(1S,3R,8S,9R,10S)-2,2-Dichloro-3,7,7,10-tetra-methyl-9,10-ep-oxy-tricyclo-[6.4.0.0]dodeca-ne.

The title compound, C(16)H(24)Cl(2)O, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (cedrus atlantica). The mol-ecule forms an extended sheet of two fused rings which exhibit different conformations. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a chair conformation; the dihedral angle between the two rings is 38.2 (1)°.

Related literature

For the isolation of β-himachalene, see: Joseph & Dev (1968 ▶); Plattier & Teiseire (1974 ▶). For the reactivity of this sesquiterpene, see: Lassaba et al. (1998 ▶); Chekroun et al. (2000 ▶); El Jamili et al. (2002 ▶); Sbai et al. (2002 ▶); Dakir et al. (2004 ▶). For its biological activity, see: Daoubi et al. (2004 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H24Cl2O

M = 303.24

Orthorhombic,

a = 8.4995 (3) Å

b = 10.2461 (4) Å

c = 18.1656 (6) Å

V = 1581.98 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.40 mm−1

T = 298 K

0.67 × 0.41 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008) ▶ T min = 0.609, T max = 0.745

7171 measured reflections

3369 independent reflections

2830 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.106

S = 1.01

3369 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▶), 1423 Friedel pairs

Flack parameter: 0.04 (7)

Data collection: APEX2 (Bruker, 2009 ▶); 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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810045344/im2241sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045344/im2241Isup2.hkl

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

C16H24Cl2O	F(000) = 648
Mr = 303.24	Dx = 1.273 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3372 reflections
a = 8.4995 (3) Å	θ = 2.3–26.9°
b = 10.2461 (4) Å	µ = 0.40 mm−1
c = 18.1656 (6) Å	T = 298 K
V = 1581.98 (10) Å3	Prism, colourless
Z = 4	0.67 × 0.41 × 0.26 mm

Bruker APEXII CCD diffractometer	3369 independent reflections
Radiation source: fine-focus sealed tube	2830 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 8.3333 pixels mm-1	θmax = 26.9°, θmin = 2.3°
ω and φ scans	h = −9→10
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −13→10
Tmin = 0.609, Tmax = 0.745	l = −16→22
7171 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0568P)2 + 0.1767P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.106	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.22 e Å−3
3369 reflections	Δρmin = −0.29 e Å−3
177 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.073 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack & Bernardinelli (2000), 1423 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.04 (7)

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.

