(1S,3R,8R,11S)-2,2-Dichloro-3,7,7,10-tetra-methyl-tricyclo-[6.4.0.0]dodec-9-en-11-ol.

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 essential oil of the Atlas cedar (Cedrus atlantica). The two fused rings exhibit different conformations: the six-membered ring has a screw-boat conformation, while the seven-membered ring displays a boat conformation. The dihedral angle between the two rings is 56.56 (18)°. In the crystal, mol-ecules aggregate into supra-molecular chains along the c axis mediated by O-H⋯O hydrogen bonds.

Related literature

For the isolation of β-himachalene, see: Joseph & Dev (1968 ▶); Plattier & Teisseire (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 conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H24Cl2O

M = 303.25

Trigonal,

a = 13.2323 (13) Å

c = 7.9807 (8) Å

V = 1210.2 (2) Å3

Z = 3

Mo Kα radiation

μ = 0.39 mm−1

T = 298 K

0.41 × 0.33 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer

8123 measured reflections

3135 independent reflections

2995 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.126

S = 1.09

3135 reflections

180 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.33 e Å−3

Absolute structure: Flack (1983 ▶), 1940 Friedel pairs

Flack parameter: −0.11 (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/S1600536811004788/tk2714sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004788/tk2714Isup2.hkl

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

C16H24Cl2O	Dx = 1.244 Mg m−3
Mr = 303.25	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P32	Cell parameters from 8123 reflections
Hall symbol: P 32	θ = 4–26.4°
a = 13.2323 (13) Å	µ = 0.39 mm−1
c = 7.9807 (8) Å	T = 298 K
V = 1210.2 (2) Å3	Prism, colourless
Z = 3	0.41 × 0.33 × 0.26 mm
F(000) = 486

Bruker APEXII CCD diffractometer	2995 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
graphite	θmax = 26.4°, θmin = 4.0°
ω and φ scans	h = −15→16
8123 measured reflections	k = −14→16
3135 independent reflections	l = −9→9

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)] = 0.045	H-atom parameters constrained
wR(F2) = 0.126	w = 1/[σ2(Fo2) + (0.0761P)2 + 0.4405P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
3135 reflections	Δρmax = 0.52 e Å−3
180 parameters	Δρmin = −0.33 e Å−3
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 1940 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.11 (7)

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.

