rac-8a'-Methyl-3',4',8',8a'-tetra-hydro-2'H-spiro-[[1,3]dioxolane-2,1'-naphthalen]-6'(7'H)-one.

The title racemic compound, C(13)H(18)O(3), a common precursor in the total synthesis of terpenes, crystallizes with two molecules in the asymmetric unit. The crystal structure is made up of triple chains, formed by weak inter-molecular C-H⋯O contacts, propagating in the a-axis direction.

Related literature

For the synthesis of the title compound, see: Smith et al. (2007 ▶). For the crystal structure of the educt, 9-methyl-Δ5,10-deca­lin-1,6-dione, see: Jones et al. (1973 ▶). For application of the title compound as a precursor in the synthesis of terpenes, see: Foot et al. (2006 ▶); Hatzellis et al. (2004 ▶); Coltart & Danishefsky (2003 ▶).

Experimental

Crystal data

C13H18O3

M = 222.27

Triclinic,

a = 9.6841 (15) Å

b = 10.5515 (14) Å

c = 12.8717 (19) Å

α = 102.493 (4)°

β = 111.938 (4)°

γ = 98.665 (4)°

V = 1151.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 200 K

0.60 × 0.40 × 0.40 mm

Data collection

Bruker SMART X2S diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.948, T max = 0.965

11107 measured reflections

4037 independent reflections

3265 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.106

S = 1.05

4037 reflections

291 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.19 e Å−3

Data collection: GIS (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶), OLEX2 (Dolomanov et al., 2009 ▶) and VESTA (Momma & Izumi, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034349/su2308sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034349/su2308Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034349/su2308Isup3.cml

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

C13H18O3	Z = 4
Mr = 222.27	F(000) = 480
Triclinic, P1	Dx = 1.282 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6841 (15) Å	Cell parameters from 4738 reflections
b = 10.5515 (14) Å	θ = 2.3–25.0°
c = 12.8717 (19) Å	µ = 0.09 mm−1
α = 102.493 (4)°	T = 200 K
β = 111.938 (4)°	Needle, colourless
γ = 98.665 (4)°	0.60 × 0.40 × 0.40 mm
V = 1151.6 (3) Å3

