(1S,3R,8R,11S)-11-Bromo-10-bromo-methyl-2,2-di-chloro-3,7,7-tri-methyl-tricyclo-[6.4.0.0(1,3)]dodec-9-ene.

The title compound, C16H22Br2Cl2, was synthesized from β-him-achalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an appended three-membered ring. The six-membered ring has a half-chair conformation, whereas the seven-membered ring displays a chair conformation. The dihedral angle between the two best plane through each ring is 59.5 (2)°. No specific inter-molecular inter-actions were discerned in the crystal packing.

Related literature

For the reactivity and biological properties of β-himachalene, see: El Haib et al. (2011 ▶); El Jamili et al. (2002 ▶); Daoubi et al. (2004 ▶). For related structures, see: Oukhrib et al. (2013 ▶); Ourhriss et al. (2013 ▶); Benharref et al.(2013 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H22Br2Cl2

M = 445.06

Orthorhombic,

a = 8.2594 (7) Å

b = 13.0352 (11) Å

c = 16.6241 (13) Å

V = 1789.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.82 mm−1

T = 293 K

0.20 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SHELXS97; Sheldrick,2008 ▶) T min = 0.423, T max = 0.617

10693 measured reflections

3654 independent reflections

3183 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.102

S = 1.05

3654 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.54 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▶), 614 Friedel pairs

Absolute structure parameter: 0.022 (13)

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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813019697/tk5241sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019697/tk5241Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813019697/tk5241Isup3.cml

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

C16H22Br2Cl2	F(000) = 888
Mr = 445.06	Dx = 1.652 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3653 reflections
a = 8.2594 (7) Å	θ = 2.8–26.4°
b = 13.0352 (11) Å	µ = 4.82 mm−1
c = 16.6241 (13) Å	T = 293 K
V = 1789.8 (3) Å3	Block, colourless
Z = 4	0.20 × 0.15 × 0.12 mm

Bruker APEXII CCD diffractometer	3654 independent reflections
Radiation source: fine-focus sealed tube	3183 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan SHELXS97 (Sheldrick,2008)	h = −10→10
Tmin = 0.423, Tmax = 0.617	k = −13→16
10693 measured reflections	l = −11→20