	x	y	z	Uiso*/Ueq
C1	0.6413 (2)	0.5366 (2)	0.38517 (10)	0.0356 (4)
C2	0.5713 (3)	0.5121 (2)	0.46043 (13)	0.0457 (5)
C3	0.6259 (3)	0.3964 (2)	0.41628 (12)	0.0460 (5)
C4	0.7701 (3)	0.3249 (3)	0.44259 (15)	0.0630 (7)
H4A	0.7375	0.2445	0.4663	0.076*
H4B	0.8230	0.3780	0.4792	0.076*
C5	0.8864 (3)	0.2922 (3)	0.38160 (18)	0.0675 (8)
H5A	0.9496	0.2180	0.3967	0.081*
H5B	0.8285	0.2671	0.3378	0.081*
C6	0.9941 (3)	0.4052 (3)	0.36304 (16)	0.0622 (7)
H6A	1.0759	0.3720	0.3308	0.075*
H6B	1.0451	0.4322	0.4083	0.075*
C7	0.9253 (3)	0.5290 (2)	0.32646 (13)	0.0464 (5)
C8	0.8050 (2)	0.59920 (19)	0.37903 (11)	0.0359 (4)
H8	0.8509	0.5936	0.4284	0.043*
C9	0.7899 (3)	0.7442 (2)	0.36270 (12)	0.0417 (5)
H9	0.8687	0.7990	0.3871	0.050*
C10	0.6401 (3)	0.8106 (2)	0.34700 (12)	0.0472 (5)
C11	0.4936 (3)	0.7314 (2)	0.34176 (14)	0.0513 (6)
H11A	0.4293	0.7650	0.3019	0.062*
H11B	0.4344	0.7408	0.3871	0.062*
C12	0.5260 (3)	0.5877 (2)	0.32837 (12)	0.0438 (5)
H12A	0.4284	0.5389	0.3314	0.053*
H12B	0.5692	0.5760	0.2794	0.053*
C13	0.5035 (4)	0.3054 (3)	0.38394 (17)	0.0677 (8)
H13A	0.4747	0.2411	0.4199	0.102*
H13B	0.5462	0.2627	0.3413	0.102*
H13C	0.4121	0.3547	0.3701	0.102*
C14	1.0652 (3)	0.6208 (3)	0.31365 (18)	0.0665 (8)
H14A	1.1444	0.5764	0.2855	0.100*
H14B	1.1083	0.6469	0.3602	0.100*
H14C	1.0303	0.6966	0.2872	0.100*
C15	0.8565 (3)	0.4933 (3)	0.25117 (13)	0.0575 (6)
H15A	0.8199	0.5710	0.2271	0.086*
H15B	0.7702	0.4340	0.2577	0.086*
H15C	0.9362	0.4527	0.2216	0.086*
C16	0.6208 (4)	0.9531 (3)	0.36539 (17)	0.0711 (8)
H16A	0.7209	0.9961	0.3619	0.107*
H16B	0.5809	0.9617	0.4146	0.107*
H16C	0.5484	0.9924	0.3314	0.107*
O	0.7511 (2)	0.78441 (15)	0.28799 (9)	0.0529 (4)
Cl1	0.66972 (9)	0.56107 (8)	0.54165 (3)	0.0691 (2)
Cl2	0.36713 (8)	0.53272 (8)	0.47590 (4)	0.0698 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0372 (10)	0.0357 (10)	0.0339 (9)	0.0002 (9)	0.0019 (9)	−0.0013 (8)
C2	0.0485 (11)	0.0517 (13)	0.0369 (11)	−0.0012 (10)	0.0050 (10)	0.0004 (10)
C3	0.0565 (13)	0.0393 (12)	0.0423 (11)	−0.0039 (10)	0.0074 (11)	0.0030 (9)
C4	0.0839 (18)	0.0461 (14)	0.0591 (16)	0.0145 (13)	0.0087 (14)	0.0109 (12)
C5	0.0754 (18)	0.0448 (14)	0.0822 (19)	0.0203 (13)	0.0098 (16)	0.0030 (13)
C6	0.0529 (15)	0.0563 (16)	0.0774 (17)	0.0187 (12)	0.0092 (14)	−0.0024 (13)
C7	0.0389 (11)	0.0482 (13)	0.0521 (12)	0.0031 (10)	0.0054 (10)	−0.0031 (11)
C8	0.0356 (10)	0.0379 (11)	0.0342 (10)	−0.0006 (9)	−0.0059 (9)	−0.0004 (8)
C9	0.0470 (12)	0.0384 (11)	0.0396 (11)	−0.0050 (9)	−0.0071 (10)	−0.0009 (9)
C10	0.0595 (14)	0.0389 (12)	0.0432 (11)	0.0053 (10)	−0.0069 (11)	0.0019 (9)
C11	0.0449 (13)	0.0572 (15)	0.0517 (14)	0.0121 (11)	−0.0082 (11)	0.0051 (11)
C12	0.0353 (11)	0.0537 (13)	0.0424 (11)	−0.0042 (10)	−0.0034 (9)	−0.0007 (10)
C13	0.081 (2)	0.0477 (14)	0.0743 (18)	−0.0225 (13)	0.0173 (16)	−0.0033 (13)
C14	0.0397 (13)	0.0759 (19)	0.084 (2)	−0.0028 (12)	0.0119 (14)	0.0010 (15)
C15	0.0643 (15)	0.0617 (15)	0.0467 (13)	0.0046 (13)	0.0106 (12)	−0.0106 (11)
C16	0.095 (2)	0.0450 (14)	0.0737 (17)	0.0165 (14)	−0.0216 (17)	0.0008 (13)
O	0.0632 (11)	0.0497 (10)	0.0458 (9)	−0.0048 (8)	−0.0006 (8)	0.0107 (8)
Cl1	0.0888 (5)	0.0842 (5)	0.0342 (3)	0.0068 (4)	−0.0030 (3)	−0.0063 (3)
Cl2	0.0547 (4)	0.0862 (5)	0.0683 (4)	−0.0017 (3)	0.0248 (3)	0.0005 (4)

