organic compounds
1-[(1S,6R,7S,9R)-8,8-Dibromo-5,5,9-trimethyltricyclo[4.4.0.17,9]decan-1-yl]ethanone
aLaboratoire de Chimie Biomoléculaires, Substances Naturelles et Réactivité, URAC16, Faculté des Sciences, Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, BP 1014, Avenue Ibn Battouta, Rabat, Morocco
*Correspondence e-mail: berraho@uca.ma
The title compound, C16H24Br2O, was synthesized by three steps from β-himachalene (3,5,5,9-tetramethyl-2,4a,5,6,7,8-hexahydro-1H-benzocycloheptene), which was isolated from essential oil of the Atlas cedar cedrus atlantica. The contains two independent molecules with almost identical conformations. Each molecule is built up from two fused six-membered rings, one having a chair conformation and the other a boat conformation, and an additional three-membered ring arising from the reaction of himachalene with dibromocarbene. In the crystal, there are no significant intermolecular interactions present. The of the title compound was confirmed by resonance scattering.
CCDC reference: 990889
Related literature
For background to the reactivity and biological properties of β-himachalene, see: El Haib et al. (2011); El Jamili et al. (2002); Daoubi et al. (2004). For a related structure, see: Benharref et al. (2013). For ring see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell 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).
Supporting information
CCDC reference: 990889
10.1107/S1600536814005431/bt6967sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005431/bt6967Isup2.hkl
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 the 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-ethyle 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 70% (686 mg, 1.75 mmol). The title compound was recrystallized from its cyclohexane 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).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).C16H24Br2O | Dx = 1.596 Mg m−3 |
Mr = 392.17 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 6542 reflections |
a = 13.5013 (19) Å | θ = 2.4–26.4° |
b = 14.042 (2) Å | µ = 4.96 mm−1 |
c = 17.213 (3) Å | T = 298 K |
V = 3263.3 (8) Å3 | Block, colourless |
Z = 8 | 0.5 × 0.03 × 0.03 mm |
F(000) = 1584 |
Bruker X8 APEX CCD area-detector diffractometer | 6542 independent reflections |
Radiation source: fine-focus sealed tube | 5262 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −15→16 |
Tmin = 0.557, Tmax = 0.747 | k = −12→17 |
22468 measured reflections | l = −17→21 |
