(3R,4aS,5R)-3-Hydro­xy-5-isopropenyl-3,8-di­methyl-4,4a,5,6-tetra­hydro-2(3H)-naphthalenone

In the crystal structure of C₁₅H₂₀O₂, mol­ecules are associated by intermolecular hydrogen bonds between the hydroxy function and a keto group [O...O 2.770 (2) Å], forming chains along the [100] direction in the crystal. Both six-membered rings in the decalin unit adopt envelope conformations; one section of the mol­ecule, encompassing the extended conjugation of a C=C double bond with an enone functionality [C=C—C=O = 175.6 (2)° and C=C—C=C = 176.6 (2)°], is flat, whilst the rest of the mol­ecule is folded relative to the constrained part. The stereochemistry was determined from the R-(–)-carvone starting material.

Computing details

Data collection: Locally modified CAD4-Version 5 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON.

(I)

Crystal data

C15H20O2	Dx = 1.190 Mg m^−3
Mr = 232.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 8.6663 (9) Å	θ = 9–15°
b = 9.671 (3) Å	µ = 0.08 mm^−1
c = 15.470 (4) Å	T = 150 K
V = 1296.6 (5) Å^3	Plate, colourless
Z = 4	0.50 × 0.37 × 0.20 mm
F(000) = 504

Data collection

Enraf-Nonius CAD4T diffractometer	Rint = 0.035
Radiation source: rotating anode	θmax = 27.5°, θmin = 2.5°
Graphite monochromator	h = −11→0
ω scans	k = −12→0
3441 measured reflections	l = −20→20
1720 independent reflections	3 standard reflections every 60 min
1457 reflections with I > 2σ(I)	intensity decay: 2.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 0.103P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.002
1720 reflections	Δρmax = 0.21 e Å^−3
161 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Absolute structure: see experimental
Primary atom site location: structure-invariant direct methods