Bruker SMART X2S diffractometer	4037 independent reflections
Radiation source: XOS X-beam microfocus source	3265 reflections with I > 2σ(I)
doubly curved silicon crystal	Rint = 0.032
ω scans	θmax = 25.1°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.948, Tmax = 0.965	k = −12→12
11107 measured reflections	l = −15→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0516P)2 + 0.2344P] where P = (Fo2 + 2Fc2)/3
4037 reflections	(Δ/σ)max < 0.001
291 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.19 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
O11	−0.36579 (13)	−0.13960 (12)	0.44218 (10)	0.0515 (3)
C11	−0.26520 (17)	−0.07427 (15)	0.53959 (13)	0.0353 (4)
C12	−0.11911 (18)	−0.11449 (16)	0.59416 (15)	0.0419 (4)
H12A	−0.0964	−0.1670	0.5316	0.050*
H12B	−0.1325	−0.1726	0.6425	0.050*
C13	0.01603 (17)	0.00794 (16)	0.67085 (14)	0.0391 (4)
H13A	0.0369	0.0598	0.6204	0.047*
H13B	0.1089	−0.0228	0.7088	0.047*
C14	−0.01326 (16)	0.10053 (15)	0.76622 (12)	0.0322 (3)
C15	−0.17489 (16)	0.11996 (14)	0.71628 (12)	0.0303 (3)
C16	−0.28429 (16)	0.04332 (15)	0.61172 (13)	0.0328 (3)
H16	−0.3796	0.0667	0.5828	0.039*
C17	−0.21067 (18)	0.22780 (17)	0.79299 (14)	0.0413 (4)
H17A	−0.2196	0.1967	0.8580	0.050*
H17B	−0.3115	0.2417	0.7461	0.050*
C18	−0.08923 (19)	0.36159 (17)	0.84445 (14)	0.0447 (4)
H18A	−0.0967	0.4038	0.7816	0.054*
H18B	−0.1091	0.4226	0.9044	0.054*
C19	0.07257 (18)	0.34259 (16)	0.90015 (13)	0.0414 (4)
H19A	0.1493	0.4296	0.9267	0.050*
H19B	0.0846	0.3117	0.9696	0.050*
C110	0.10215 (16)	0.24032 (16)	0.81303 (12)	0.0340 (3)
C111	0.0068 (2)	0.03947 (18)	0.86826 (15)	0.0474 (4)
H1MA	−0.0214	0.0946	0.9250	0.071*
H1MB	0.1144	0.0370	0.9070	0.071*
H1MC	−0.0598	−0.0520	0.8374	0.071*
O12	0.09080 (12)	0.28742 (11)	0.71548 (9)	0.0387 (3)
O13	0.25563 (12)	0.22675 (12)	0.86454 (10)	0.0466 (3)
C112	0.24137 (19)	0.35950 (18)	0.74068 (16)	0.0481 (4)
H1KA	0.2594	0.4560	0.7798	0.058*
H1KB	0.2570	0.3502	0.6679	0.058*
C113	0.3463 (2)	0.2976 (2)	0.82021 (19)	0.0609 (5)
H1KC	0.3867	0.2354	0.7765	0.073*
H1KD	0.4343	0.3676	0.8850	0.073*
O21	0.11049 (14)	0.70843 (14)	0.91102 (11)	0.0569 (4)
C21	0.19562 (17)	0.73622 (16)	0.86470 (13)	0.0361 (4)
C22	0.35845 (18)	0.81980 (18)	0.93451 (13)	0.0422 (4)
H22A	0.3972	0.8107	1.0147	0.051*
H22B	0.3613	0.9155	0.9410	0.051*
C23	0.46228 (17)	0.77619 (16)	0.87668 (13)	0.0362 (4)
H23A	0.4676	0.6835	0.8780	0.043*
H23B	0.5676	0.8356	0.9227	0.043*
C24	0.40501 (16)	0.78078 (14)	0.74922 (13)	0.0303 (3)
C25	0.23169 (16)	0.71959 (14)	0.68281 (12)	0.0293 (3)
C26	0.14168 (16)	0.69527 (15)	0.73754 (13)	0.0319 (3)
H26	0.0366	0.6487	0.6909	0.038*
C27	0.16356 (19)	0.68995 (19)	0.55151 (13)	0.0424 (4)
H27A	0.1637	0.7756	0.5318	0.051*
H27B	0.0552	0.6370	0.5181	0.051*
C28	0.25155 (19)	0.6126 (2)	0.49578 (14)	0.0478 (4)
H28A	0.2115	0.6063	0.4114	0.057*
H28B	0.2355	0.5202	0.5024	0.057*
C29	0.42334 (19)	0.68194 (18)	0.55581 (14)	0.0432 (4)
H29A	0.4790	0.6283	0.5206	0.052*
H29B	0.4404	0.7715	0.5437	0.052*
C210	0.48576 (16)	0.69737 (14)	0.68634 (13)	0.0307 (3)
C211	0.4437 (2)	0.92774 (16)	0.74809 (17)	0.0474 (4)
H2MA	0.3994	0.9313	0.6671	0.071*
H2MB	0.5558	0.9633	0.7825	0.071*
H2MC	0.4006	0.9819	0.7940	0.071*
O22	0.46457 (11)	0.56518 (10)	0.69896 (9)	0.0342 (3)
O23	0.64712 (11)	0.75715 (11)	0.74433 (10)	0.0404 (3)
C212	0.61156 (18)	0.54166 (18)	0.75591 (16)	0.0450 (4)
H2KA	0.6152	0.4513	0.7167	0.054*
H2KB	0.6363	0.5497	0.8394	0.054*
C213	0.72049 (19)	0.64914 (19)	0.74471 (17)	0.0504 (5)
H2KC	0.8229	0.6757	0.8119	0.061*
H2KD	0.7325	0.6191	0.6709	0.061*