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0104P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6540 reflections | Δρmax = 0.27 e Å−3 |
351 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Absolute structure: Flack & Bernardinelli (2000) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.005 (8) |
C16H24Br2O | V = 3263.3 (8) Å3 |
Mr = 392.17 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.5013 (19) Å | µ = 4.96 mm−1 |
b = 14.042 (2) Å | T = 298 K |
c = 17.213 (3) Å | 0.5 × 0.03 × 0.03 mm |
Bruker X8 APEX CCD area-detector diffractometer | 6542 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 5262 reflections with I > 2σ(I) |
Tmin = 0.557, Tmax = 0.747 | Rint = 0.040 |
22468 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.060 | Δρmax = 0.27 e Å−3 |
S = 1.02 | Δρmin = −0.39 e Å−3 |
6540 reflections | Absolute structure: Flack & Bernardinelli (2000) |
351 parameters | Absolute structure parameter: −0.005 (8) |
0 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 > 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 | 0.7516 (2) | 1.0732 (2) | −0.03701 (18) | 0.0342 (8) | |
C2 | 0.6483 (3) | 1.1166 (3) | −0.0456 (2) | 0.0518 (10) | |
H2A | 0.6508 | 1.1658 | −0.0851 | 0.062* | |
H2B | 0.6032 | 1.0676 | −0.0636 | 0.062* | |
C3 | 0.6068 (3) | 1.1596 (3) | 0.0284 (2) | 0.0628 (12) | |
H3A | 0.6465 | 1.2142 | 0.0431 | 0.075* | |
H3B | 0.5398 | 1.1815 | 0.0189 | 0.075* | |
C4 | 0.6060 (3) | 1.0889 (3) | 0.0941 (2) | 0.0544 (10) | |
H4A | 0.5600 | 1.0379 | 0.0819 | 0.065* | |
H4B | 0.5827 | 1.1202 | 0.1409 | 0.065* | |
C5 | 0.7090 (2) | 1.0460 (3) | 0.10960 (19) | 0.0394 (9) | |
C6 | 0.7513 (2) | 1.0035 (2) | 0.03386 (15) | 0.0250 (7) | |
H6 | 0.8204 | 0.9864 | 0.0442 | 0.030* | |
C7 | 0.6976 (2) | 0.9125 (2) | 0.01156 (17) | 0.0298 (8) | |
H7 | 0.6264 | 0.9124 | 0.0228 | 0.036* | |
C8 | 0.7455 (2) | 0.8170 (2) | 0.01354 (18) | 0.0329 (8) | |
C9 | 0.7266 (2) | 0.8636 (2) | −0.06406 (17) | 0.0320 (8) | |
C10 | 0.8094 (2) | 0.9159 (2) | −0.1044 (2) | 0.0393 (9) | |
H10A | 0.8216 | 0.8877 | −0.1549 | 0.047* | |
H10B | 0.8696 | 0.9114 | −0.0739 | 0.047* | |
C11 | 0.7797 (3) | 1.0195 (3) | −0.11368 (18) | 0.0435 (9) | |
H11A | 0.7235 | 1.0225 | −0.1488 | 0.052* | |
H11B | 0.8340 | 1.0532 | −0.1382 | 0.052* | |
C12 | 0.8323 (3) | 1.1502 (3) | −0.0304 (2) | 0.0452 (9) | |
C13 | 0.9368 (3) | 1.1193 (3) | −0.0122 (2) | 0.0568 (11) | |
H13A | 0.9824 | 1.1549 | −0.0437 | 0.085* | |
