organic compounds
(1R,4R,6S,7R)-5,5-Dibromo-1,4,8,8-tetramethyltricyclo[5.4.1.04,6]dodecan-12-one
aLaboratoire de Chimie des Substances Naturelles, "Unité Associé au CNRST (URAC16)", Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco, and bLaboratoire de Chimie de Coordination, 205 Route de Narbone, 31077 Toulouse Cedex 04, France
*Correspondence e-mail: zaki4692@gmail.com
The title compound, C16H24Br2O, was synthesized from the reaction of β-himachalene (3,5,5,9-tetramethyl-2,4a,5,6,7,8-hexahydro-1H-benzocycloheptene), which was isolated from Atlas cedar (Cedrus atlantica). The contains two independent molecules with similar conformations. Each molecule is built up from two fused seven-membered rings and an additional three-membered ring. In both molecules, one of the seven-membered rings has a chair conformation, whereas the other displays a screw-boat conformation.
CCDC reference: 995040
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); Oukhrib et al. (2013). For their potential antifungal activity against the phytopathogen Botrytis cinerea, see: Daoubi et al. (2004). For puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2012); cell 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: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 995040
10.1107/S1600536814007351/bt6972sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814007351/bt6972Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814007351/bt6972Isup3.cml
To obtain the title compound, BF3—Et2O(1 mL) was added dropwise to a solution of (1S,2R,7R,8S,10R)-9,9-dibromo- 1α,2α-epoxy-2,6,6,10-tetramethyltricyclo[5.5.0.08,10]dodecane (1 g, 2.5 mmol) in 60 ml of dichloromethane at 195 K under nitrogen. The reaction mixture was stirred for two hours at a constant temperature of 195 K and left at ambient temperature for 24 h. Water (60 ml) was added in order to separate the two phases, and the organic phase was dried and concentrated. The residue obtained was chromatographed on silica-gel eluting with hexane-ethyl acetate (98/2), which allowed the isolation of pure(1S,6R,7S,9R)-12-acetyl-8,8-dibromo-5,5,9- trimethyltricyclo[4.4.0,17,9]decane in a yield of 20% (196 mg, 0.5 mmol). The title compound was recrystallized from its pentane solution.
All H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl), 0.97 Å (methylene), 0.98 Å (methine) with Uiso(H) = 1.2Ueq(methylene, methine) or Uiso(H) = 1.5Ueq(methyl). The methyl groups were allowed to rotate but not to tip.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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: publCIF (Westrip, 2010).C16H24Br2O | Z = 2 |
