(1S,3R,8R,10R)-2,2-Di-bromo-3,7,7,10-tetra-methyl-tri-cyclo-[6.4.0.0(1,3)]dodecan-9-one.

The title compound, C16H24Br2O was synthesized by 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 essential oil of the Atlas cedar (Cedrus atlantica). The mol-ecule is built up from a seven-membered ring to which a six- and a three-membered ring are fused. The six-membered ring shows a chair conformation. One C atom in the seven-membered ring and two methyl groups attached to the ring are disordered over two sets of sites, with an occupancy ratio of 0.658 (7):0.342 (7).

Related literature

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

Experimental

Crystal data

C16H24Br2O

M = 392.17

Monoclinic,

a = 6.5975 (2) Å

b = 15.2612 (3) Å

c = 8.2688 (2) Å

β = 100.045 (3)°

V = 819.79 (4) Å3

Z = 2

Cu Kα radiation

μ = 6.19 mm−1

T = 180 K

0.5 × 0.03 × 0.03 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T min = 0.269, T max = 1.000

6201 measured reflections

2416 independent reflections

2399 reflections with I > 2σ(I)

R int = 0.021

θmax = 60.5°

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.057

S = 1.07

2416 reflections

206 parameters

13 restraints

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.46 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▶), 1127 Friedel pairs

Absolute structure parameter: 0.01 (2)

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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/S1600536813030936/bt6944sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813030936/bt6944Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813030936/bt6944Isup3.cml

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

C16H24Br2O	F(000) = 396
Mr = 392.17	Dx = 1.589 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 6.5975 (2) Å	Cell parameters from 5144 reflections
b = 15.2612 (3) Å	θ = 5.4–60.5°
c = 8.2688 (2) Å	µ = 6.19 mm−1
β = 100.045 (3)°	T = 180 K
V = 819.79 (4) Å3	Box, colourless
Z = 2	0.5 × 0.03 × 0.03 mm

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	2416 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2399 reflections with I > 2σ(I)
Miror monochromator	Rint = 0.021
Detector resolution: 16.1978 pixels mm-1	θmax = 60.5°, θmin = 5.4°
ω scans	h = −7→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −17→17
Tmin = 0.269, Tmax = 1.000	l = −9→9
6201 measured reflections

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)] = 0.022	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.0402P)2 + 0.1798P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
2416 reflections	Δρmax = 0.28 e Å−3
206 parameters	Δρmin = −0.46 e Å−3
13 restraints	Absolute structure: Flack & Bernardinelli (2000), 1127 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Experimental. 'Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent Technologies, 2013 )

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.