H13B | 0.9439 | 1.0526 | −0.0231 | 0.085* | |
H13C | 0.9506 | 1.1309 | 0.0417 | 0.085* | |
C14 | 0.7777 (3) | 1.1229 (3) | 0.1434 (2) | 0.0547 (11) | |
H14A | 0.7492 | 1.1479 | 0.1902 | 0.082* | |
H14B | 0.7855 | 1.1734 | 0.1062 | 0.082* | |
H14C | 0.8412 | 1.0955 | 0.1547 | 0.082* | |
C15 | 0.6990 (3) | 0.9672 (3) | 0.1702 (2) | 0.0553 (11) | |
H15A | 0.6551 | 0.9188 | 0.1512 | 0.083* | |
H15B | 0.6728 | 0.9935 | 0.2175 | 0.083* | |
H15C | 0.7629 | 0.9398 | 0.1802 | 0.083* | |
C16 | 0.6480 (3) | 0.8239 (3) | −0.1165 (2) | 0.0517 (10) | |
H16A | 0.6738 | 0.7697 | −0.1438 | 0.077* | |
H16B | 0.6282 | 0.8717 | −0.1532 | 0.077* | |
H16C | 0.5918 | 0.8049 | −0.0861 | 0.077* | |
Br1 | 0.87872 (2) | 0.80148 (3) | 0.05270 (2) | 0.04524 (10) | |
Br2 | 0.66521 (3) | 0.71109 (3) | 0.04601 (3) | 0.05635 (12) | |
O1 | 0.8142 (2) | 1.23284 (19) | −0.04537 (18) | 0.0746 (9) | |
C17 | 0.8403 (2) | 0.5321 (2) | 0.30776 (18) | 0.0353 (8) | |
C18 | 0.9200 (3) | 0.4590 (3) | 0.3290 (2) | 0.0536 (11) | |
H18A | 0.9638 | 0.4872 | 0.3674 | 0.064* | |
H18B | 0.8881 | 0.4046 | 0.3531 | 0.064* | |
C19 | 0.9822 (3) | 0.4239 (3) | 0.2615 (2) | 0.0645 (12) | |
H19A | 1.0214 | 0.4762 | 0.2412 | 0.077* | |
H19B | 1.0274 | 0.3750 | 0.2796 | 0.077* | |
C20 | 0.9176 (3) | 0.3837 (3) | 0.1974 (2) | 0.0532 (10) | |
H20A | 0.8836 | 0.3276 | 0.2166 | 0.064* | |
H20B | 0.9593 | 0.3643 | 0.1543 | 0.064* | |
C21 | 0.8409 (2) | 0.4558 (2) | 0.16839 (19) | 0.0358 (8) | |
C22 | 0.7784 (2) | 0.4940 (2) | 0.23762 (17) | 0.0297 (7) | |
H22 | 0.7397 | 0.5479 | 0.2178 | 0.036* | |
C23 | 0.7047 (2) | 0.4204 (2) | 0.26590 (18) | 0.0319 (8) | |
H23 | 0.7282 | 0.3544 | 0.2648 | 0.038* | |
C24 | 0.5956 (2) | 0.4328 (2) | 0.25512 (19) | 0.0365 (8) | |
C25 | 0.6391 (2) | 0.4460 (2) | 0.33457 (19) | 0.0331 (8) | |
C26 | 0.6622 (2) | 0.5442 (3) | 0.3653 (2) | 0.0411 (9) | |
H26A | 0.6258 | 0.5554 | 0.4130 | 0.049* | |
H26B | 0.6426 | 0.5920 | 0.3276 | 0.049* | |
C27 | 0.7733 (2) | 0.5508 (3) | 0.38072 (18) | 0.0437 (9) | |
H27A | 0.7906 | 0.5052 | 0.4208 | 0.052* | |
H27B | 0.7880 | 0.6139 | 0.4007 | 0.052* | |
C28 | 0.8851 (3) | 0.6296 (3) | 0.2910 (2) | 0.0501 (10) | |
C29 | 0.8180 (3) | 0.7092 (3) | 0.2652 (2) | 0.0614 (11) | |
H29A | 0.8507 | 0.7691 | 0.2729 | 0.092* | |
H29B | 0.7580 | 0.7077 | 0.2951 | 0.092* | |
H29C | 0.8024 | 0.7014 | 0.2112 | 0.092* | |
C30 | 0.8932 (3) | 0.5378 (3) | 0.1257 (2) | 0.0517 (10) | |
H30A | 0.9371 | 0.5699 | 0.1609 | 0.078* | |
H30B | 0.8446 | 0.5820 | 0.1067 | 0.078* | |