Mr = 392.17 | F(000) = 396 |
Triclinic, P1 | Dx = 1.620 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6550 (3) Å | Cell parameters from 2828 reflections |
b = 9.4142 (4) Å | θ = 3.7–26.6° |
c = 12.9389 (13) Å | µ = 5.03 mm−1 |
α = 86.008 (6)° | T = 173 K |
β = 83.921 (6)° | Needle, colourless |
γ = 89.511 (4)° | 0.38 × 0.11 × 0.10 mm |
V = 804.13 (9) Å3 |
Agilent Xcalibur (Eos, Gemini ultra) diffractometer | 6327 independent reflections |
Radiation source: fine-focus sealed tube | 5209 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 16.1978 pixels mm-1 | θmax = 26.4°, θmin = 3.2° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −11→11 |
Tmin = 0.670, Tmax = 1.00 | l = −16→16 |
11451 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)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0447P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
6327 reflections | Δρmax = 0.77 e Å−3 |
351 parameters | Δρmin = −0.62 e Å−3 |
3 restraints | Absolute structure: Flack & Bernardinelli (2000), 3035 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.017 (15) |
C16H24Br2O | γ = 89.511 (4)° |
Mr = 392.17 | V = 804.13 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6550 (3) Å | Mo Kα radiation |
b = 9.4142 (4) Å | µ = 5.03 mm−1 |
c = 12.9389 (13) Å | T = 173 K |
α = 86.008 (6)° | 0.38 × 0.11 × 0.10 mm |
β = 83.921 (6)° |
Agilent Xcalibur (Eos, Gemini ultra) diffractometer | 6327 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 5209 reflections with I > 2σ(I) |
Tmin = 0.670, Tmax = 1.00 | Rint = 0.057 |
11451 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.119 | Δρmax = 0.77 e Å−3 |
S = 1.01 | Δρmin = −0.62 e Å−3 |
6327 reflections | Absolute structure: Flack & Bernardinelli (2000), 3035 Friedel pairs |
351 parameters | Absolute structure parameter: −0.017 (15) |
3 restraints |
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 > σ(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 | 0.5880 (12) | −0.1550 (8) | 1.2375 (6) | 0.0276 (18) | |
C2 | 0.5505 (13) | −0.0914 (9) | 1.3464 (6) | 0.034 (2) | |
H2A | 0.4417 | −0.1471 | 1.3886 | 0.040* | |
H2B | 0.6748 | −0.1053 | 1.3818 | 0.040* | |
C3 | 0.4926 (12) | 0.0666 (9) | 1.3462 (7) | 0.028 (2) | |
H3A | 0.4717 | 0.0941 | 1.4191 | 0.034* | |
H3B | 0.6059 | 0.1241 | 1.3098 | 0.034* | |
C4 | 0.3007 (11) | 0.1013 (8) | 1.2934 (6) | 0.0252 (18) | |
C5 | 0.2942 (11) | 0.2374 (8) | 1.2238 (6) | 0.0225 (17) | |
C6 | 0.3148 (11) | 0.0978 (7) | 1.1734 (6) | 0.0191 (17) | |
H6 | 0.1873 | 0.0660 | 1.1475 | 0.023* | |