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	Occ. (<1)
Br1	0.99187 (4)	0.122716 (16)	0.78691 (3)	0.03410 (11)
Br2	0.52030 (5)	0.08850 (2)	0.71788 (4)	0.04828 (14)
C1	0.7175 (4)	0.19420 (18)	1.0114 (3)	0.0248 (5)
C2	0.7326 (4)	0.1623 (2)	0.8397 (3)	0.0291 (6)
C3	0.6907 (5)	0.2575 (2)	0.8643 (3)	0.0326 (7)
C4	0.8580 (6)	0.3239 (2)	0.8543 (4)	0.0410 (8)
H4A	0.8283	0.3534	0.7461	0.049*
H4B	0.9909	0.2928	0.8611	0.049*
C5	0.8797 (7)	0.3936 (2)	0.9896 (4)	0.0503 (9)
H5A	0.7420	0.4081	1.0143	0.060*	0.658 (7)
H5B	0.9391	0.4476	0.9509	0.060*	0.658 (7)
H5C	1.0260	0.4115	1.0157	0.060*	0.342 (7)
H5D	0.7990	0.4457	0.9457	0.060*	0.342 (7)
C6	1.0237 (8)	0.3596 (3)	1.1520 (6)	0.0392 (15)	0.658 (7)
H6A	1.1545	0.3392	1.1218	0.047*	0.658 (7)
H6B	1.0568	0.4102	1.2269	0.047*	0.658 (7)
C7	0.9428 (5)	0.2883 (2)	1.2449 (4)	0.0328 (7)
C14	0.7534 (9)	0.3152 (3)	1.3157 (8)	0.0413 (14)	0.658 (7)
H14A	0.7838	0.3687	1.3809	0.062*	0.658 (7)
H14B	0.7166	0.2682	1.3858	0.062*	0.658 (7)
H14C	0.6383	0.3261	1.2258	0.062*	0.658 (7)
C15	1.1166 (8)	0.2667 (3)	1.3978 (6)	0.0365 (13)	0.658 (7)
H15A	1.2357	0.2410	1.3593	0.055*	0.658 (7)
H15B	1.0630	0.2250	1.4701	0.055*	0.658 (7)
H15C	1.1584	0.3207	1.4585	0.055*	0.658 (7)
C14A	1.1692 (14)	0.3197 (7)	1.2660 (14)	0.045 (3)	0.342 (7)
H14D	1.1823	0.3768	1.3210	0.067*	0.342 (7)
H14E	1.2096	0.3250	1.1579	0.067*	0.342 (7)
H14F	1.2588	0.2772	1.3325	0.067*	0.342 (7)
C15A	0.866 (2)	0.2882 (7)	1.4049 (13)	0.044 (3)	0.342 (7)
H15D	0.9478	0.2471	1.4808	0.065*	0.342 (7)
H15E	0.7213	0.2702	1.3864	0.065*	0.342 (7)
H15F	0.8787	0.3472	1.4521	0.065*	0.342 (7)
C6A	0.8140 (16)	0.3676 (5)	1.1417 (10)	0.039 (3)	0.342 (7)
H6A1	0.6676	0.3499	1.1154	0.047*	0.342 (7)
H6A2	0.8219	0.4196	1.2140	0.047*	0.342 (7)
C8	0.9178 (4)	0.20156 (19)	1.1383 (3)	0.0246 (6)
H8	1.0321	0.2026	1.0731	0.030*
C9	0.9510 (5)	0.1190 (2)	1.2426 (4)	0.0317 (6)
C10	0.7707 (5)	0.07818 (19)	1.3066 (4)	0.0325 (6)
H10	0.7333	0.1186	1.3919	0.039*
C11	0.5854 (5)	0.0733 (2)	1.1673 (4)	0.0360 (7)
H11A	0.6147	0.0305	1.0844	0.043*
H11B	0.4645	0.0519	1.2117	0.043*
C12	0.5341 (4)	0.1611 (2)	1.0847 (4)	0.0324 (6)
H12A	0.5006	0.2040	1.1660	0.039*
H12B	0.4123	0.1550	0.9967	0.039*
C101	0.8255 (6)	−0.0096 (2)	1.3886 (4)	0.0468 (9)
H10A	0.8667	−0.0504	1.3089	0.070*
H10B	0.7056	−0.0331	1.4293	0.070*
H10C	0.9396	−0.0019	1.4808	0.070*
C311	0.4754 (6)	0.2933 (3)	0.7987 (5)	0.0508 (10)
H31A	0.4663	0.3099	0.6832	0.076*
H31B	0.4496	0.3448	0.8628	0.076*
H31C	0.3726	0.2481	0.8081	0.076*
O1	1.1188 (4)	0.08460 (19)	1.2698 (4)	0.0608 (8)