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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0406P)2 + 1.2463P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3654 reflections	Δρmax = 0.55 e Å−3
184 parameters	Δρmin = −0.54 e Å−3
0 restraints	Absolute structure: Flack & Bernardinelli (2000), 614 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.022 (13)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.3469 (4)	0.4202 (3)	0.7271 (2)	0.0346 (8)
C2	0.1795 (4)	0.3776 (4)	0.7462 (3)	0.0440 (9)
C3	0.2012 (4)	0.4409 (4)	0.6715 (2)	0.0446 (9)
C4	0.1967 (6)	0.3884 (4)	0.5903 (3)	0.0570 (12)
H4A	0.0915	0.3999	0.5659	0.068*
H4B	0.2095	0.3151	0.5979	0.068*
C5	0.3291 (6)	0.4270 (5)	0.5327 (3)	0.0598 (13)
H5A	0.2927	0.4188	0.4775	0.072*
H5B	0.3480	0.4994	0.5421	0.072*
C6	0.4858 (7)	0.3684 (5)	0.5444 (3)	0.0721 (15)
H6A	0.5565	0.3853	0.4998	0.086*
H6B	0.4610	0.2959	0.5401	0.086*
C7	0.5838 (5)	0.3841 (3)	0.6231 (2)	0.0446 (9)
C8	0.4798 (5)	0.3470 (3)	0.6986 (2)	0.0354 (8)
H8	0.4247	0.2840	0.6817	0.043*
C9	0.5846 (5)	0.3179 (3)	0.7684 (2)	0.0384 (8)
H9	0.6527	0.2619	0.7611	0.046*
C10	0.5903 (4)	0.3636 (3)	0.8394 (2)	0.0373 (8)
C11	0.4874 (5)	0.4553 (3)	0.8571 (2)	0.0370 (8)
H11	0.4009	0.4346	0.8940	0.044*
C12	0.4109 (5)	0.5026 (3)	0.7827 (2)	0.0391 (8)
H12A	0.3228	0.5475	0.7987	0.047*
H12B	0.4908	0.5436	0.7545	0.047*
C13	0.1283 (6)	0.5488 (4)	0.6685 (3)	0.0684 (14)
H13A	0.1301	0.5784	0.7214	0.103*
H13B	0.0185	0.5448	0.6498	0.103*
H13C	0.1904	0.5907	0.6325	0.103*
C14	0.7278 (9)	0.3099 (6)	0.6141 (4)	0.093 (2)
H14A	0.8067	0.3242	0.6550	0.139*
H14B	0.7761	0.3188	0.5620	0.139*
H14C	0.6904	0.2406	0.6196	0.139*
C15	0.6474 (9)	0.4891 (5)	0.6292 (4)	0.0845 (19)
H15A	0.5591	0.5365	0.6345	0.127*
H15B	0.7083	0.5052	0.5816	0.127*
H15C	0.7165	0.4943	0.6754	0.127*
C16	0.6964 (5)	0.3222 (4)	0.9042 (3)	0.0507 (10)
H16A	0.7645	0.3769	0.9247	0.061*
H16B	0.7665	0.2698	0.8817	0.061*
Cl3	0.14150 (16)	0.24471 (10)	0.74083 (8)	0.0694 (3)
Cl4	0.06998 (15)	0.42878 (14)	0.82812 (8)	0.0734 (4)
Br1	0.61787 (8)	0.56321 (4)	0.90951 (3)	0.07068 (18)
Br2	0.57150 (8)	0.26329 (6)	0.99305 (4)	0.0885 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0338 (17)	0.035 (2)	0.0352 (18)	−0.0032 (15)	−0.0007 (13)	0.0027 (15)
C2	0.0327 (18)	0.053 (3)	0.046 (2)	−0.0103 (17)	0.0056 (15)	0.0024 (19)
C3	0.0342 (18)	0.051 (2)	0.048 (2)	−0.0075 (18)	−0.0073 (15)	0.010 (2)
C4	0.051 (2)	0.076 (3)	0.045 (2)	−0.021 (2)	−0.0154 (19)	0.004 (2)
C5	0.066 (3)	0.080 (3)	0.033 (2)	−0.020 (3)	−0.0090 (18)	0.011 (2)
C6	0.075 (3)	0.091 (4)	0.051 (3)	−0.017 (3)	0.001 (2)	−0.001 (3)
C7	0.045 (2)	0.055 (2)	0.0338 (19)	−0.007 (2)	0.0081 (16)	−0.0015 (17)
C8	0.0395 (19)	0.033 (2)	0.0341 (19)	−0.0040 (15)	0.0043 (14)	−0.0020 (15)
C9	0.0385 (19)	0.0315 (19)	0.045 (2)	0.0062 (15)	0.0033 (16)	0.0031 (16)
C10	0.0346 (18)	0.040 (2)	0.0373 (19)	−0.0006 (16)	0.0011 (15)	0.0059 (16)
C11	0.0401 (19)	0.037 (2)	0.0336 (19)	0.0006 (15)	0.0026 (14)	−0.0077 (16)
C12	0.040 (2)	0.036 (2)	0.041 (2)	0.0055 (16)	−0.0017 (16)	−0.0041 (16)
C13	0.052 (3)	0.075 (4)	0.079 (3)	0.019 (3)	−0.015 (2)	0.016 (3)
C14	0.085 (4)	0.112 (5)	0.082 (4)	0.024 (4)	0.046 (4)	0.006 (4)
C15	0.097 (5)	0.082 (4)	0.074 (4)	−0.046 (4)	0.021 (3)	−0.004 (3)
C16	0.046 (2)	0.057 (3)	0.049 (2)	0.0047 (18)	0.0030 (19)	0.017 (2)
Cl3	0.0657 (7)	0.0632 (8)	0.0793 (8)	−0.0286 (6)	0.0057 (6)	0.0147 (6)
Cl4	0.0472 (6)	0.1082 (11)	0.0649 (7)	0.0060 (7)	0.0215 (5)	0.0002 (8)
Br1	0.0901 (4)	0.0583 (3)	0.0637 (3)	−0.0039 (3)	−0.0277 (3)	−0.0181 (2)
Br2	0.0869 (4)	0.1127 (5)	0.0659 (4)	−0.0004 (4)	0.0151 (3)	0.0420 (3)