C7 | 0.5057 (11) | 0.0591 (8) | 1.1050 (6) | 0.0226 (17) | |
H7 | 0.5764 | 0.1510 | 1.0817 | 0.027* | |
C8 | 0.4504 (11) | −0.0078 (8) | 1.0021 (6) | 0.0275 (18) | |
C9 | 0.3174 (14) | −0.1435 (8) | 1.0270 (7) | 0.033 (2) | |
H9A | 0.1841 | −0.1137 | 1.0599 | 0.039* | |
H9B | 0.2948 | −0.1823 | 0.9600 | 0.039* | |
C10 | 0.3944 (13) | −0.2635 (8) | 1.0963 (7) | 0.032 (2) | |
H10A | 0.5336 | −0.2882 | 1.0683 | 0.039* | |
H10B | 0.3086 | −0.3484 | 1.0942 | 0.039* | |
C11 | 0.3955 (12) | −0.2268 (8) | 1.2106 (6) | 0.0281 (19) | |
H11A | 0.2794 | −0.1633 | 1.2280 | 0.034* | |
H11B | 0.3738 | −0.3158 | 1.2557 | 0.034* | |
C12 | 0.6585 (11) | −0.0347 (8) | 1.1572 (6) | 0.0221 (17) | |
C13 | 0.7592 (14) | −0.2668 (10) | 1.2418 (8) | 0.039 (2) | |
H13A | 0.7752 | −0.3149 | 1.1767 | 0.059* | |
H13B | 0.7249 | −0.3370 | 1.3004 | 0.059* | |
H13C | 0.8859 | −0.2193 | 1.2510 | 0.059* | |
C14 | 0.6448 (14) | −0.0429 (10) | 0.9350 (6) | 0.037 (2) | |
H14A | 0.6112 | −0.0806 | 0.8703 | 0.056* | |
H14B | 0.7220 | −0.1143 | 0.9732 | 0.056* | |
H14C | 0.7259 | 0.0437 | 0.9186 | 0.056* | |
C15 | 0.3312 (14) | 0.1068 (9) | 0.9411 (6) | 0.031 (2) | |
H15A | 0.3025 | 0.0710 | 0.8748 | 0.046* | |
H15B | 0.4121 | 0.1939 | 0.9274 | 0.046* | |
H15C | 0.2038 | 0.1277 | 0.9825 | 0.046* | |
C16 | 0.1080 (12) | 0.0472 (9) | 1.3566 (7) | 0.037 (2) | |
H16A | 0.0519 | 0.1213 | 1.4010 | 0.055* | |
H16B | 0.1382 | −0.0379 | 1.4004 | 0.055* | |
H16C | 0.0094 | 0.0233 | 1.3094 | 0.055* | |
O1 | 0.8370 (8) | −0.0058 (6) | 1.1385 (5) | 0.0370 (15) | |
Br1 | 0.51009 (11) | 0.37150 (8) | 1.21049 (7) | 0.0329 (3) | |
Br2 | 0.04085 (11) | 0.33708 (9) | 1.21682 (7) | 0.0376 (3) | |
C1A | 0.2236 (11) | 0.6190 (8) | 0.6230 (6) | 0.0250 (17) | |
C2A | 0.2439 (12) | 0.5548 (8) | 0.5146 (6) | 0.0284 (19) | |
H2C | 0.1584 | 0.6115 | 0.4690 | 0.034* | |
H2D | 0.3858 | 0.5664 | 0.4836 | 0.034* | |
C3A | 0.1869 (11) | 0.3985 (9) | 0.5135 (7) | 0.024 (2) | |
H3C | 0.2845 | 0.3398 | 0.5505 | 0.029* | |
H3D | 0.1994 | 0.3720 | 0.4403 | 0.029* | |
C4A | −0.0271 (11) | 0.3624 (8) | 0.5636 (6) | 0.0237 (17) | |
C5A | −0.0676 (11) | 0.2274 (8) | 0.6295 (6) | 0.0208 (17) | |
C6A | −0.0769 (11) | 0.3672 (7) | 0.6818 (6) | 0.0193 (16) | |
H6A1 | −0.2177 | 0.3998 | 0.7029 | 0.023* | |
C7A | 0.0724 (11) | 0.4048 (7) | 0.7548 (6) | 0.0208 (16) | |
H7A1 | 0.1292 | 0.3125 | 0.7819 | 0.025* | |
C8A | −0.0317 (11) | 0.4772 (7) | 0.8529 (5) | 0.0233 (17) | |
C9A | −0.1548 (13) | 0.6092 (8) | 0.8239 (6) | 0.027 (2) | |
H9A1 | −0.2120 | 0.6492 | 0.8895 | 0.032* | |
H9A2 | −0.2699 | 0.5776 | 0.7887 | 0.032* | |
C10A | −0.0473 (13) | 0.7314 (8) | 0.7539 (6) | 0.034 (2) | |