	U11	U22	U33	U12	U13	U23
O11	0.0446 (7)	0.0560 (8)	0.0396 (6)	0.0102 (6)	0.0118 (5)	−0.0010 (6)
C11	0.0356 (8)	0.0356 (8)	0.0373 (8)	0.0059 (7)	0.0185 (7)	0.0120 (7)
C12	0.0409 (9)	0.0356 (9)	0.0503 (10)	0.0126 (7)	0.0197 (8)	0.0121 (7)
C13	0.0312 (8)	0.0383 (9)	0.0489 (9)	0.0115 (7)	0.0173 (7)	0.0126 (7)
C14	0.0288 (7)	0.0356 (8)	0.0339 (8)	0.0068 (6)	0.0124 (6)	0.0157 (6)
C15	0.0318 (8)	0.0333 (8)	0.0323 (7)	0.0078 (6)	0.0173 (6)	0.0159 (6)
C16	0.0278 (7)	0.0368 (8)	0.0351 (8)	0.0094 (6)	0.0129 (6)	0.0132 (7)
C17	0.0393 (9)	0.0487 (10)	0.0374 (8)	0.0138 (7)	0.0184 (7)	0.0093 (7)
C18	0.0508 (10)	0.0426 (10)	0.0354 (8)	0.0139 (8)	0.0164 (7)	0.0035 (7)
C19	0.0431 (9)	0.0406 (9)	0.0308 (8)	0.0023 (7)	0.0100 (7)	0.0072 (7)
C110	0.0289 (8)	0.0416 (9)	0.0305 (8)	0.0059 (7)	0.0087 (6)	0.0180 (7)
C111	0.0452 (10)	0.0507 (10)	0.0469 (10)	0.0079 (8)	0.0134 (8)	0.0297 (8)
O12	0.0366 (6)	0.0430 (6)	0.0369 (6)	0.0022 (5)	0.0142 (5)	0.0208 (5)
O13	0.0284 (6)	0.0571 (7)	0.0505 (7)	0.0056 (5)	0.0091 (5)	0.0259 (6)
C112	0.0457 (10)	0.0418 (10)	0.0585 (11)	−0.0007 (8)	0.0275 (8)	0.0162 (8)
C113	0.0383 (10)	0.0721 (14)	0.0739 (13)	0.0040 (9)	0.0248 (9)	0.0291 (11)
O21	0.0482 (7)	0.0828 (9)	0.0488 (7)	0.0105 (7)	0.0316 (6)	0.0214 (7)
C21	0.0356 (8)	0.0407 (9)	0.0388 (8)	0.0134 (7)	0.0199 (7)	0.0144 (7)
C22	0.0397 (9)	0.0511 (10)	0.0296 (8)	0.0078 (8)	0.0147 (7)	0.0024 (7)
C23	0.0278 (8)	0.0430 (9)	0.0304 (8)	0.0041 (7)	0.0096 (6)	0.0045 (7)
C24	0.0291 (7)	0.0288 (8)	0.0342 (8)	0.0053 (6)	0.0152 (6)	0.0098 (6)
C25	0.0300 (7)	0.0275 (7)	0.0316 (7)	0.0116 (6)	0.0116 (6)	0.0107 (6)
C26	0.0256 (7)	0.0333 (8)	0.0349 (8)	0.0068 (6)	0.0112 (6)	0.0093 (6)
C27	0.0386 (9)	0.0596 (11)	0.0319 (8)	0.0185 (8)	0.0134 (7)	0.0174 (7)
C28	0.0480 (10)	0.0699 (12)	0.0254 (8)	0.0208 (9)	0.0148 (7)	0.0113 (8)
C29	0.0492 (10)	0.0544 (10)	0.0416 (9)	0.0204 (8)	0.0292 (8)	0.0213 (8)
C210	0.0283 (7)	0.0313 (8)	0.0369 (8)	0.0054 (6)	0.0175 (6)	0.0129 (6)
C211	0.0495 (10)	0.0315 (9)	0.0670 (12)	0.0072 (7)	0.0319 (9)	0.0147 (8)
O22	0.0310 (5)	0.0301 (6)	0.0454 (6)	0.0088 (4)	0.0180 (5)	0.0144 (5)
O23	0.0283 (5)	0.0391 (6)	0.0552 (7)	0.0036 (5)	0.0222 (5)	0.0120 (5)
C212	0.0372 (9)	0.0516 (10)	0.0562 (10)	0.0202 (8)	0.0222 (8)	0.0243 (8)
C213	0.0349 (9)	0.0589 (11)	0.0648 (12)	0.0165 (8)	0.0245 (8)	0.0228 (9)

