(1S,2S,4R)-3,3-Dichloro-4,8,12,12-tetra-methyl-tricyclo-[5.5.0.0]dodeca-6,8-diene.

The title compound, C(16)H(22)Cl(2), a derivative of β-himachalene, was semi-synthesized from natural essential oils of Cedrus atlantica. The mol-ecule is built up from two fused six- and seven-membered rings. The six-membered ring has a perfect chair conformation, whereas the seven-membered ring displays a screw boat conformation; the dihedral angle between the rings is 46.48 (9)°.

Related literature

For background to himachalene derivatives, see: Plattier & Teiseire (1974 ▶); Sbai et al. (2002 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For the synthesis of the title compound, see: Lassaba et al. (1997 ▶). For the reactivity of this sesquiterpene, see: El Jamili et al. (2002 ▶; Sbai et al. (2002 ▶). For the olfactive properties of β-himachalene, see: Benharref et al. (1991 ▶); Bisarya & Dev (1968 ▶); Chekroun et al. (2000 ▶).

Experimental

Crystal data

C16H22Cl2

M = 285.24

Orthorhombic,

a = 7.4356 (17) Å

b = 8.3124 (18) Å

c = 24.108 (6) Å

V = 1490.1 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.42 mm−1

T = 298 K

0.27 × 0.18 × 0.12 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer

10992 measured reflections

3691 independent reflections

3282 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.096

S = 1.11

3691 reflections

175 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1985 ▶), 1535 Friedel pairs

Flack parameter: −0.06 (6)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus; 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/S1600536810034070/er2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034070/er2079Isup2.hkl

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

C16H22Cl2	F(000) = 608
Mr = 285.24	Dx = 1.271 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10992 reflections
a = 7.4356 (17) Å	θ = 1.7–28.4°
b = 8.3124 (18) Å	µ = 0.42 mm−1
c = 24.108 (6) Å	T = 298 K
V = 1490.1 (6) Å3	Prism, colourless
Z = 4	0.27 × 0.18 × 0.12 mm

Bruker X8 APEXII CCD area-detector diffractometer	3282 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
graphite	θmax = 28.4°, θmin = 1.7°
φ and ω scans	h = −7→9
10992 measured reflections	k = −8→11
3691 independent reflections	l = −32→28

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0579P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
3691 reflections	Δρmax = 0.34 e Å−3
175 parameters	Δρmin = −0.29 e Å−3
0 restraints	Absolute structure: Flack (1985), 1535 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.06 (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.