H10C | −0.1388 | 0.8148 | 0.7518 | 0.040* | |
H10D | 0.0745 | 0.7597 | 0.7852 | 0.040* | |
C11A | 0.0146 (11) | 0.6919 (8) | 0.6438 (6) | 0.0258 (18) | |
H11C | 0.0137 | 0.7796 | 0.5969 | 0.031* | |
H11D | −0.0896 | 0.6275 | 0.6240 | 0.031* | |
C12A | 0.2523 (11) | 0.4925 (7) | 0.7042 (6) | 0.0237 (17) | |
C13A | 0.3950 (13) | 0.7266 (9) | 0.6268 (7) | 0.035 (2) | |
H13D | 0.3753 | 0.8098 | 0.5791 | 0.053* | |
H13E | 0.5252 | 0.6818 | 0.6059 | 0.053* | |
H13F | 0.3939 | 0.7566 | 0.6979 | 0.053* | |
C14A | −0.1763 (13) | 0.3701 (8) | 0.9151 (7) | 0.032 (2) | |
H14D | −0.2433 | 0.4139 | 0.9761 | 0.049* | |
H14E | −0.1004 | 0.2861 | 0.9378 | 0.049* | |
H14F | −0.2782 | 0.3416 | 0.8711 | 0.049* | |
C15A | 0.1302 (13) | 0.5154 (8) | 0.9242 (6) | 0.0308 (19) | |
H15D | 0.2236 | 0.5859 | 0.8868 | 0.046* | |
H15E | 0.2053 | 0.4294 | 0.9437 | 0.046* | |
H15F | 0.0639 | 0.5550 | 0.9871 | 0.046* | |
C16A | −0.1904 (12) | 0.4126 (9) | 0.4946 (7) | 0.036 (2) | |
H16D | −0.1881 | 0.3525 | 0.4356 | 0.054* | |
H16E | −0.1646 | 0.5117 | 0.4687 | 0.054* | |
H16F | −0.3231 | 0.4056 | 0.5354 | 0.054* | |
O2 | 0.4216 (8) | 0.4614 (6) | 0.7244 (5) | 0.0338 (14) | |
Br3 | 0.14860 (10) | 0.09484 (7) | 0.65374 (6) | 0.0290 (2) | |
Br4 | −0.31319 (12) | 0.12276 (9) | 0.62628 (7) | 0.0378 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.029 (5) | 0.015 (4) | 0.039 (5) | 0.006 (3) | −0.006 (4) | −0.002 (3) |
C2 | 0.032 (5) | 0.042 (5) | 0.027 (5) | 0.003 (4) | −0.011 (4) | 0.003 (4) |
C3 | 0.028 (5) | 0.038 (6) | 0.021 (5) | 0.002 (4) | −0.012 (4) | −0.006 (4) |
C4 | 0.020 (4) | 0.028 (4) | 0.027 (4) | 0.000 (3) | −0.003 (3) | 0.005 (3) |
C5 | 0.014 (4) | 0.030 (4) | 0.022 (4) | 0.011 (3) | 0.002 (3) | −0.002 (3) |
C6 | 0.018 (4) | 0.019 (4) | 0.022 (4) | 0.002 (3) | −0.008 (3) | −0.001 (3) |
C7 | 0.020 (4) | 0.021 (4) | 0.025 (4) | 0.005 (3) | 0.004 (3) | −0.003 (3) |
C8 | 0.030 (5) | 0.027 (4) | 0.025 (5) | 0.008 (3) | 0.002 (4) | −0.002 (3) |
C9 | 0.029 (5) | 0.030 (5) | 0.042 (6) | −0.008 (4) | −0.015 (4) | −0.007 (4) |
C10 | 0.036 (5) | 0.021 (4) | 0.041 (5) | 0.005 (3) | −0.013 (4) | −0.004 (4) |
C11 | 0.030 (4) | 0.023 (5) | 0.031 (5) | 0.000 (3) | −0.004 (4) | 0.004 (4) |
C12 | 0.019 (4) | 0.021 (4) | 0.027 (4) | 0.001 (3) | −0.003 (3) | −0.009 (3) |
C13 | 0.040 (6) | 0.037 (5) | 0.043 (6) | 0.006 (4) | −0.018 (5) | 0.006 (4) |
C14 | 0.048 (6) | 0.046 (6) | 0.018 (5) | 0.012 (4) | 0.003 (4) | −0.007 (4) |
C15 | 0.044 (6) | 0.034 (5) | 0.017 (4) | 0.015 (4) | −0.012 (4) | −0.009 (4) |
C16 | 0.024 (5) | 0.050 (6) | 0.034 (5) | −0.008 (4) | 0.007 (4) | −0.003 (4) |