	x	y	z	Uiso*/Ueq
C1	1.0043 (2)	0.6432 (2)	0.5388 (3)	0.0304 (5)
C2	0.9057 (2)	0.5880 (2)	0.4113 (4)	0.0370 (5)
C3	0.8790 (2)	0.5564 (2)	0.5938 (4)	0.0392 (6)
C4	0.8143 (3)	0.6069 (3)	0.6915 (4)	0.0464 (7)
H4A	0.8228	0.6749	0.6329	0.056*
H4B	0.7319	0.5493	0.6955	0.056*
C5	0.8600 (3)	0.6411 (3)	0.8682 (5)	0.0541 (8)
H5A	0.8234	0.5720	0.9384	0.065*
H5B	0.8370	0.6953	0.9106	0.065*
C6	0.9973 (3)	0.6991 (4)	0.8854 (5)	0.0591 (9)
H6A	1.0178	0.7232	1.0010	0.071*
H6B	1.0175	0.6394	0.8633	0.071*
C7	1.0733 (2)	0.8032 (3)	0.7746 (4)	0.0426 (6)
C8	1.0545 (2)	0.7728 (2)	0.5810 (3)	0.0308 (5)
H8	0.9966	0.7933	0.5426	0.041 (8)*
C9	1.1625 (2)	0.8449 (2)	0.4781 (4)	0.0394 (6)
H9	1.1895	0.9246	0.4721	0.039 (8)*
C10	1.2228 (2)	0.8058 (2)	0.3951 (4)	0.0367 (5)
C11	1.1869 (2)	0.6778 (2)	0.3958 (3)	0.0333 (5)
H11	1.1523	0.6443	0.2867	0.029 (7)*
C12	1.0980 (2)	0.6089 (2)	0.5320 (4)	0.0364 (5)
H12A	1.0624	0.5260	0.5090	0.044*
H12B	1.1371	0.6242	0.6396	0.044*
C13	1.3285 (3)	0.8828 (3)	0.2905 (5)	0.0549 (8)
H13A	1.3407	0.9607	0.2893	0.082*
H13B	1.3164	0.8532	0.1780	0.082*
H13C	1.3957	0.8837	0.3373	0.082*
C14	0.8465 (3)	0.4338 (3)	0.6503 (6)	0.0633 (10)
H14A	0.7653	0.3913	0.6796	0.095*
H14B	0.8927	0.4386	0.7459	0.095*
H14C	0.8611	0.3943	0.5608	0.095*
C15	1.0481 (4)	0.9031 (4)	0.8042 (6)	0.0718 (11)
H15A	0.9719	0.8811	0.7621	0.108*
H15B	1.1055	0.9718	0.7469	0.108*
H15C	1.0512	0.9188	0.9221	0.108*
C16	1.2019 (4)	0.8507 (4)	0.8255 (6)	0.0730 (11)
H16A	1.2122	0.8740	0.9410	0.109*
H16B	1.2515	0.9168	0.7568	0.109*
H16C	1.2219	0.7909	0.8102	0.109*
O1	1.28683 (18)	0.6633 (2)	0.4212 (3)	0.0453 (5)
H1	1.3211	0.6727	0.3319	0.068*
Cl1	0.85533 (6)	0.67322 (7)	0.30875 (9)	0.0497 (2)
Cl2	0.90015 (7)	0.48357 (7)	0.26866 (11)	0.0605 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0314 (11)	0.0304 (11)	0.0315 (12)	0.0170 (10)	0.0015 (9)	0.0018 (9)
C2	0.0353 (12)	0.0343 (12)	0.0391 (14)	0.0157 (10)	−0.0032 (10)	−0.0049 (10)
C3	0.0350 (13)	0.0374 (13)	0.0431 (15)	0.0164 (11)	0.0042 (11)	0.0079 (11)
C4	0.0365 (14)	0.0604 (18)	0.0436 (16)	0.0253 (13)	0.0107 (11)	0.0114 (13)
C5	0.0556 (19)	0.069 (2)	0.0418 (16)	0.0344 (17)	0.0144 (14)	0.0117 (15)
C6	0.065 (2)	0.079 (2)	0.0401 (17)	0.0407 (19)	−0.0012 (14)	0.0047 (16)
C7	0.0435 (14)	0.0539 (16)	0.0364 (14)	0.0289 (13)	−0.0053 (11)	−0.0123 (12)
C8	0.0306 (11)	0.0319 (12)	0.0351 (12)	0.0197 (10)	0.0012 (9)	−0.0015 (9)
C9	0.0409 (14)	0.0287 (12)	0.0461 (16)	0.0155 (10)	0.0048 (11)	0.0006 (10)
C10	0.0320 (12)	0.0339 (13)	0.0409 (14)	0.0141 (10)	0.0025 (10)	−0.0003 (10)
C11	0.0327 (12)	0.0367 (12)	0.0365 (14)	0.0218 (10)	−0.0017 (9)	−0.0045 (10)
C12	0.0369 (12)	0.0343 (12)	0.0451 (14)	0.0230 (11)	0.0031 (10)	0.0023 (10)
C13	0.0452 (16)	0.0493 (17)	0.064 (2)	0.0190 (14)	0.0200 (15)	0.0072 (14)
C14	0.0562 (19)	0.0404 (16)	0.082 (3)	0.0158 (15)	0.0123 (17)	0.0191 (16)
C15	0.078 (3)	0.071 (2)	0.078 (3)	0.046 (2)	0.002 (2)	−0.023 (2)
C16	0.058 (2)	0.087 (3)	0.069 (3)	0.033 (2)	−0.0150 (19)	−0.023 (2)
O1	0.0410 (10)	0.0614 (13)	0.0479 (12)	0.0365 (10)	0.0009 (8)	−0.0025 (9)
Cl1	0.0471 (4)	0.0680 (5)	0.0384 (3)	0.0321 (4)	−0.0065 (3)	0.0047 (3)
Cl2	0.0541 (4)	0.0536 (4)	0.0643 (5)	0.0199 (4)	−0.0071 (4)	−0.0266 (4)