	x	y	z	Uiso*/Ueq
C1	0.6213 (2)	0.33418 (19)	0.89982 (6)	0.0375 (3)
C2	0.4484 (2)	0.3173 (2)	0.92944 (6)	0.0476 (4)
C3	0.3427 (3)	0.4400 (3)	0.94246 (7)	0.0551 (5)
C4	0.3834 (3)	0.6154 (3)	0.93795 (8)	0.0588 (5)
H4A	0.3146	0.6730	0.9658	0.071*
H4B	0.3451	0.6535	0.9018	0.071*
C5	0.5809 (2)	0.6534 (2)	0.94551 (7)	0.0514 (4)
H5A	0.6290	0.5834	0.9741	0.062*
H5B	0.5919	0.7633	0.9587	0.062*
C6	0.6957 (2)	0.63474 (18)	0.89326 (6)	0.0405 (3)
C7	0.6413 (2)	0.47755 (17)	0.86197 (6)	0.0341 (3)
H7	0.5234	0.4970	0.8451	0.041*
C8	0.7727 (2)	0.44941 (18)	0.81513 (6)	0.0384 (3)
H8	0.8138	0.5487	0.7973	0.046*
C9	0.7663 (2)	0.30866 (19)	0.77693 (7)	0.0427 (3)
C10	0.9167 (2)	0.3203 (2)	0.81854 (7)	0.0438 (3)
C11	0.9108 (2)	0.2114 (2)	0.86840 (8)	0.0497 (4)
H11A	0.9257	0.1014	0.8558	0.060*
H11B	1.0127	0.2368	0.8920	0.060*
C12	0.7456 (3)	0.2200 (2)	0.90240 (7)	0.0457 (4)
C13	1.1028 (3)	0.3568 (3)	0.79848 (9)	0.0628 (5)
H13A	1.1600	0.2590	0.7867	0.094*
H13B	1.1712	0.4044	0.8280	0.094*
H13C	1.0966	0.4304	0.7679	0.094*
C14	0.8912 (3)	0.6291 (2)	0.91128 (8)	0.0546 (4)
H14A	0.9119	0.5336	0.9328	0.082*
H14B	0.9181	0.7221	0.9334	0.082*
H14C	0.9673	0.6280	0.8791	0.082*
C15	0.6651 (3)	0.7795 (2)	0.85566 (8)	0.0573 (5)
H15A	0.7378	0.7690	0.8229	0.086*
H15B	0.6978	0.8761	0.8750	0.086*
H15C	0.5406	0.7847	0.8453	0.086*
C16	0.3883 (3)	0.1489 (3)	0.94230 (11)	0.0727 (6)
H16A	0.4725	0.0996	0.9673	0.109*
H16B	0.3825	0.0876	0.9086	0.109*
H16C	0.2716	0.1518	0.9593	0.109*
Cl1	0.59995 (6)	0.16140 (5)	0.781164 (18)	0.05350 (13)
Cl2	0.81596 (8)	0.34714 (7)	0.706600 (17)	0.06577 (16)
H3	0.223 (3)	0.414 (3)	0.9587 (9)	0.074 (6)*
H12	0.732 (3)	0.127 (3)	0.9270 (9)	0.064 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0388 (7)	0.0457 (7)	0.0281 (6)	−0.0004 (7)	0.0008 (5)	−0.0004 (6)
C2	0.0430 (9)	0.0676 (11)	0.0323 (7)	−0.0041 (8)	0.0017 (6)	0.0061 (7)
C3	0.0393 (9)	0.0868 (13)	0.0391 (9)	−0.0009 (9)	0.0065 (7)	−0.0031 (9)
C4	0.0457 (10)	0.0781 (12)	0.0526 (10)	0.0142 (9)	0.0084 (8)	−0.0187 (9)
C5	0.0500 (9)	0.0632 (10)	0.0411 (8)	0.0055 (9)	−0.0002 (7)	−0.0196 (8)
C6	0.0404 (8)	0.0440 (8)	0.0370 (7)	0.0023 (7)	−0.0012 (6)	−0.0080 (6)
C7	0.0324 (7)	0.0403 (7)	0.0297 (6)	0.0027 (6)	−0.0007 (5)	−0.0020 (5)
C8	0.0422 (8)	0.0404 (7)	0.0326 (7)	−0.0017 (6)	0.0054 (6)	−0.0022 (6)
C9	0.0434 (8)	0.0512 (8)	0.0334 (7)	−0.0048 (6)	0.0071 (6)	−0.0074 (6)
C10	0.0374 (8)	0.0520 (8)	0.0420 (8)	0.0002 (7)	0.0066 (6)	−0.0116 (7)
C11	0.0441 (9)	0.0517 (9)	0.0532 (10)	0.0111 (7)	−0.0005 (8)	−0.0033 (7)
C12	0.0526 (10)	0.0458 (8)	0.0388 (8)	0.0016 (7)	−0.0013 (7)	0.0033 (7)
C13	0.0432 (9)	0.0831 (13)	0.0621 (11)	−0.0044 (10)	0.0113 (8)	−0.0171 (11)
C14	0.0431 (9)	0.0663 (11)	0.0545 (10)	−0.0054 (9)	−0.0050 (8)	−0.0144 (8)
C15	0.0744 (14)	0.0392 (8)	0.0583 (11)	0.0027 (9)	−0.0033 (10)	−0.0024 (8)
C16	0.0590 (12)	0.0815 (13)	0.0776 (14)	−0.0113 (12)	0.0084 (11)	0.0310 (12)
Cl1	0.0529 (2)	0.0574 (2)	0.0502 (2)	−0.0120 (2)	−0.00032 (18)	−0.00975 (19)
Cl2	0.0750 (3)	0.0874 (3)	0.0349 (2)	−0.0115 (3)	0.0142 (2)	−0.0107 (2)