O11—C11	1.2277 (18)	O21—C21	1.2211 (18)
C11—C16	1.461 (2)	C21—C26	1.458 (2)
C11—C12	1.497 (2)	C21—C22	1.500 (2)
C12—C13	1.526 (2)	C22—C23	1.526 (2)
C12—H12A	0.9900	C22—H22A	0.9900
C12—H12B	0.9900	C22—H22B	0.9900
C13—C14	1.538 (2)	C23—C24	1.538 (2)
C13—H13A	0.9900	C23—H23A	0.9900
C13—H13B	0.9900	C23—H23B	0.9900
C14—C15	1.519 (2)	C24—C25	1.526 (2)
C14—C111	1.546 (2)	C24—C211	1.544 (2)
C14—C110	1.550 (2)	C24—C210	1.553 (2)
C15—C16	1.339 (2)	C25—C26	1.338 (2)
C15—C17	1.509 (2)	C25—C27	1.505 (2)
C16—H16	0.9500	C26—H26	0.9500
C17—C18	1.526 (2)	C27—C28	1.523 (2)
C17—H17A	0.9900	C27—H27A	0.9900
C17—H17B	0.9900	C27—H27B	0.9900
C18—C19	1.525 (2)	C28—C29	1.526 (2)
C18—H18A	0.9900	C28—H28A	0.9900
C18—H18B	0.9900	C28—H28B	0.9900
C19—C110	1.521 (2)	C29—C210	1.519 (2)
C19—H19A	0.9900	C29—H29A	0.9900
C19—H19B	0.9900	C29—H29B	0.9900
C110—O12	1.4209 (17)	C210—O23	1.4229 (17)
C110—O13	1.4276 (18)	C210—O22	1.4320 (18)
C111—H1MA	0.9800	C211—H2MA	0.9800
C111—H1MB	0.9800	C211—H2MB	0.9800
C111—H1MC	0.9800	C211—H2MC	0.9800
O12—C112	1.4197 (19)	O22—C212	1.4250 (18)
O13—C113	1.420 (2)	O23—C213	1.431 (2)
C112—C113	1.490 (3)	C212—C213	1.498 (2)
C112—H1KA	0.9900	C212—H2KA	0.9900
C112—H1KB	0.9900	C212—H2KB	0.9900
C113—H1KC	0.9900	C213—H2KC	0.9900
C113—H1KD	0.9900	C213—H2KD	0.9900
O11—C11—C16	121.98 (14)	O21—C21—C26	121.53 (14)
O11—C11—C12	121.98 (14)	O21—C21—C22	122.15 (14)
C16—C11—C12	115.96 (13)	C26—C21—C22	116.25 (13)
C11—C12—C13	111.41 (13)	C21—C22—C23	110.97 (12)
C11—C12—H12A	109.3	C21—C22—H22A	109.4
C13—C12—H12A	109.3	C23—C22—H22A	109.4
C11—C12—H12B	109.3	C21—C22—H22B	109.4
C13—C12—H12B	109.3	C23—C22—H22B	109.4
H12A—C12—H12B	108.0	H22A—C22—H22B	108.0
C12—C13—C14	113.01 (12)	C22—C23—C24	112.62 (13)
C12—C13—H13A	109.0	C22—C23—H23A	109.1
C14—C13—H13A	109.0	C24—C23—H23A	109.1
C12—C13—H13B	109.0	C22—C23—H23B	109.1
C14—C13—H13B	109.0	C24—C23—H23B	109.1
H13A—C13—H13B	107.8	H23A—C23—H23B	107.8
C15—C14—C13	110.68 (12)	C25—C24—C23	110.83 (11)
C15—C14—C111	109.19 (12)	C25—C24—C211	109.70 (13)
C13—C14—C111	110.03 (13)	C23—C24—C211	109.57 (13)
C15—C14—C110	107.85 (12)	C25—C24—C210	108.00 (11)
C13—C14—C110	109.46 (12)	C23—C24—C210	109.07 (12)
C111—C14—C110	109.59 (12)	C211—C24—C210	109.64 (12)
C16—C15—C17	120.37 (13)	C26—C25—C27	120.58 (13)
C16—C15—C14	122.92 (13)	C26—C25—C24	122.30 (13)
C17—C15—C14	116.66 (13)	C27—C25—C24	117.11 (12)
C15—C16—C11	123.62 (14)	C25—C26—C21	123.76 (13)
C15—C16—H16	118.2	C25—C26—H26	118.1
