Crystal structure of (1S,3R,8R,9S,10R)-10-bromo-methyl-2,2-di-chloro-9,10-ep-oxy-3,7,7-tri-methyl-tri-cyclo-[6.4.0.0(1,3)]dodeca-ne.

The title compound, C16H23BrCl2O, was synthesized in three steps from β-himachalene (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 two fused six- and seven-membered rings, each linked to a three-membered ring. The six-membered ring has a screw-boat conformation, whereas the seven-membered ring displays a twist-boat conformation. The absolute structure was established unambiguously from anomalous dispersion effects.

Related literature

For background to β-himachalene, see: El Haib et al. (2011 ▸). For the reactivity of this sesquiterpene and its derivatives, see: El Jamili et al. (2002 ▸); Benharref et al. (2013 ▸); Zaki et al. (2014 ▸). For the synthesis of the title compound, see: Bimoussa et al. (2013 ▸). For their potential anti­fungal activity against the phytopathogen Botrytis cinerea, see: Daoubi et al. (2004 ▸).

Experimental

Crystal data

C16H23BrCl2O

M = 382.15

Orthorhombic,

a = 8.8748 (5) Å

b = 11.2102 (6) Å

c = 16.8597 (8) Å

V = 1677.34 (15) Å3

Z = 4

Mo Kα radiation

μ = 2.76 mm−1

T = 296 K

0.35 × 0.25 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▸) T min = 0.648, T max = 0.746

23384 measured reflections

3419 independent reflections

3135 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.088

S = 1.04

3419 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.53 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▸), 1450 Friedel pairs

Absolute structure parameter: 0.012 (9)

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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500657X/rz5154sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500657X/rz5154Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500657X/rz5154Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500657X/rz5154fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

CCDC reference: 1057239

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H23BrCl2O	F(000) = 784
Mr = 382.15	Dx = 1.513 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3419 reflections
a = 8.8748 (5) Å	θ = 2.2–26.4°
b = 11.2102 (6) Å	µ = 2.76 mm−1
c = 16.8597 (8) Å	T = 296 K
V = 1677.34 (15) Å3	Prism, colourless
Z = 4	0.35 × 0.25 × 0.16 mm

Bruker APEXII CCD diffractometer	3419 independent reflections
Radiation source: fine-focus sealed tube	3135 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and φ scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→11
Tmin = 0.648, Tmax = 0.746	k = −14→14
23384 measured reflections	l = −21→14

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)] = 0.033	H-atom parameters constrained
wR(F2) = 0.088	w = 1/[σ2(Fo2) + (0.035P)2 + 1.0813P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3419 reflections	Δρmax = 0.65 e Å−3
184 parameters	Δρmin = −0.52 e Å−3
0 restraints	Absolute structure: Flack & Bernardinelli (2000), 1450 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.012 (9)