	U11	U22	U33	U12	U13	U23
Br1	0.03127 (18)	0.04181 (18)	0.03046 (17)	−0.00328 (14)	0.00880 (13)	−0.00787 (14)
Br2	0.0335 (2)	0.0641 (3)	0.0454 (2)	−0.01004 (16)	0.00180 (17)	−0.02435 (18)
C1	0.0237 (14)	0.0255 (12)	0.0249 (13)	0.0003 (12)	0.0029 (11)	0.0001 (11)
C2	0.0238 (13)	0.0362 (14)	0.0263 (12)	−0.0054 (13)	0.0016 (11)	−0.0060 (12)
C3	0.0347 (16)	0.0360 (15)	0.0258 (13)	0.0046 (13)	0.0011 (12)	0.0022 (12)
C4	0.060 (2)	0.0321 (16)	0.0289 (15)	−0.0066 (15)	0.0024 (15)	0.0089 (13)
C5	0.077 (3)	0.0221 (15)	0.052 (2)	−0.0032 (16)	0.0115 (19)	0.0029 (14)
C6	0.057 (4)	0.023 (2)	0.035 (3)	−0.011 (2)	0.000 (2)	−0.005 (2)
C7	0.0376 (16)	0.0305 (16)	0.0301 (14)	−0.0034 (13)	0.0056 (14)	−0.0104 (13)
C14	0.053 (3)	0.029 (2)	0.042 (3)	0.001 (3)	0.010 (3)	−0.015 (2)
C15	0.044 (3)	0.029 (2)	0.032 (2)	−0.003 (2)	−0.006 (2)	−0.0076 (19)
C14A	0.038 (6)	0.045 (5)	0.052 (6)	−0.010 (5)	0.008 (5)	−0.019 (5)
C15A	0.067 (8)	0.030 (5)	0.037 (6)	−0.008 (5)	0.020 (6)	−0.015 (4)
C6A	0.052 (7)	0.024 (4)	0.045 (5)	0.002 (4)	0.016 (4)	−0.004 (4)
C8	0.0238 (14)	0.0258 (13)	0.0247 (13)	−0.0026 (12)	0.0053 (11)	−0.0044 (11)
C9	0.0354 (16)	0.0320 (14)	0.0267 (12)	0.0054 (16)	0.0027 (12)	−0.0014 (15)
C10	0.0455 (18)	0.0254 (13)	0.0297 (14)	0.0012 (14)	0.0152 (13)	0.0005 (11)
C11	0.0316 (15)	0.0377 (17)	0.0417 (16)	−0.0064 (14)	0.0149 (13)	−0.0003 (14)
C12	0.0224 (14)	0.0378 (14)	0.0379 (14)	−0.0011 (13)	0.0081 (12)	−0.0046 (14)
C101	0.070 (3)	0.0292 (16)	0.0422 (18)	0.0018 (16)	0.0138 (17)	0.0041 (14)
C311	0.048 (2)	0.050 (2)	0.049 (2)	0.0172 (16)	−0.0070 (18)	0.0059 (15)
O1	0.0390 (13)	0.0750 (18)	0.0715 (17)	0.0250 (14)	0.0177 (12)	0.0388 (15)