C11—C16—H16	118.2	C21—C26—H26	118.1
C15—C17—C18	113.34 (13)	C25—C27—C28	112.53 (13)
C15—C17—H17A	108.9	C25—C27—H27A	109.1
C18—C17—H17A	108.9	C28—C27—H27A	109.1
C15—C17—H17B	108.9	C25—C27—H27B	109.1
C18—C17—H17B	108.9	C28—C27—H27B	109.1
H17A—C17—H17B	107.7	H27A—C27—H27B	107.8
C19—C18—C17	111.26 (14)	C27—C28—C29	110.82 (14)
C19—C18—H18A	109.4	C27—C28—H28A	109.5
C17—C18—H18A	109.4	C29—C28—H28A	109.5
C19—C18—H18B	109.4	C27—C28—H28B	109.5
C17—C18—H18B	109.4	C29—C28—H28B	109.5
H18A—C18—H18B	108.0	H28A—C28—H28B	108.1
C110—C19—C18	110.78 (12)	C210—C29—C28	110.28 (12)
C110—C19—H19A	109.5	C210—C29—H29A	109.6
C18—C19—H19A	109.5	C28—C29—H29A	109.6
C110—C19—H19B	109.5	C210—C29—H29B	109.6
C18—C19—H19B	109.5	C28—C29—H29B	109.6
H19A—C19—H19B	108.1	H29A—C29—H29B	108.1
O12—C110—O13	106.21 (11)	O23—C210—O22	106.12 (11)
O12—C110—C19	109.37 (13)	O23—C210—C29	111.74 (12)
O13—C110—C19	110.38 (12)	O22—C210—C29	107.31 (12)
O12—C110—C14	107.96 (11)	O23—C210—C24	108.53 (11)
O13—C110—C14	109.50 (12)	O22—C210—C24	109.70 (11)
C19—C110—C14	113.15 (12)	C29—C210—C24	113.19 (13)
C14—C111—H1MA	109.5	C24—C211—H2MA	109.5
C14—C111—H1MB	109.5	C24—C211—H2MB	109.5
H1MA—C111—H1MB	109.5	H2MA—C211—H2MB	109.5
C14—C111—H1MC	109.5	C24—C211—H2MC	109.5
H1MA—C111—H1MC	109.5	H2MA—C211—H2MC	109.5
H1MB—C111—H1MC	109.5	H2MB—C211—H2MC	109.5
C112—O12—C110	106.80 (11)	C212—O22—C210	109.00 (11)
C113—O13—C110	108.60 (13)	C210—O23—C213	106.50 (12)
O12—C112—C113	104.81 (13)	O22—C212—C213	103.85 (13)
O12—C112—H1KA	110.8	O22—C212—H2KA	111.0
C113—C112—H1KA	110.8	C213—C212—H2KA	111.0
O12—C112—H1KB	110.8	O22—C212—H2KB	111.0
C113—C112—H1KB	110.8	C213—C212—H2KB	111.0
H1KA—C112—H1KB	108.9	H2KA—C212—H2KB	109.0
O13—C113—C112	105.70 (14)	O23—C213—C212	103.06 (13)
O13—C113—H1KC	110.6	O23—C213—H2KC	111.2
C112—C113—H1KC	110.6	C212—C213—H2KC	111.2
O13—C113—H1KD	110.6	O23—C213—H2KD	111.2
C112—C113—H1KD	110.6	C212—C213—H2KD	111.2
H1KC—C113—H1KD	108.7	H2KC—C213—H2KD	109.1

D—H···A	D—H	H···A	D···A	D—H···A
C213—H2KC···O21i	0.99	2.52	3.450 (2)	156.
C16—H16···O11ii	0.95	2.62	3.547 (2)	166.
C17—H17A···O21iii	0.99	2.65	3.441 (2)	137.
C113—H1KC···O11iv	0.99	2.70	3.515 (3)	140.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C213—H2KC⋯O21i	0.99	2.52	3.450 (2)	156
C16—H16⋯O11ii	0.95	2.62	3.547 (2)	166
C17—H17A⋯O21iii	0.99	2.65	3.441 (2)	137
C113—H1KC⋯O11iv	0.99	2.70	3.515 (3)	140

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .