10—C1	−72.4 (2)
C4—C3—C5—C6	79.5 (2)	C6—C5—C10—C1	164.08 (15)
C2—C3—C5—C6	−155.67 (15)	C3—C5—C10—C1	44.09 (17)
C20—C5—C6—C7	−106.20 (19)	C10—C9—C11—C12	−104.3 (2)
C10—C5—C6—C7	16.8 (2)	C8—C9—C11—C12	108.9 (2)
C3—C5—C6—C7	127.63 (17)	C9—C11—C12—C13	−112.3 (2)
C5—C6—C7—O2	−148.2 (2)	C10—C9—C12—C11	111.6 (2)
C5—C6—C7—C8	36.7 (3)	C8—C9—C12—C11	−107.7 (2)
O2—C7—C8—C15	16.3 (3)	C11—C9—C12—C13	110.0 (2)
C6—C7—C8—C15	−168.73 (18)	C10—C9—C12—C13	−138.4 (2)
O2—C7—C8—C9	138.6 (2)	C8—C9—C12—C13	2.3 (3)
C6—C7—C8—C9	−46.4 (2)	C11—C12—C13—O1	173.55 (19)
O2—C7—C8—C17	−99.8 (2)	C9—C12—C13—O1	101.3 (2)
C6—C7—C8—C17	75.2 (2)	C11—C12—C13—C16	−68.6 (3)
C7—C8—C9—C11	150.51 (18)	C9—C12—C13—C16	−140.9 (2)
C15—C8—C9—C11	−87.4 (2)	C11—C12—C13—C14	55.5 (3)
C17—C8—C9—C11	35.7 (3)	C9—C12—C13—C14	−16.7 (3)
C7—C8—C9—C10	1.4 (2)	O1—C13—C14—C15	−67.2 (2)
C15—C8—C9—C10	123.40 (17)	C12—C13—C14—C15	48.2 (2)
C17—C8—C9—C10	−113.48 (19)	C16—C13—C14—C15	172.11 (18)
C7—C8—C9—C12	−140.47 (18)	C13—C14—C15—C8	−68.4 (2)
C15—C8—C9—C12	−18.4 (2)	C7—C8—C15—C14	172.31 (18)
C17—C8—C9—C12	104.7 (2)	C9—C8—C15—C14	50.3 (2)
C11—C9—C10—C1	30.3 (3)	C17—C8—C15—C14	−75.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.99 (3)	1.93 (3)	2.916 (2)	172 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.99 (3)	1.93 (3)	2.916 (2)	172 (3)

Symmetry code: (i) .