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	0.8156 (3)	0.2763 (2)	0.75464 (16)	0.0311 (5)
H1	0.8658	0.3365	0.7875	0.037*
C2	0.7910 (3)	0.3332 (2)	0.67448 (17)	0.0349 (6)
H2	0.8806	0.3401	0.6408	0.042*
C3	0.6468 (3)	0.3276 (2)	0.63277 (17)	0.0382 (6)
C4	0.5134 (3)	0.2638 (3)	0.66859 (18)	0.0439 (7)
H4A	0.4679	0.2133	0.6285	0.053*
H4B	0.4389	0.3224	0.6845	0.053*
C5	0.5541 (3)	0.1874 (3)	0.74026 (17)	0.0362 (6)
H5A	0.4632	0.1688	0.7697	0.043*
H5B	0.5976	0.1128	0.7221	0.043*
C6	0.6652 (3)	0.2497 (2)	0.79482 (15)	0.0286 (5)
C7	0.6026 (3)	0.3367 (2)	0.85487 (16)	0.0347 (6)
C8	0.6680 (4)	0.2217 (2)	0.88460 (16)	0.0398 (6)
C9	0.8207 (4)	0.2258 (3)	0.9237 (2)	0.0570 (9)
H9A	0.8075	0.2281	0.9808	0.068*
H9B	0.8719	0.2985	0.9079	0.068*
C10	0.9190 (5)	0.1185 (4)	0.9020 (3)	0.0755 (13)
H10A	1.0238	0.1393	0.9107	0.091*
H10B	0.8946	0.0530	0.9373	0.091*
C11	0.9007 (5)	0.0760 (3)	0.8162 (3)	0.0603 (10)
H11A	0.7992	0.0451	0.8104	0.072*
H11B	0.9693	0.0098	0.8081	0.072*
C12	0.9274 (3)	0.1671 (3)	0.7491 (2)	0.0457 (7)
C13	0.5657 (5)	0.1268 (3)	0.9185 (2)	0.0592 (9)
H13A	0.5498	0.1418	0.9739	0.089*
H13B	0.6116	0.0499	0.9118	0.089*
H13C	0.4707	0.1284	0.8913	0.089*
C14	1.0895 (4)	0.2161 (4)	0.7539 (3)	0.0668 (11)
H14A	1.1026	0.2583	0.8029	0.100*
H14B	1.1071	0.2694	0.7103	0.100*
H14C	1.1597	0.1511	0.7514	0.100*
C15	0.9119 (4)	0.0994 (3)	0.6701 (3)	0.0586 (10)
H15A	0.9802	0.0329	0.6697	0.088*
H15B	0.9354	0.1520	0.6270	0.088*
H15C	0.8105	0.0709	0.6645	0.088*
C16	0.6457 (5)	0.3478 (3)	0.54456 (19)	0.0554 (9)
H16A	0.7275	0.4010	0.5303	0.067*
H16B	0.5517	0.3854	0.5293	0.067*
Br1	0.66817 (6)	0.19765 (4)	0.48772 (2)	0.07821 (17)
O4	0.6911 (3)	0.43512 (16)	0.67456 (12)	0.0418 (5)
Cl1	0.40574 (9)	0.36000 (8)	0.85958 (5)	0.0521 (2)
Cl2	0.69214 (10)	0.47409 (6)	0.87514 (5)	0.04980 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0274 (12)	0.0251 (11)	0.0408 (14)	−0.0013 (10)	−0.0036 (11)	−0.0025 (10)
C2	0.0353 (13)	0.0311 (13)	0.0383 (14)	−0.0042 (10)	0.0061 (11)	−0.0017 (11)
C3	0.0477 (15)	0.0347 (14)	0.0323 (13)	0.0006 (11)	−0.0016 (12)	−0.0043 (11)
C4	0.0345 (14)	0.0591 (19)	0.0382 (15)	−0.0083 (13)	−0.0069 (12)	−0.0046 (13)
C5	0.0305 (13)	0.0362 (13)	0.0418 (15)	−0.0096 (11)	0.0009 (12)	−0.0039 (12)
C6	0.0271 (11)	0.0265 (11)	0.0323 (12)	−0.0027 (10)	−0.0045 (11)	0.0017 (9)
C7	0.0353 (13)	0.0355 (14)	0.0331 (14)	−0.0013 (11)	−0.0001 (11)	0.0001 (11)
C8	0.0485 (16)	0.0368 (14)	0.0341 (14)	−0.0056 (13)	−0.0056 (13)	0.0077 (11)
C9	0.064 (2)	0.061 (2)	0.0459 (18)	−0.0004 (18)	−0.0205 (18)	0.0138 (15)
C10	0.075 (3)	0.071 (3)	0.081 (3)	0.017 (2)	−0.029 (2)	0.027 (2)
C11	0.0554 (19)	0.0392 (16)	0.086 (3)	0.0153 (15)	−0.009 (2)	0.0085 (17)
C12	0.0330 (15)	0.0369 (15)	0.067 (2)	0.0061 (12)	−0.0024 (14)	−0.0027 (14)
C13	0.076 (3)	0.052 (2)	0.049 (2)	−0.0088 (18)	0.0071 (18)	0.0157 (16)
C14	0.0316 (16)	0.060 (2)	0.109 (3)	0.0024 (15)	−0.0107 (18)	−0.006 (2)
C15	0.0434 (17)	0.0463 (18)	0.086 (3)	0.0076 (14)	0.0107 (18)	−0.0195 (18)
C16	0.079 (2)	0.0550 (19)	0.0326 (15)	0.0012 (18)	−0.0015 (16)	−0.0008 (14)
Br1	0.0966 (3)	0.0883 (3)	0.0497 (2)	0.0133 (3)	−0.0049 (2)	−0.0260 (2)
O4	0.0549 (12)	0.0313 (9)	0.0394 (11)	0.0054 (9)	−0.0052 (10)	0.0000 (8)
Cl1	0.0415 (4)	0.0631 (5)	0.0516 (5)	0.0067 (4)	0.0126 (3)	0.0000 (4)
Cl2	0.0638 (5)	0.0353 (3)	0.0504 (4)	−0.0044 (3)	−0.0037 (4)	−0.0109 (3)