C1—C12	1.513 (5)	C8—H8	0.9800
C1—C2	1.524 (5)	C9—C10	1.323 (6)
C1—C8	1.529 (5)	C9—H9	0.9300
C1—C3	1.541 (5)	C10—C16	1.489 (6)
C2—C3	1.502 (6)	C10—C11	1.495 (5)
C2—Cl3	1.763 (5)	C11—C12	1.520 (5)
C2—Cl4	1.765 (4)	C11—Br1	1.975 (4)
C3—C4	1.514 (7)	C11—H11	0.9800
C3—C13	1.531 (7)	C12—H12A	0.9700
C4—C5	1.538 (6)	C12—H12B	0.9700
C4—H4A	0.9700	C13—H13A	0.9600
C4—H4B	0.9700	C13—H13B	0.9600
C5—C6	1.515 (8)	C13—H13C	0.9600
C5—H5A	0.9700	C14—H14A	0.9600
C5—H5B	0.9700	C14—H14B	0.9600
C6—C7	1.552 (7)	C14—H14C	0.9600
C6—H6A	0.9700	C15—H15A	0.9600
C6—H6B	0.9700	C15—H15B	0.9600
C7—C15	1.470 (7)	C15—H15C	0.9600
C7—C14	1.540 (8)	C16—Br2	1.959 (4)
C7—C8	1.596 (5)	C16—H16A	0.9700
C8—C9	1.497 (5)	C16—H16B	0.9700
C12—C1—C2	116.6 (3)	C9—C8—H8	106.2
C12—C1—C8	112.4 (3)	C1—C8—H8	106.2
C2—C1—C8	119.2 (3)	C7—C8—H8	106.2
C12—C1—C3	121.0 (3)	C10—C9—C8	126.8 (3)
C2—C1—C3	58.7 (3)	C10—C9—H9	116.6
C8—C1—C3	118.9 (3)	C8—C9—H9	116.6
C3—C2—C1	61.2 (2)	C9—C10—C16	120.2 (4)
C3—C2—Cl3	121.2 (3)	C9—C10—C11	121.0 (3)
C1—C2—Cl3	120.6 (3)	C16—C10—C11	118.8 (3)
C3—C2—Cl4	119.5 (3)	C10—C11—C12	113.6 (3)
C1—C2—Cl4	119.2 (3)	C10—C11—Br1	110.2 (3)
Cl3—C2—Cl4	108.6 (2)	C12—C11—Br1	107.3 (3)
C2—C3—C4	119.1 (4)	C10—C11—H11	108.5
C2—C3—C13	118.9 (4)	C12—C11—H11	108.5
C4—C3—C13	112.1 (4)	Br1—C11—H11	108.5
C2—C3—C1	60.1 (2)	C1—C12—C11	110.7 (3)
C4—C3—C1	118.4 (4)	C1—C12—H12A	109.5
C13—C3—C1	119.2 (4)	C11—C12—H12A	109.5
C3—C4—C5	112.9 (4)	C1—C12—H12B	109.5
C3—C4—H4A	109.0	C11—C12—H12B	109.5
C5—C4—H4A	109.0	H12A—C12—H12B	108.1
C3—C4—H4B	109.0	C3—C13—H13A	109.5
C5—C4—H4B	109.0	C3—C13—H13B	109.5
H4A—C4—H4B	107.8	H13A—C13—H13B	109.5
C6—C5—C4	111.3 (4)	C3—C13—H13C	109.5
C6—C5—H5A	109.4	H13A—C13—H13C	109.5
C4—C5—H5A	109.4	H13B—C13—H13C	109.5
C6—C5—H5B	109.4	C7—C14—H14A	109.5
C4—C5—H5B	109.4	C7—C14—H14B	109.5
H5A—C5—H5B	108.0	H14A—C14—H14B	109.5
C5—C6—C7	119.2 (5)	C7—C14—H14C	109.5
C5—C6—H6A	107.5	H14A—C14—H14C	109.5
C7—C6—H6A	107.5	H14B—C14—H14C	109.5
C5—C6—H6B	107.5	C7—C15—H15A	109.5
C7—C6—H6B	107.5	C7—C15—H15B	109.5
H6A—C6—H6B	107.0	H15A—C15—H15B	109.5
C15—C7—C14	108.4 (5)	C7—C15—H15C	109.5
C15—C7—C6	111.6 (5)	H15A—C15—H15C	109.5
C14—C7—C6	103.8 (4)	H15B—C15—H15C	109.5
C15—C7—C8	114.9 (4)	C10—C16—Br2	112.2 (3)
C14—C7—C8	107.6 (4)	C10—C16—H16A	109.2
C6—C7—C8	110.0 (4)	Br2—C16—H16A	109.2
C9—C8—C1	109.4 (3)	C10—C16—H16B	109.2
C9—C8—C7	112.0 (3)	Br2—C16—H16B	109.2
C1—C8—C7	116.2 (3)	H16A—C16—H16B	107.9