O1 | 0.017 (3) | 0.034 (3) | 0.059 (4) | 0.005 (2) | −0.001 (3) | 0.000 (3) |
Br1 | 0.0291 (5) | 0.0234 (5) | 0.0468 (6) | 0.0026 (3) | −0.0041 (4) | −0.0068 (4) |
Br2 | 0.0272 (5) | 0.0480 (6) | 0.0380 (6) | 0.0191 (4) | −0.0027 (4) | −0.0084 (5) |
C1A | 0.017 (4) | 0.031 (4) | 0.024 (4) | 0.000 (3) | 0.005 (3) | 0.000 (3) |
C2A | 0.028 (4) | 0.028 (4) | 0.026 (5) | 0.006 (3) | 0.010 (4) | 0.001 (3) |
C3A | 0.020 (4) | 0.024 (5) | 0.027 (5) | 0.001 (3) | 0.005 (4) | −0.003 (4) |
C4A | 0.015 (4) | 0.022 (4) | 0.035 (5) | 0.000 (3) | −0.004 (3) | 0.000 (3) |
C5A | 0.018 (4) | 0.029 (4) | 0.016 (4) | −0.002 (3) | −0.001 (3) | −0.006 (3) |
C6A | 0.018 (4) | 0.014 (4) | 0.024 (4) | 0.005 (3) | 0.004 (3) | 0.002 (3) |
C7A | 0.024 (4) | 0.016 (4) | 0.023 (4) | 0.004 (3) | −0.003 (3) | −0.006 (3) |
C8A | 0.034 (5) | 0.023 (4) | 0.013 (4) | 0.003 (3) | −0.003 (3) | −0.002 (3) |
C9A | 0.021 (4) | 0.030 (4) | 0.027 (5) | 0.008 (3) | 0.011 (4) | −0.004 (4) |
C10A | 0.038 (5) | 0.017 (4) | 0.043 (5) | 0.013 (3) | 0.009 (4) | 0.001 (4) |
C11A | 0.024 (4) | 0.012 (4) | 0.039 (5) | 0.004 (3) | 0.002 (4) | 0.003 (3) |
C12A | 0.021 (4) | 0.018 (4) | 0.031 (5) | 0.004 (3) | 0.002 (3) | −0.006 (3) |
C13A | 0.034 (5) | 0.026 (5) | 0.045 (6) | −0.004 (4) | 0.003 (4) | −0.001 (4) |
C14A | 0.029 (5) | 0.024 (4) | 0.041 (5) | 0.005 (4) | 0.006 (4) | 0.004 (4) |
C15A | 0.045 (5) | 0.024 (4) | 0.025 (5) | 0.003 (4) | −0.010 (4) | −0.005 (3) |
C16A | 0.027 (5) | 0.051 (6) | 0.030 (5) | 0.002 (4) | −0.006 (4) | −0.003 (4) |
O2 | 0.016 (3) | 0.035 (3) | 0.050 (4) | 0.001 (2) | −0.003 (3) | −0.001 (3) |
Br3 | 0.0281 (5) | 0.0210 (5) | 0.0387 (6) | 0.0047 (3) | −0.0057 (4) | −0.0052 (4) |
Br4 | 0.0263 (5) | 0.0444 (6) | 0.0443 (6) | −0.0121 (4) | −0.0082 (4) | −0.0074 (5) |
C1—C12 | 1.525 (11) | C1A—C13A | 1.539 (11) |
C1—C11 | 1.537 (11) | C1A—C11A | 1.552 (10) |
C1—C13 | 1.547 (11) | C1A—C12A | 1.557 (10) |
C1—C2 | 1.564 (11) | C1A—C2A | 1.557 (11) |
C2—C3 | 1.534 (12) | C2A—C3A | 1.524 (11) |
C2—H2A | 0.9900 | C2A—H2C | 0.9900 |
C2—H2B | 0.9900 | C2A—H2D | 0.9900 |
C3—C4 | 1.534 (10) | C3A—C4A | 1.532 (9) |
C3—H3A | 0.9900 | C3A—H3C | 0.9900 |
C3—H3B | 0.9900 | C3A—H3D | 0.9900 |
C4—C5 | 1.517 (10) | C4A—C5A | 1.490 (10) |
C4—C16 | 1.519 (10) | C4A—C16A | 1.529 (11) |
C4—C6 | 1.548 (10) | C4A—C6A | 1.534 (10) |
C5—C6 | 1.506 (11) | C5A—C6A | 1.518 (10) |
C5—Br1 | 1.907 (8) | C5A—Br4 | 1.921 (7) |
C5—Br2 | 1.930 (7) | C5A—Br3 | 1.933 (8) |
C6—C7 | 1.527 (9) | C6A—C7A | 1.503 (10) |
C6—H6 | 1.0000 | C6A—H6A1 | 1.0000 |
C7—C12 | 1.522 (10) | C7A—C12A | 1.523 (10) |