C1—C2	1.510 (4)	C9—C10	1.531 (6)
C1—C6	1.527 (4)	C9—H9A	0.9700
C1—C12	1.579 (4)	C9—H9B	0.9700
C1—H1	0.9800	C10—C11	1.530 (6)
C2—O4	1.446 (3)	C10—H10A	0.9700
C2—C3	1.462 (4)	C10—H10B	0.9700
C2—H2	0.9800	C11—C12	1.543 (5)
C3—O4	1.451 (3)	C11—H11A	0.9700
C3—C16	1.504 (4)	C11—H11B	0.9700
C3—C4	1.509 (4)	C12—C15	1.538 (5)
C4—C5	1.524 (4)	C12—C14	1.542 (4)
C4—H4A	0.9700	C13—H13A	0.9600
C4—H4B	0.9700	C13—H13B	0.9600
C5—C6	1.519 (4)	C13—H13C	0.9600
C5—H5A	0.9700	C14—H14A	0.9600
C5—H5B	0.9700	C14—H14B	0.9600
C6—C7	1.512 (4)	C14—H14C	0.9600
C6—C8	1.546 (4)	C15—H15A	0.9600
C7—C8	1.500 (4)	C15—H15B	0.9600
C7—Cl2	1.766 (3)	C15—H15C	0.9600
C7—Cl1	1.769 (3)	C16—Br1	1.947 (3)
C8—C9	1.507 (5)	C16—H16A	0.9700
C8—C13	1.511 (4)	C16—H16B	0.9700
C2—C1—C6	110.7 (2)	C8—C9—H9A	109.1
C2—C1—C12	111.4 (2)	C10—C9—H9A	109.1
C6—C1—C12	115.1 (2)	C8—C9—H9B	109.1
C2—C1—H1	106.3	C10—C9—H9B	109.1
C6—C1—H1	106.3	H9A—C9—H9B	107.8
C12—C1—H1	106.3	C11—C10—C9	114.2 (3)
O4—C2—C3	59.83 (17)	C11—C10—H10A	108.7
O4—C2—C1	114.9 (2)	C9—C10—H10A	108.7
C3—C2—C1	122.6 (2)	C11—C10—H10B	108.7
O4—C2—H2	115.8	C9—C10—H10B	108.7
C3—C2—H2	115.8	H10A—C10—H10B	107.6
C1—C2—H2	115.8	C10—C11—C12	118.1 (3)
O4—C3—C2	59.54 (17)	C10—C11—H11A	107.8
O4—C3—C16	110.9 (2)	C12—C11—H11A	107.8
C2—C3—C16	118.3 (3)	C10—C11—H11B	107.8
O4—C3—C4	114.4 (2)	C12—C11—H11B	107.8
C2—C3—C4	121.0 (2)	H11A—C11—H11B	107.1
C16—C3—C4	117.5 (3)	C15—C12—C14	107.7 (3)
C3—C4—C5	113.4 (2)	C15—C12—C11	107.1 (3)
C3—C4—H4A	108.9	C14—C12—C11	109.9 (3)
C5—C4—H4A	108.9	C15—C12—C1	112.2 (3)
C3—C4—H4B	108.9	C14—C12—C1	107.9 (2)
C5—C4—H4B	108.9	C11—C12—C1	111.9 (3)
H4A—C4—H4B	107.7	C8—C13—H13A	109.5
C6—C5—C4	112.1 (2)	C8—C13—H13B	109.5
C6—C5—H5A	109.2	H13A—C13—H13B	109.5
C4—C5—H5A	109.2	C8—C13—H13C	109.5
C6—C5—H5B	109.2	H13A—C13—H13C	109.5
C4—C5—H5B	109.2	H13B—C13—H13C	109.5
H5A—C5—H5B	107.9	C12—C14—H14A	109.5
C7—C6—C5	117.7 (2)	C12—C14—H14B	109.5
C7—C6—C1	119.5 (2)	H14A—C14—H14B	109.5
C5—C6—C1	112.9 (2)	C12—C14—H14C	109.5
C7—C6—C8	58.76 (18)	H14A—C14—H14C	109.5
C5—C6—C8	120.7 (2)	H14B—C14—H14C	109.5
C1—C6—C8	117.4 (2)	C12—C15—H15A	109.5
C8—C7—C6	61.77 (18)	C12—C15—H15B	109.5
C8—C7—Cl2	120.7 (2)	H15A—C15—H15B	109.5
C6—C7—Cl2	121.82 (19)	C12—C15—H15C	109.5
C8—C7—Cl1	119.6 (2)	H15A—C15—H15C	109.5
C6—C7—Cl1	119.2 (2)	H15B—C15—H15C	109.5
Cl2—C7—Cl1	107.87 (15)	C3—C16—Br1	110.8 (2)
C7—C8—C9	117.9 (2)	C3—C16—H16A	109.5
C7—C8—C13	119.9 (3)	Br1—C16—H16A	109.5
C9—C8—C13	113.3 (3)	C3—C16—H16B	109.5
C7—C8—C6	59.47 (17)	Br1—C16—H16B	109.5
C9—C8—C6	115.9 (3)	H16A—C16—H16B	108.1
C13—C8—C6	120.2 (3)	C2—O4—C3	60.63 (18)
C8—C9—C10	112.6 (3)