H30C | 0.9305 | 0.5128 | 0.0828 | 0.078* | |
C31 | 0.7714 (3) | 0.4076 (3) | 0.1084 (2) | 0.0541 (11) | |
H31A | 0.8092 | 0.3880 | 0.0640 | 0.081* | |
H31B | 0.7213 | 0.4521 | 0.0925 | 0.081* | |
H31C | 0.7406 | 0.3530 | 0.1317 | 0.081* | |
C32 | 0.6193 (3) | 0.3715 (3) | 0.3973 (2) | 0.0520 (10) | |
H32A | 0.5559 | 0.3833 | 0.4206 | 0.078* | |
H32B | 0.6699 | 0.3751 | 0.4364 | 0.078* | |
H32C | 0.6196 | 0.3091 | 0.3744 | 0.078* | |
Br3 | 0.54217 (3) | 0.53917 (3) | 0.19802 (2) | 0.04941 (11) | |
Br4 | 0.51892 (3) | 0.32022 (3) | 0.23283 (2) | 0.06195 (13) | |
O2 | 0.9721 (2) | 0.6461 (2) | 0.30335 (19) | 0.0872 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0425 (19) | 0.0318 (19) | 0.0284 (19) | −0.0034 (16) | −0.0046 (16) | 0.0053 (15) |
C2 | 0.060 (2) | 0.041 (2) | 0.054 (2) | 0.0080 (18) | −0.018 (2) | 0.009 (2) |
C3 | 0.048 (2) | 0.052 (3) | 0.089 (3) | 0.025 (2) | −0.011 (2) | −0.007 (2) |
C4 | 0.051 (2) | 0.049 (3) | 0.063 (3) | 0.0153 (19) | 0.011 (2) | −0.014 (2) |
C5 | 0.044 (2) | 0.040 (2) | 0.0341 (19) | 0.0017 (17) | 0.0072 (16) | −0.0049 (18) |
C6 | 0.0288 (15) | 0.0211 (16) | 0.0249 (17) | 0.0002 (13) | 0.0003 (13) | 0.0007 (13) |
C7 | 0.0280 (17) | 0.030 (2) | 0.0310 (18) | 0.0021 (14) | 0.0019 (14) | −0.0011 (14) |
C8 | 0.0285 (16) | 0.0267 (19) | 0.0435 (19) | −0.0038 (15) | −0.0005 (15) | 0.0008 (15) |
C9 | 0.0354 (18) | 0.0330 (19) | 0.0277 (18) | −0.0013 (15) | 0.0005 (15) | −0.0085 (15) |
C10 | 0.047 (2) | 0.041 (2) | 0.0297 (19) | −0.0038 (16) | 0.0077 (16) | −0.0060 (16) |
C11 | 0.056 (2) | 0.043 (2) | 0.0315 (19) | −0.0121 (18) | 0.0011 (17) | 0.0059 (17) |
C12 | 0.069 (3) | 0.034 (2) | 0.033 (2) | −0.0144 (19) | 0.0010 (19) | 0.0014 (17) |
C13 | 0.054 (2) | 0.052 (3) | 0.064 (3) | −0.024 (2) | 0.006 (2) | 0.001 (2) |
C14 | 0.067 (3) | 0.055 (3) | 0.042 (2) | −0.004 (2) | 0.003 (2) | −0.0179 (19) |
C15 | 0.077 (3) | 0.060 (3) | 0.0290 (19) | −0.002 (2) | 0.0176 (19) | −0.001 (2) |
C16 | 0.054 (2) | 0.047 (2) | 0.054 (2) | −0.0055 (19) | −0.0146 (19) | −0.0152 (19) |
Br1 | 0.04248 (19) | 0.0378 (2) | 0.0554 (2) | 0.00669 (16) | −0.01088 (17) | 0.00135 (19) |
Br2 | 0.0576 (2) | 0.0342 (2) | 0.0772 (3) | −0.01247 (18) | 0.0117 (2) | 0.0086 (2) |
O1 | 0.108 (2) | 0.0304 (17) | 0.086 (2) | −0.0148 (15) | −0.0083 (19) | 0.0137 (15) |
C17 | 0.0281 (16) | 0.042 (2) | 0.0356 (18) | −0.0008 (16) | −0.0081 (15) | 0.0005 (17) |
C18 | 0.045 (2) | 0.069 (3) | 0.047 (2) | 0.005 (2) | −0.0138 (18) | 0.007 (2) |