C7—C8 | 1.591 (10) | C7A—C8A | 1.575 (10) |
C7—H7 | 1.0000 | C7A—H7A1 | 1.0000 |
C8—C14 | 1.526 (10) | C8A—C14A | 1.526 (10) |
C8—C15 | 1.555 (10) | C8A—C9A | 1.530 (10) |
C8—C9 | 1.556 (11) | C8A—C15A | 1.551 (10) |
C9—C10 | 1.513 (11) | C9A—C10A | 1.545 (11) |
C9—H9A | 0.9900 | C9A—H9A1 | 0.9900 |
C9—H9B | 0.9900 | C9A—H9A2 | 0.9900 |
C10—C11 | 1.542 (11) | C10A—C11A | 1.512 (11) |
C10—H10A | 0.9900 | C10A—H10C | 0.9900 |
C10—H10B | 0.9900 | C10A—H10D | 0.9900 |
C11—H11A | 0.9900 | C11A—H11C | 0.9900 |
C11—H11B | 0.9900 | C11A—H11D | 0.9900 |
C12—O1 | 1.217 (9) | C12A—O2 | 1.212 (9) |
C13—H13A | 0.9800 | C13A—H13D | 0.9800 |
C13—H13B | 0.9800 | C13A—H13E | 0.9800 |
C13—H13C | 0.9800 | C13A—H13F | 0.9800 |
C14—H14A | 0.9800 | C14A—H14D | 0.9800 |
C14—H14B | 0.9800 | C14A—H14E | 0.9800 |
C14—H14C | 0.9800 | C14A—H14F | 0.9800 |
C15—H15A | 0.9800 | C15A—H15D | 0.9800 |
C15—H15B | 0.9800 | C15A—H15E | 0.9800 |
C15—H15C | 0.9800 | C15A—H15F | 0.9800 |
C16—H16A | 0.9800 | C16A—H16D | 0.9800 |
C16—H16B | 0.9800 | C16A—H16E | 0.9800 |
C16—H16C | 0.9800 | C16A—H16F | 0.9800 |
C12—C1—C11 | 111.9 (7) | C13A—C1A—C11A | 110.5 (7) |
C12—C1—C13 | 108.5 (7) | C13A—C1A—C12A | 108.2 (7) |
C11—C1—C13 | 109.4 (6) | C11A—C1A—C12A | 112.0 (6) |
C12—C1—C2 | 108.1 (6) | C13A—C1A—C2A | 109.6 (6) |
C11—C1—C2 | 110.6 (7) | C11A—C1A—C2A | 110.4 (7) |
C13—C1—C2 | 108.3 (7) | C12A—C1A—C2A | 106.0 (6) |
C3—C2—C1 | 116.4 (7) | C3A—C2A—C1A | 116.6 (6) |
C3—C2—H2A | 108.2 | C3A—C2A—H2C | 108.2 |
C1—C2—H2A | 108.2 | C1A—C2A—H2C | 108.2 |
C3—C2—H2B | 108.2 | C3A—C2A—H2D | 108.2 |
C1—C2—H2B | 108.2 | C1A—C2A—H2D | 108.2 |
H2A—C2—H2B | 107.3 | H2C—C2A—H2D | 107.3 |
C4—C3—C2 | 113.0 (7) | C2A—C3A—C4A | 114.3 (6) |
C4—C3—H3A | 109.0 | C2A—C3A—H3C | 108.7 |
C2—C3—H3A | 109.0 | C4A—C3A—H3C | 108.7 |
C4—C3—H3B | 109.0 | C2A—C3A—H3D | 108.7 |
C2—C3—H3B | 109.0 | C4A—C3A—H3D | 108.7 |
H3A—C3—H3B | 107.8 | H3C—C3A—H3D | 107.6 |
C5—C4—C16 | 119.2 (7) | C5A—C4A—C16A | 116.7 (6) |
C5—C4—C3 | 118.8 (6) | C5A—C4A—C3A | 120.5 (6) |
C16—C4—C3 | 113.7 (7) | C16A—C4A—C3A | 112.8 (7) |
C5—C4—C6 | 58.9 (5) | C5A—C4A—C6A | 60.2 (5) |
C16—C4—C6 | 118.0 (7) | C16A—C4A—C6A | 117.5 (7) |
C3—C4—C6 | 117.7 (7) | C3A—C4A—C6A | 119.6 (6) |
C6—C5—C4 | 61.6 (5) | C4A—C5A—C6A | 61.3 (5) |
C6—C5—Br1 | 121.7 (5) | C4A—C5A—Br4 | 121.0 (5) |
C4—C5—Br1 | 121.1 (5) | C6A—C5A—Br4 | 118.9 (5) |
C6—C5—Br2 | 116.7 (6) | C4A—C5A—Br3 | 120.7 (5) |
C4—C5—Br2 | 119.3 (5) | C6A—C5A—Br3 | 119.2 (5) |
Br1—C5—Br2 | 109.6 (4) | Br4—C5A—Br3 | 109.0 (3) |
C5—C6—C7 | 121.8 (7) | C7A—C6A—C5A | 122.4 (6) |