C1—C12	1.521 (3)	C9—C10	1.326 (4)
C1—C2	1.522 (3)	C9—H9	0.9300
C1—C3	1.534 (3)	C10—C13	1.506 (4)
C1—C8	1.535 (3)	C10—C11	1.513 (4)
C2—C3	1.507 (4)	C11—O1	1.442 (3)
C2—Cl2	1.764 (3)	C11—C12	1.524 (4)
C2—Cl1	1.771 (3)	C11—H11	0.9800
C3—C14	1.524 (4)	C12—H12A	0.9700
C3—C4	1.535 (4)	C12—H12B	0.9700
C4—C5	1.512 (5)	C13—H13A	0.9600
C4—H4A	0.9700	C13—H13B	0.9600
C4—H4B	0.9700	C13—H13C	0.9600
C5—C6	1.584 (5)	C14—H14A	0.9600
C5—H5A	0.9700	C14—H14B	0.9600
C5—H5B	0.9700	C14—H14C	0.9600
C6—C7	1.518 (5)	C15—H15A	0.9600
C6—H6A	0.9700	C15—H15B	0.9600
C6—H6B	0.9700	C15—H15C	0.9600
C7—C15	1.534 (5)	C16—H16A	0.9600
C7—C16	1.545 (5)	C16—H16B	0.9600
C7—C8	1.585 (4)	C16—H16C	0.9600
C8—C9	1.505 (3)	O1—H1	0.8200
C8—H8	0.9800
C12—C1—C2	117.7 (2)	C1—C8—H8	106.2
C12—C1—C3	121.6 (2)	C7—C8—H8	106.2
C2—C1—C3	59.08 (17)	C10—C9—C8	126.2 (2)
C12—C1—C8	112.3 (2)	C10—C9—H9	116.9
C2—C1—C8	118.1 (2)	C8—C9—H9	116.9
C3—C1—C8	118.4 (2)	C9—C10—C13	123.3 (3)
C3—C2—C1	60.86 (17)	C9—C10—C11	121.5 (2)
C3—C2—Cl2	119.6 (2)	C13—C10—C11	115.2 (2)
C1—C2—Cl2	119.77 (19)	O1—C11—C10	110.7 (2)
C3—C2—Cl1	120.9 (2)	O1—C11—C12	107.7 (2)
C1—C2—Cl1	120.59 (18)	C10—C11—C12	112.9 (2)
Cl2—C2—Cl1	108.61 (15)	O1—C11—H11	108.5
C2—C3—C14	118.9 (3)	C10—C11—H11	108.5
C2—C3—C1	60.06 (16)	C12—C11—H11	108.5
C14—C3—C1	120.3 (3)	C1—C12—C11	110.3 (2)
C2—C3—C4	118.3 (2)	C1—C12—H12A	109.6
C14—C3—C4	113.0 (3)	C11—C12—H12A	109.6
C1—C3—C4	116.7 (2)	C1—C12—H12B	109.6
C5—C4—C3	112.2 (3)	C11—C12—H12B	109.6
C5—C4—H4A	109.2	H12A—C12—H12B	108.1
C3—C4—H4A	109.2	C10—C13—H13A	109.5
C5—C4—H4B	109.2	C10—C13—H13B	109.5
C3—C4—H4B	109.2	H13A—C13—H13B	109.5
H4A—C4—H4B	107.9	C10—C13—H13C	109.5
C4—C5—C6	114.6 (3)	H13A—C13—H13C	109.5
C4—C5—H5A	108.6	H13B—C13—H13C	109.5
C6—C5—H5A	108.6	C3—C14—H14A	109.5
C4—C5—H5B	108.6	C3—C14—H14B	109.5
C6—C5—H5B	108.6	H14A—C14—H14B	109.5
H5A—C5—H5B	107.6	C3—C14—H14C	109.5
C7—C6—C5	118.0 (3)	H14A—C14—H14C	109.5
C7—C6—H6A	107.8	H14B—C14—H14C	109.5
C5—C6—H6A	107.8	C7—C15—H15A	109.5
C7—C6—H6B	107.8	C7—C15—H15B	109.5
C5—C6—H6B	107.8	H15A—C15—H15B	109.5
H6A—C6—H6B	107.2	C7—C15—H15C	109.5
C6—C7—C15	111.2 (3)	H15A—C15—H15C	109.5
C6—C7—C16	108.2 (3)	H15B—C15—H15C	109.5
C15—C7—C16	106.2 (3)	C7—C16—H16A	109.5
C6—C7—C8	112.8 (2)	C7—C16—H16B	109.5
C15—C7—C8	107.1 (3)	H16A—C16—H16B	109.5
C16—C7—C8	111.1 (3)	C7—C16—H16C	109.5
C9—C8—C1	109.4 (2)	H16A—C16—H16C	109.5
C9—C8—C7	113.1 (2)	H16B—C16—H16C	109.5
C1—C8—C7	115.0 (2)	C11—O1—H1	109.5
C9—C8—H8	106.2

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1i	0.82	2.10	2.853 (4)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1i	0.82	2.10	2.853 (4)	153

Symmetry code: (i) .