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2457 (2)	0.4434 (2)	0.04387 (13)	0.0239 (4)
H1	0.1465	0.4053	0.0331	0.029*
C2	0.3757 (2)	0.38714 (19)	−0.00305 (13)	0.0237 (4)
O2	0.36124 (19)	0.28725 (15)	−0.05168 (11)	0.0397 (4)
C3	0.5350 (2)	0.4513 (2)	0.01162 (12)	0.0217 (4)
C4	0.5182 (2)	0.5986 (2)	0.04361 (13)	0.0237 (4)
H4A	0.4750	0.6566	−0.0033	0.028*
H4B	0.6214	0.6356	0.0585	0.028*
C4A	0.4131 (2)	0.60801 (19)	0.12296 (12)	0.0211 (4)
H4C	0.4603	0.5501	0.1695	0.025*
C5	0.4018 (2)	0.7570 (2)	0.15740 (13)	0.0246 (4)
H5	0.3616	0.8162	0.1094	0.030*
C6	0.2853 (2)	0.7642 (2)	0.23170 (14)	0.0298 (5)
H6A	0.3302	0.7195	0.2835	0.036*
H6B	0.2651	0.8623	0.2460	0.036*
C7	0.1372 (2)	0.6952 (2)	0.20969 (14)	0.0318 (5)
H7	0.0476	0.7225	0.2406	0.038*
C8	0.1216 (2)	0.5972 (2)	0.14920 (13)	0.0278 (4)
C8A	0.2570 (2)	0.54715 (19)	0.10213 (13)	0.0217 (4)
O31	0.60097 (18)	0.37244 (16)	0.08043 (9)	0.0325 (4)
H31	0.680 (3)	0.323 (3)	0.0656 (17)	0.043 (7)*
C32	0.6319 (2)	0.4434 (2)	−0.07056 (13)	0.0301 (4)
H32A	0.7372	0.4745	−0.0581	0.045*
H32B	0.5863	0.5029	−0.1150	0.045*
H32C	0.6345	0.3477	−0.0913	0.045*
C51	0.5567 (2)	0.8149 (2)	0.18432 (14)	0.0298 (5)
C52	0.6110 (3)	0.9293 (3)	0.14863 (16)	0.0470 (6)
H52A	0.7062	0.9670	0.1678	0.056*
H52B	0.5547	0.9737	0.1038	0.056*
C53	0.6421 (3)	0.7414 (2)	0.25534 (16)	0.0374 (5)
H53A	0.6553	0.6439	0.2398	0.056*
H53B	0.5830	0.7482	0.3092	0.056*
H53C	0.7435	0.7843	0.2633	0.056*
C81	−0.0341 (2)	0.5352 (3)	0.12878 (18)	0.0447 (7)
H81A	−0.1121	0.5752	0.1672	0.067*
H81B	−0.0301	0.4349	0.1374	0.067*
H81C	−0.0610	0.5553	0.0685	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0210 (9)	0.0237 (8)	0.0269 (10)	−0.0029 (8)	−0.0017 (7)	0.0004 (8)
C2	0.0263 (9)	0.0205 (8)	0.0245 (9)	−0.0025 (8)	−0.0002 (8)	−0.0009 (8)
O2	0.0337 (8)	0.0362 (8)	0.0492 (10)	−0.0095 (7)	0.0101 (8)	−0.0211 (7)
C3	0.0229 (9)	0.0215 (8)	0.0207 (9)	0.0001 (8)	0.0007 (7)	0.0009 (8)
C4	0.0238 (9)	0.0243 (9)	0.0231 (10)	−0.0027 (8)	0.0035 (8)	−0.0040 (8)
C4A	0.0222 (9)	0.0221 (8)	0.0192 (9)	0.0001 (8)	−0.0005 (7)	−0.0012 (7)
C5	0.0272 (9)	0.0232 (8)	0.0235 (9)	0.0006 (8)	0.0003 (8)	−0.0021 (7)
C6	0.0278 (10)	0.0301 (10)	0.0313 (11)	0.0024 (9)	0.0031 (9)	−0.0100 (9)
C7	0.0227 (10)	0.0353 (10)	0.0374 (12)	0.0028 (9)	0.0080 (9)	−0.0071 (9)
C8	0.0221 (9)	0.0305 (10)	0.0308 (11)	0.0007 (9)	0.0017 (8)	−0.0044 (8)
C8A	0.0215 (9)	0.0212 (8)	0.0224 (9)	−0.0003 (8)	0.0002 (7)	0.0025 (8)
O31	0.0308 (8)	0.0396 (8)	0.0271 (8)	0.0145 (7)	0.0026 (6)	0.0044 (7)
C32	0.0323 (11)	0.0288 (9)	0.0294 (10)	−0.0033 (9)	0.0074 (9)	−0.0046 (9)
C51	0.0304 (10)	0.0304 (10)	0.0285 (11)	−0.0035 (9)	0.0050 (9)	−0.0128 (9)
C52	0.0525 (15)	0.0447 (13)	0.0438 (14)	−0.0211 (13)	0.0076 (12)	−0.0090 (11)
C53	0.0271 (10)	0.0448 (12)	0.0402 (12)	0.0014 (10)	−0.0053 (10)	−0.0153 (10)
C81	0.0221 (10)	0.0537 (15)	0.0584 (16)	−0.0053 (11)	0.0088 (10)	−0.0237 (13)

Geometric parameters (Å, º)