C5—C6—C4 | 59.5 (5) | C7A—C6A—C4A | 124.3 (6) |
C7—C6—C4 | 124.2 (6) | C5A—C6A—C4A | 58.5 (5) |
C5—C6—H6 | 113.6 | C7A—C6A—H6A1 | 113.6 |
C7—C6—H6 | 113.6 | C5A—C6A—H6A1 | 113.6 |
C4—C6—H6 | 113.6 | C4A—C6A—H6A1 | 113.6 |
C12—C7—C6 | 116.5 (6) | C6A—C7A—C12A | 114.9 (6) |
C12—C7—C8 | 110.2 (6) | C6A—C7A—C8A | 112.2 (6) |
C6—C7—C8 | 110.8 (6) | C12A—C7A—C8A | 110.7 (6) |
C12—C7—H7 | 106.2 | C6A—C7A—H7A1 | 106.1 |
C6—C7—H7 | 106.2 | C12A—C7A—H7A1 | 106.1 |
C8—C7—H7 | 106.2 | C8A—C7A—H7A1 | 106.1 |
C14—C8—C15 | 108.8 (7) | C14A—C8A—C9A | 107.6 (6) |
C14—C8—C9 | 110.2 (7) | C14A—C8A—C15A | 107.6 (6) |
C15—C8—C9 | 109.0 (7) | C9A—C8A—C15A | 110.3 (6) |
C14—C8—C7 | 109.3 (6) | C14A—C8A—C7A | 108.5 (6) |
C15—C8—C7 | 107.4 (6) | C9A—C8A—C7A | 112.9 (6) |
C9—C8—C7 | 112.0 (6) | C15A—C8A—C7A | 109.7 (6) |
C10—C9—C8 | 118.1 (7) | C8A—C9A—C10A | 118.4 (7) |
C10—C9—H9A | 107.8 | C8A—C9A—H9A1 | 107.7 |
C8—C9—H9A | 107.8 | C10A—C9A—H9A1 | 107.7 |
C10—C9—H9B | 107.8 | C8A—C9A—H9A2 | 107.7 |
C8—C9—H9B | 107.8 | C10A—C9A—H9A2 | 107.7 |
H9A—C9—H9B | 107.1 | H9A1—C9A—H9A2 | 107.1 |
C9—C10—C11 | 113.4 (7) | C11A—C10A—C9A | 113.2 (7) |
C9—C10—H10A | 108.9 | C11A—C10A—H10C | 108.9 |
C11—C10—H10A | 108.9 | C9A—C10A—H10C | 108.9 |
C9—C10—H10B | 108.9 | C11A—C10A—H10D | 108.9 |
C11—C10—H10B | 108.9 | C9A—C10A—H10D | 108.9 |
H10A—C10—H10B | 107.7 | H10C—C10A—H10D | 107.7 |
C1—C11—C10 | 116.0 (7) | C10A—C11A—C1A | 116.8 (7) |
C1—C11—H11A | 108.3 | C10A—C11A—H11C | 108.1 |
C10—C11—H11A | 108.3 | C1A—C11A—H11C | 108.1 |
C1—C11—H11B | 108.3 | C10A—C11A—H11D | 108.1 |
C10—C11—H11B | 108.3 | C1A—C11A—H11D | 108.1 |
H11A—C11—H11B | 107.4 | H11C—C11A—H11D | 107.3 |
O1—C12—C7 | 118.5 (7) | O2—C12A—C7A | 120.0 (7) |
O1—C12—C1 | 120.7 (7) | O2—C12A—C1A | 119.0 (7) |
C7—C12—C1 | 120.6 (6) | C7A—C12A—C1A | 121.0 (6) |
C1—C13—H13A | 109.5 | C1A—C13A—H13D | 109.5 |
C1—C13—H13B | 109.5 | C1A—C13A—H13E | 109.5 |
H13A—C13—H13B | 109.5 | H13D—C13A—H13E | 109.5 |
C1—C13—H13C | 109.5 | C1A—C13A—H13F | 109.5 |
H13A—C13—H13C | 109.5 | H13D—C13A—H13F | 109.5 |
H13B—C13—H13C | 109.5 | H13E—C13A—H13F | 109.5 |
C8—C14—H14A | 109.5 | C8A—C14A—H14D | 109.5 |
C8—C14—H14B | 109.5 | C8A—C14A—H14E | 109.5 |
H14A—C14—H14B | 109.5 | H14D—C14A—H14E | 109.5 |
C8—C14—H14C | 109.5 | C8A—C14A—H14F | 109.5 |
H14A—C14—H14C | 109.5 | H14D—C14A—H14F | 109.5 |
H14B—C14—H14C | 109.5 | H14E—C14A—H14F | 109.5 |
C8—C15—H15A | 109.5 | C8A—C15A—H15D | 109.5 |
C8—C15—H15B | 109.5 | C8A—C15A—H15E | 109.5 |
H15A—C15—H15B | 109.5 | H15D—C15A—H15E | 109.5 |
C8—C15—H15C | 109.5 | C8A—C15A—H15F | 109.5 |
H15A—C15—H15C | 109.5 | H15D—C15A—H15F | 109.5 |