C19 | 0.041 (2) | 0.077 (3) | 0.075 (3) | 0.023 (2) | −0.003 (2) | 0.012 (2) |
C20 | 0.052 (2) | 0.046 (2) | 0.061 (2) | 0.0181 (19) | 0.015 (2) | 0.002 (2) |
C21 | 0.0389 (18) | 0.031 (2) | 0.0372 (18) | 0.0057 (16) | 0.0062 (16) | −0.0015 (16) |
C22 | 0.0327 (17) | 0.0252 (18) | 0.0312 (17) | 0.0045 (14) | 0.0006 (14) | 0.0011 (14) |
C23 | 0.0324 (17) | 0.0258 (19) | 0.0374 (19) | 0.0012 (14) | −0.0019 (15) | 0.0062 (15) |
C24 | 0.0353 (18) | 0.0303 (19) | 0.044 (2) | −0.0014 (15) | −0.0059 (16) | 0.0011 (16) |
C25 | 0.0297 (17) | 0.034 (2) | 0.0351 (18) | 0.0026 (15) | 0.0022 (14) | 0.0030 (16) |
C26 | 0.045 (2) | 0.045 (2) | 0.0334 (19) | 0.0048 (18) | 0.0052 (16) | −0.0004 (17) |
C27 | 0.052 (2) | 0.045 (2) | 0.034 (2) | −0.0074 (18) | −0.0054 (17) | 0.0005 (17) |
C28 | 0.049 (2) | 0.054 (3) | 0.047 (2) | −0.018 (2) | −0.0040 (19) | −0.0065 (19) |
C29 | 0.086 (3) | 0.036 (2) | 0.062 (2) | −0.009 (2) | −0.003 (2) | 0.004 (2) |
C30 | 0.051 (2) | 0.053 (3) | 0.051 (2) | 0.000 (2) | 0.0137 (19) | 0.012 (2) |
C31 | 0.061 (2) | 0.062 (3) | 0.039 (2) | 0.001 (2) | 0.006 (2) | −0.015 (2) |
C32 | 0.055 (2) | 0.054 (2) | 0.047 (2) | 0.006 (2) | 0.009 (2) | 0.018 (2) |
Br3 | 0.03866 (19) | 0.0577 (3) | 0.0519 (2) | 0.00694 (18) | −0.00959 (18) | 0.01018 (19) |
Br4 | 0.0534 (2) | 0.0531 (3) | 0.0794 (3) | −0.0209 (2) | −0.0020 (2) | −0.0105 (2) |
O2 | 0.0579 (18) | 0.085 (2) | 0.119 (3) | −0.0333 (18) | −0.020 (2) | 0.004 (2) |
C1—C2 | 1.529 (5) | C17—C28 | 1.524 (5) |
C1—C12 | 1.540 (5) | C17—C18 | 1.532 (5) |
C1—C6 | 1.564 (4) | C17—C22 | 1.563 (4) |
C1—C11 | 1.567 (4) | C17—C27 | 1.570 (5) |
C2—C3 | 1.516 (5) | C18—C19 | 1.516 (5) |
C2—H2A | 0.9700 | C18—H18A | 0.9700 |
C2—H2B | 0.9700 | C18—H18B | 0.9700 |
C3—C4 | 1.506 (5) | C19—C20 | 1.515 (5) |
C3—H3A | 0.9700 | C19—H19A | 0.9700 |
C3—H3B | 0.9700 | C19—H19B | 0.9700 |
C4—C5 | 1.539 (5) | C20—C21 | 1.531 (4) |
C4—H4A | 0.9700 | C20—H20A | 0.9700 |
C4—H4B | 0.9700 | C20—H20B | 0.9700 |
C5—C15 | 1.527 (5) | C21—C30 | 1.538 (4) |
C5—C14 | 1.537 (5) | C21—C31 | 1.550 (5) |
C5—C6 | 1.543 (4) | C21—C22 | 1.556 (4) |
C6—C7 | 1.519 (4) | C22—C23 | 1.515 (4) |
C6—H6 | 0.9800 | C22—H22 | 0.9800 |
C7—C8 | 1.489 (4) | C23—C24 | 1.496 (4) |
C7—C9 | 1.523 (4) | C23—C25 | 1.520 (4) |
C7—H7 | 0.9800 | C23—H23 | 0.9800 |
C8—C9 | 1.510 (4) | C24—C25 | 1.500 (4) |
C8—Br2 | 1.924 (3) | C24—Br4 | 1.928 (3) |
C8—Br1 | 1.933 (3) | C24—Br3 | 1.928 (3) |
C9—C16 | 1.501 (4) | C25—C26 | 1.509 (5) |
C9—C10 | 1.506 (4) | C25—C32 | 1.528 (4) |