C1—C2	1.447 (3)	C6—H6B	0.9900
C1—C8A	1.352 (3)	C7—C8	1.339 (3)
C1—H1	0.9500	C7—H7	0.9500
C2—O2	1.231 (2)	C8—C8A	1.463 (3)
C2—C3	1.531 (3)	C8—C81	1.510 (3)
C3—O31	1.429 (2)	O31—H31	0.86 (3)
C3—C4	1.515 (3)	C32—H32A	0.9800
C3—C32	1.526 (3)	C32—H32B	0.9800
C4—C4A	1.531 (2)	C32—H32C	0.9800
C4—H4A	0.9900	C51—C52	1.323 (3)
C4—H4B	0.9900	C51—C53	1.503 (3)
C4A—C8A	1.510 (2)	C52—H52A	0.9500
C4A—C5	1.540 (3)	C52—H52B	0.9500
C4A—H4C	1.0000	C53—H53A	0.9800
C5—C51	1.513 (3)	C53—H53B	0.9800
C5—C6	1.531 (3)	C53—H53C	0.9800
C5—H5	1.0000	C81—H81A	0.9800
C6—C7	1.486 (3)	C81—H81B	0.9800
C6—H6A	0.9900	C81—H81C	0.9800
C8A—C1—C2	123.87 (16)	H6A—C6—H6B	107.9
C8A—C1—H1	118.1	C8—C7—C6	124.42 (18)
C2—C1—H1	118.1	C8—C7—H7	117.8
O2—C2—C1	121.53 (19)	C6—C7—H7	117.8
O2—C2—C3	120.05 (18)	C7—C8—C8A	120.08 (18)
C1—C2—C3	118.39 (15)	C7—C8—C81	121.18 (19)
O31—C3—C4	107.28 (16)	C8A—C8—C81	118.74 (17)
O31—C3—C32	111.93 (15)	C1—C8A—C8	121.28 (16)
C4—C3—C32	111.87 (15)	C1—C8A—C4A	119.75 (15)
O31—C3—C2	104.76 (15)	C8—C8A—C4A	118.89 (16)
C4—C3—C2	110.07 (15)	C3—O31—H31	114.4 (18)
C32—C3—C2	110.65 (16)	C3—C32—H32A	109.5
C3—C4—C4A	112.00 (15)	C3—C32—H32B	109.5
C3—C4—H4A	109.2	H32A—C32—H32B	109.5
C4A—C4—H4A	109.2	C3—C32—H32C	109.5
C3—C4—H4B	109.2	H32A—C32—H32C	109.5
C4A—C4—H4B	109.2	H32B—C32—H32C	109.5
H4A—C4—H4B	107.9	C52—C51—C53	121.7 (2)
C8A—C4A—C4	109.80 (14)	C52—C51—C5	120.6 (2)
C8A—C4A—C5	112.41 (15)	C53—C51—C5	117.58 (18)
C4—C4A—C5	111.77 (15)	C51—C52—H52A	120.0
C8A—C4A—H4C	107.5	C51—C52—H52B	120.0
C4—C4A—H4C	107.5	H52A—C52—H52B	120.0
C5—C4A—H4C	107.5	C51—C53—H53A	109.5
C51—C5—C6	111.19 (16)	C51—C53—H53B	109.5
C51—C5—C4A	112.63 (16)	H53A—C53—H53B	109.5
C6—C5—C4A	110.15 (16)	C51—C53—H53C	109.5
C51—C5—H5	107.5	H53A—C53—H53C	109.5
C6—C5—H5	107.5	H53B—C53—H53C	109.5
C4A—C5—H5	107.5	C8—C81—H81A	109.5
C7—C6—C5	112.14 (17)	C8—C81—H81B	109.5
C7—C6—H6A	109.2	H81A—C81—H81B	109.5
C5—C6—H6A	109.2	C8—C81—H81C	109.5
C7—C6—H6B	109.2	H81A—C81—H81C	109.5
C5—C6—H6B	109.2	H81B—C81—H81C	109.5
C8A—C1—C2—O2	175.6 (2)	C4A—C5—C6—C7	−48.7 (2)
C8A—C1—C2—C3	−2.1 (3)	C5—C6—C7—C8	23.0 (3)
O2—C2—C3—O31	−86.5 (2)	C6—C7—C8—C8A	2.6 (3)
C1—C2—C3—O31	91.20 (19)	C6—C7—C8—C81	−178.1 (2)
O2—C2—C3—C4	158.42 (18)	C2—C1—C8A—C8	−178.38 (19)
C1—C2—C3—C4	−23.9 (2)	C2—C1—C8A—C4A	−1.7 (3)
O2—C2—C3—C32	34.3 (2)	C7—C8—C8A—C1	176.6 (2)
C1—C2—C3—C32	−148.01 (18)	C81—C8—C8A—C1	−2.7 (3)
O31—C3—C4—C4A	−60.27 (19)	C7—C8—C8A—C4A	−0.1 (3)
C32—C3—C4—C4A	176.62 (16)	C81—C8—C8A—C4A	−179.4 (2)
C2—C3—C4—C4A	53.2 (2)	C4—C4A—C8A—C1	30.6 (2)
C3—C4—C4A—C8A	−56.9 (2)	C5—C4A—C8A—C1	155.65 (17)
C3—C4—C4A—C5	177.68 (16)	C4—C4A—C8A—C8	−152.66 (17)
C8A—C4A—C5—C51	175.94 (16)	C5—C4A—C8A—C8	−27.6 (2)
C4—C4A—C5—C51	−60.1 (2)	C6—C5—C51—C52	−113.9 (2)
C8A—C4A—C5—C6	51.2 (2)	C4A—C5—C51—C52	121.9 (2)
C4—C4A—C5—C6	175.18 (16)	C6—C5—C51—C53	63.4 (2)
C51—C5—C6—C7	−174.25 (17)	C4A—C5—C51—C53	−60.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O2^i	0.86 (3)	1.91 (3)	2.770 (2)	171 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z.