H15B—C15—H15C | 109.5 | H15E—C15A—H15F | 109.5 |
C4—C16—H16A | 109.5 | C4A—C16A—H16D | 109.5 |
C4—C16—H16B | 109.5 | C4A—C16A—H16E | 109.5 |
H16A—C16—H16B | 109.5 | H16D—C16A—H16E | 109.5 |
C4—C16—H16C | 109.5 | C4A—C16A—H16F | 109.5 |
H16A—C16—H16C | 109.5 | H16D—C16A—H16F | 109.5 |
H16B—C16—H16C | 109.5 | H16E—C16A—H16F | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C16H24Br2O |
Mr | 392.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.6550 (3), 9.4142 (4), 12.9389 (13) |
α, β, γ (°) | 86.008 (6), 83.921 (6), 89.511 (4) |
V (Å3) | 804.13 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.03 |
Crystal size (mm) | 0.38 × 0.11 × 0.10 |
Data collection | |
Diffractometer | Agilent Xcalibur (Eos, Gemini ultra) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.670, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11451, 6327, 5209 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.119, 1.01 |
No. of reflections | 6327 |
No. of parameters | 351 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.62 |
Absolute structure | Flack & Bernardinelli (2000), 3035 Friedel pairs |
Absolute structure parameter | −0.017 (15) |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Our work lies within the framework of the valorization of the most abundant essential oils in Morocco, such as the one from Cedrus atlantica. This oil is made up mainly (75%) of bicyclic sesquiterpenes hydrocarbons, among which is found β-himachalene (El Haib et al., 2011). The reactivity of this sesquiterpene and its derivatives has been studied extensively by our team in order to prepare new products having biological properties (El Jamili et al., 2002; Benharref et al., 2013; Oukhrib et al., 2013). Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against phytopathogen Botrytis cinerea (Daoubi et al., 2004). In this work we present the crystal structure of the title compound. The asymmetric unit contains two independent molecules with almost identical conformations (Fig. 1). Each molecule is built up from two fused seven-membered rings, one having a chair conformation as indicated by the total puckering amplitude QT = 0.8469 (8) Å and spherical polar angle θ = 38.29 (6)° with ϕ2 = 126.14 (8)°, and ϕ3 = -139.18 (6)°, while the other shows a screw boat conformation, with QT = 1.0407 (8) Å, θ = 76.80 (4)°, ϕ2 = 153.32 (4)° and ϕ3 = 115.21 (2)° (Cremer & Pople, 1975). Owing to the presence of Br atoms, the absolute configuration could be fully confirmed, by refining the Flack parameter (Flack & Bernardinelli, 2000) as C1(R), C4(R), C6(S) and C7(R).