C1—C2	1.512 (3)	C9—O	1.456 (3)
C1—C12	1.517 (3)	C9—C10	1.472 (3)
C1—C8	1.536 (3)	C9—H9	0.9800
C1—C3	1.550 (3)	C10—O	1.453 (3)
C2—C3	1.505 (3)	C10—C11	1.489 (3)
C2—Cl1	1.769 (2)	C10—C16	1.507 (3)
C2—Cl2	1.770 (2)	C11—C12	1.517 (3)
C3—C4	1.506 (3)	C11—H11A	0.9700
C3—C13	1.516 (4)	C11—H11B	0.9700
C4—C5	1.522 (4)	C12—H12A	0.9700
C4—H4A	0.9700	C12—H12B	0.9700
C4—H4B	0.9700	C13—H13A	0.9600
C5—C6	1.515 (4)	C13—H13B	0.9600
C5—H5A	0.9700	C13—H13C	0.9600
C5—H5B	0.9700	C14—H14A	0.9600
C6—C7	1.546 (3)	C14—H14B	0.9600
C6—H6A	0.9700	C14—H14C	0.9600
C6—H6B	0.9700	C15—H15A	0.9600
C7—C15	1.532 (3)	C15—H15B	0.9600
C7—C14	1.534 (4)	C15—H15C	0.9600
C7—C8	1.574 (3)	C16—H16A	0.9600
C8—C9	1.521 (3)	C16—H16B	0.9600
C8—H8	0.9800	C16—H16C	0.9600
C2—C1—C12	114.70 (17)	O—C9—C8	118.51 (17)
C2—C1—C8	119.45 (17)	C10—C9—C8	124.23 (19)
C12—C1—C8	113.09 (17)	O—C9—H9	114.5
C2—C1—C3	58.86 (14)	C10—C9—H9	114.5
C12—C1—C3	120.89 (19)	C8—C9—H9	114.5
C8—C1—C3	119.35 (18)	O—C10—C9	59.71 (14)
C3—C2—C1	61.81 (14)	O—C10—C11	113.26 (19)
C3—C2—Cl1	121.47 (17)	C9—C10—C11	118.93 (18)
C1—C2—Cl1	121.38 (16)	O—C10—C16	114.4 (2)
C3—C2—Cl2	118.75 (17)	C9—C10—C16	120.0 (2)
C1—C2—Cl2	120.64 (16)	C11—C10—C16	116.8 (2)
Cl1—C2—Cl2	107.30 (12)	C10—C11—C12	112.81 (18)
C2—C3—C4	117.7 (2)	C10—C11—H11A	109.0
C2—C3—C13	118.7 (2)	C12—C11—H11A	109.0
C4—C3—C13	112.5 (2)	C10—C11—H11B	109.0
C2—C3—C1	59.33 (14)	C12—C11—H11B	109.0
C4—C3—C1	119.9 (2)	H11A—C11—H11B	107.8
C13—C3—C1	119.2 (2)	C1—C12—C11	110.06 (18)
C3—C4—C5	113.9 (2)	C1—C12—H12A	109.6
C3—C4—H4A	108.8	C11—C12—H12A	109.6
C5—C4—H4A	108.8	C1—C12—H12B	109.6
C3—C4—H4B	108.8	C11—C12—H12B	109.6
C5—C4—H4B	108.8	H12A—C12—H12B	108.2
H4A—C4—H4B	107.7	C3—C13—H13A	109.5
C6—C5—C4	112.7 (2)	C3—C13—H13B	109.5
C6—C5—H5A	109.0	H13A—C13—H13B	109.5
C4—C5—H5A	109.0	C3—C13—H13C	109.5
C6—C5—H5B	109.0	H13A—C13—H13C	109.5
C4—C5—H5B	109.0	H13B—C13—H13C	109.5
H5A—C5—H5B	107.8	C7—C14—H14A	109.5
C5—C6—C7	119.6 (2)	C7—C14—H14B	109.5
C5—C6—H6A	107.4	H14A—C14—H14B	109.5
C7—C6—H6A	107.4	C7—C14—H14C	109.5
C5—C6—H6B	107.4	H14A—C14—H14C	109.5
C7—C6—H6B	107.4	H14B—C14—H14C	109.5
H6A—C6—H6B	107.0	C7—C15—H15A	109.5
C15—C7—C14	107.9 (2)	C7—C15—H15B	109.5
C15—C7—C6	109.4 (2)	H15A—C15—H15B	109.5
C14—C7—C6	106.0 (2)	C7—C15—H15C	109.5
C15—C7—C8	113.74 (18)	H15A—C15—H15C	109.5
C14—C7—C8	108.4 (2)	H15B—C15—H15C	109.5
C6—C7—C8	111.10 (19)	C10—C16—H16A	109.5
C9—C8—C1	110.22 (17)	C10—C16—H16B	109.5
C9—C8—C7	112.54 (18)	H16A—C16—H16B	109.5
C1—C8—C7	116.23 (17)	C10—C16—H16C	109.5
C9—C8—H8	105.6	H16A—C16—H16C	109.5
C1—C8—H8	105.6	H16B—C16—H16C	109.5
C7—C8—H8	105.6	C10—O—C9	60.78 (14)
O—C9—C10	59.51 (14)