Br1—C2	1.934 (3)	C15—H15A	0.9800
Br2—C2	1.938 (3)	C15—H15B	0.9800
C1—C2	1.521 (4)	C15—H15C	0.9800
C1—C12	1.530 (4)	C14A—H14D	0.9800
C1—C3	1.539 (4)	C14A—H14E	0.9800
C1—C8	1.542 (4)	C14A—H14F	0.9800
C2—C3	1.499 (4)	C15A—H15D	0.9800
C3—C4	1.512 (5)	C15A—H15E	0.9800
C3—C311	1.530 (4)	C15A—H15F	0.9800
C4—C5	1.533 (5)	C6A—H6A1	0.9900
C4—H4A	0.9900	C6A—H6A2	0.9900
C4—H4B	0.9900	C8—C9	1.521 (4)
C5—C6A	1.455 (9)	C8—H8	1.0000
C5—C6	1.590 (6)	C9—O1	1.210 (4)
C5—H5A	0.9900	C9—C10	1.517 (4)
C5—H5B	0.9900	C10—C101	1.516 (4)
C5—H5C	0.9900	C10—C11	1.528 (4)
C5—H5D	0.9900	C10—H10	1.0000
C6—C7	1.484 (6)	C11—C12	1.515 (5)
C6—H6A	0.9900	C11—H11A	0.9900
C6—H6B	0.9900	C11—H11B	0.9900
C7—C15A	1.496 (9)	C12—H12A	0.9900
C7—C14	1.525 (6)	C12—H12B	0.9900
C7—C14A	1.549 (9)	C101—H10A	0.9800
C7—C8	1.583 (4)	C101—H10B	0.9800
C7—C15	1.586 (5)	C101—H10C	0.9800
C7—C6A	1.632 (8)	C311—H31A	0.9800
C14—H14A	0.9800	C311—H31B	0.9800
C14—H14B	0.9800	C311—H31C	0.9800
C14—H14C	0.9800
C2—C1—C12	116.7 (2)	C14—C7—C6A	67.3 (4)
C2—C1—C3	58.67 (19)	C14A—C7—C6A	103.5 (6)
C12—C1—C3	122.0 (2)	C8—C7—C6A	109.6 (4)
C2—C1—C8	118.1 (2)	C15—C7—C6A	144.0 (4)
C12—C1—C8	113.4 (2)	C7—C14—H14A	109.5
C3—C1—C8	117.3 (2)	C7—C14—H14B	109.5
C3—C2—C1	61.27 (19)	C7—C14—H14C	109.5
C3—C2—Br1	121.7 (2)	C7—C15—H15A	109.5
C1—C2—Br1	121.02 (19)	C7—C15—H15B	109.5
C3—C2—Br2	120.0 (2)	C7—C15—H15C	109.5
C1—C2—Br2	120.8 (2)	C7—C14A—H14D	109.5
Br1—C2—Br2	106.78 (14)	C7—C14A—H14E	109.5
C2—C3—C4	119.2 (3)	H14D—C14A—H14E	109.5
C2—C3—C311	118.7 (3)	C7—C14A—H14F	109.5
C4—C3—C311	112.5 (3)	H14D—C14A—H14F	109.5
C2—C3—C1	60.06 (19)	H14E—C14A—H14F	109.5
C4—C3—C1	118.7 (2)	C7—C15A—H15D	109.5
C311—C3—C1	118.4 (3)	C7—C15A—H15E	109.5
C3—C4—C5	113.7 (3)	H15D—C15A—H15E	109.5
C3—C4—H4A	108.8	C7—C15A—H15F	109.5
C5—C4—H4A	108.8	H15D—C15A—H15F	109.5
C3—C4—H4B	108.8	H15E—C15A—H15F	109.5
C5—C4—H4B	108.8	C5—C6A—C7	116.6 (6)
H4A—C4—H4B	107.7	C5—C6A—H6A1	108.1
C6A—C5—C4	116.0 (4)	C7—C6A—H6A1	108.1
C6A—C5—C6	53.5 (5)	C5—C6A—H6A2	108.1
C4—C5—C6	110.9 (3)	C7—C6A—H6A2	108.1
C6A—C5—H5A	57.4	H6A1—C6A—H6A2	107.3
C4—C5—H5A	109.5	C9—C8—C1	110.3 (2)
C6—C5—H5A	109.5	C9—C8—C7	112.7 (2)
C6A—C5—H5B	134.6	C1—C8—C7	115.7 (2)
C4—C5—H5B	109.5	C9—C8—H8	105.8
C6—C5—H5B	109.5	C1—C8—H8	105.8
H5A—C5—H5B	108.1	C7—C8—H8	105.8
C6A—C5—H5C	108.3	O1—C9—C10	120.3 (3)
C4—C5—H5C	108.3	O1—C9—C8	120.1 (3)
C6—C5—H5C	59.4	C10—C9—C8	119.6 (2)
H5A—C5—H5C	142.0	C101—C10—C9	112.3 (3)
H5B—C5—H5C	54.1	C101—C10—C11	113.0 (3)
C6A—C5—H5D	108.3	C9—C10—C11	109.3 (2)
C4—C5—H5D	108.3	C101—C10—H10	107.3
C6—C5—H5D	140.8	C9—C10—H10	107.3
H5A—C5—H5D	56.1	C11—C10—H10	107.3
H5B—C5—H5D	55.3	C12—C11—C10	112.5 (3)
H5C—C5—H5D	107.4	C12—C11—H11A	109.1
C7—C6—C5	117.4 (4)	C10—C11—H11A	109.1
C7—C6—H6A	107.9	C12—C11—H11B	109.1
C5—C6—H6A	107.9	C10—C11—H11B	109.1
C7—C6—H6B	107.9	H11A—C11—H11B	107.8
C5—C6—H6B	107.9	C11—C12—C1	109.9 (2)
H6A—C6—H6B	107.2	C11—C12—H12A	109.7
C6—C7—C15A	131.7 (5)	C1—C12—H12A	109.7
C6—C7—C14	113.1 (4)	C11—C12—H12B	109.7
C15A—C7—C14	40.1 (5)	C1—C12—H12B	109.7
C6—C7—C14A	53.5 (5)	H12A—C12—H12B	108.2
C15A—C7—C14A	111.7 (7)	C10—C101—H10A	109.5
C14—C7—C14A	135.3 (5)	C10—C101—H10B	109.5
C6—C7—C8	109.7 (3)	H10A—C101—H10B	109.5
C15A—C7—C8	118.2 (4)	C10—C101—H10C	109.5
C14—C7—C8	115.3 (3)	H10A—C101—H10C	109.5
C14A—C7—C8	109.0 (4)	H10B—C101—H10C	109.5
C6—C7—C15	106.8 (3)	C3—C311—H31A	109.5
C15A—C7—C15	66.7 (6)	C3—C311—H31B	109.5
C14—C7—C15	106.1 (4)	H31A—C311—H31B	109.5
C14A—C7—C15	55.0 (5)	C3—C311—H31C	109.5
C8—C7—C15	105.1 (3)	H31A—C311—H31C	109.5
C6—C7—C6A	52.2 (4)	H31B—C311—H31C	109.5
C15A—C7—C6A	103.7 (6)