C1—C12	1.326 (2)	C9—C10	1.505 (2)
C1—C2	1.477 (2)	C9—Cl1	1.7433 (16)
C1—C7	1.508 (2)	C9—Cl2	1.7645 (17)
C2—C3	1.326 (3)	C10—C13	1.497 (2)
C2—C16	1.502 (3)	C10—C11	1.505 (3)
C3—C4	1.493 (3)	C11—C12	1.479 (3)
C3—H3	1.00 (3)	C11—H11A	0.9700
C4—C5	1.513 (3)	C11—H11B	0.9700
C4—H4A	0.9700	C12—H12	0.98 (2)
C4—H4B	0.9700	C13—H13A	0.9600
C5—C6	1.530 (2)	C13—H13B	0.9600
C5—H5A	0.9700	C13—H13C	0.9600
C5—H5B	0.9700	C14—H14A	0.9600
C6—C14	1.519 (2)	C14—H14B	0.9600
C6—C15	1.524 (2)	C14—H14C	0.9600
C6—C7	1.562 (2)	C15—H15A	0.9600
C7—C8	1.511 (2)	C15—H15B	0.9600
C7—H7	0.9800	C15—H15C	0.9600
C8—C9	1.490 (2)	C16—H16A	0.9600
C8—C10	1.518 (2)	C16—H16B	0.9600
C8—H8	0.9800	C16—H16C	0.9600
C12—C1—C2	121.04 (16)	C8—C9—Cl2	116.42 (12)
C12—C1—C7	121.66 (14)	C10—C9—Cl2	118.25 (11)
C2—C1—C7	116.97 (14)	Cl1—C9—Cl2	109.39 (9)
C3—C2—C1	123.86 (17)	C13—C10—C11	114.00 (16)
C3—C2—C16	119.48 (18)	C13—C10—C9	118.97 (15)
C1—C2—C16	116.59 (17)	C11—C10—C9	118.17 (15)
C2—C3—C4	127.88 (17)	C13—C10—C8	119.41 (16)
C2—C3—H3	117.2 (14)	C11—C10—C8	116.60 (13)
C4—C3—H3	114.8 (13)	C9—C10—C8	59.03 (10)
C3—C4—C5	113.09 (17)	C12—C11—C10	115.96 (15)
C3—C4—H4A	109.0	C12—C11—H11A	108.3
C5—C4—H4A	109.0	C10—C11—H11A	108.3
C3—C4—H4B	109.0	C12—C11—H11B	108.3
C5—C4—H4B	109.0	C10—C11—H11B	108.3
H4A—C4—H4B	107.8	H11A—C11—H11B	107.4
C4—C5—C6	114.91 (14)	C1—C12—C11	126.00 (17)
C4—C5—H5A	108.5	C1—C12—H12	121.5 (13)
C6—C5—H5A	108.5	C11—C12—H12	112.4 (13)
C4—C5—H5B	108.5	C10—C13—H13A	109.5
C6—C5—H5B	108.5	C10—C13—H13B	109.5
H5A—C5—H5B	107.5	H13A—C13—H13B	109.5
C14—C6—C15	109.72 (16)	C10—C13—H13C	109.5
C14—C6—C5	107.57 (14)	H13A—C13—H13C	109.5
C15—C6—C5	109.07 (14)	H13B—C13—H13C	109.5
C14—C6—C7	111.10 (13)	C6—C14—H14A	109.5
C15—C6—C7	109.56 (13)	C6—C14—H14B	109.5
C5—C6—C7	109.78 (13)	H14A—C14—H14B	109.5
C1—C7—C8	113.17 (12)	C6—C14—H14C	109.5
C1—C7—C6	113.22 (12)	H14A—C14—H14C	109.5
C8—C7—C6	108.85 (12)	H14B—C14—H14C	109.5
C1—C7—H7	107.1	C6—C15—H15A	109.5
C8—C7—H7	107.1	C6—C15—H15B	109.5
C6—C7—H7	107.1	H15A—C15—H15B	109.5
C9—C8—C7	124.25 (13)	C6—C15—H15C	109.5
C9—C8—C10	60.05 (10)	H15A—C15—H15C	109.5
C7—C8—C10	121.66 (13)	H15B—C15—H15C	109.5
C9—C8—H8	113.6	C2—C16—H16A	109.5
C7—C8—H8	113.6	C2—C16—H16B	109.5
C10—C8—H8	113.6	H16A—C16—H16B	109.5
C8—C9—C10	60.92 (11)	C2—C16—H16C	109.5
C8—C9—Cl1	122.54 (11)	H16A—C16—H16C	109.5
C10—C9—Cl1	122.22 (12)	H16B—C16—H16C	109.5