C10—C11 | 1.517 (5) | C26—C27 | 1.526 (5) |
C10—H10A | 0.9700 | C26—H26A | 0.9700 |
C10—H10B | 0.9700 | C26—H26B | 0.9700 |
C11—H11A | 0.9700 | C27—H27A | 0.9700 |
C11—H11B | 0.9700 | C27—H27B | 0.9700 |
C12—O1 | 1.213 (4) | C28—O2 | 1.215 (4) |
C12—C13 | 1.509 (5) | C28—C29 | 1.506 (5) |
C13—H13A | 0.9600 | C29—H29A | 0.9600 |
C13—H13B | 0.9600 | C29—H29B | 0.9600 |
C13—H13C | 0.9600 | C29—H29C | 0.9600 |
C14—H14A | 0.9600 | C30—H30A | 0.9600 |
C14—H14B | 0.9600 | C30—H30B | 0.9600 |
C14—H14C | 0.9600 | C30—H30C | 0.9600 |
C15—H15A | 0.9600 | C31—H31A | 0.9600 |
C15—H15B | 0.9600 | C31—H31B | 0.9600 |
C15—H15C | 0.9600 | C31—H31C | 0.9600 |
C16—H16A | 0.9600 | C32—H32A | 0.9600 |
C16—H16B | 0.9600 | C32—H32B | 0.9600 |
C16—H16C | 0.9600 | C32—H32C | 0.9600 |
C2—C1—C12 | 111.9 (3) | C28—C17—C18 | 111.5 (3) |
C2—C1—C6 | 108.8 (3) | C28—C17—C22 | 112.0 (3) |
C12—C1—C6 | 112.5 (3) | C18—C17—C22 | 109.3 (3) |
C2—C1—C11 | 109.4 (3) | C28—C17—C27 | 103.3 (3) |
C12—C1—C11 | 103.3 (3) | C18—C17—C27 | 109.0 (3) |
C6—C1—C11 | 110.9 (3) | C22—C17—C27 | 111.6 (2) |
C3—C2—C1 | 114.5 (3) | C19—C18—C17 | 115.1 (3) |
C3—C2—H2A | 108.6 | C19—C18—H18A | 108.5 |
C1—C2—H2A | 108.6 | C17—C18—H18A | 108.5 |
C3—C2—H2B | 108.6 | C19—C18—H18B | 108.5 |
C1—C2—H2B | 108.6 | C17—C18—H18B | 108.5 |
H2A—C2—H2B | 107.6 | H18A—C18—H18B | 107.5 |
C4—C3—C2 | 111.8 (3) | C20—C19—C18 | 111.1 (3) |
C4—C3—H3A | 109.3 | C20—C19—H19A | 109.4 |
C2—C3—H3A | 109.3 | C18—C19—H19A | 109.4 |
C4—C3—H3B | 109.3 | C20—C19—H19B | 109.4 |
C2—C3—H3B | 109.3 | C18—C19—H19B | 109.4 |
H3A—C3—H3B | 107.9 | H19A—C19—H19B | 108.0 |
C3—C4—C5 | 112.4 (3) | C19—C20—C21 | 112.4 (3) |
C3—C4—H4A | 109.1 | C19—C20—H20A | 109.1 |
C5—C4—H4A | 109.1 | C21—C20—H20A | 109.1 |
C3—C4—H4B | 109.1 | C19—C20—H20B | 109.1 |
C5—C4—H4B | 109.1 | C21—C20—H20B | 109.1 |
H4A—C4—H4B | 107.8 | H20A—C20—H20B | 107.9 |
C15—C5—C14 | 107.7 (3) | C20—C21—C30 | 109.9 (3) |
C15—C5—C4 | 108.8 (3) | C20—C21—C31 | 109.8 (3) |
C14—C5—C4 | 109.6 (3) | C30—C21—C31 | 106.6 (3) |
C15—C5—C6 | 109.3 (3) | C20—C21—C22 | 110.2 (3) |
C14—C5—C6 | 111.6 (3) | C30—C21—C22 | 110.9 (3) |
C4—C5—C6 | 109.8 (3) | C31—C21—C22 | 109.4 (3) |
C7—C6—C5 | 111.2 (3) | C23—C22—C21 | 111.5 (3) |
C7—C6—C1 | 109.3 (2) | C23—C22—C17 | 109.7 (2) |
C5—C6—C1 | 114.7 (3) | C21—C22—C17 | 114.8 (2) |
C7—C6—H6 | 107.1 | C23—C22—H22 | 106.8 |
C5—C6—H6 | 107.1 | C21—C22—H22 | 106.8 |
C1—C6—H6 | 107.1 | C17—C22—H22 | 106.8 |
C8—C7—C6 | 123.0 (2) | C24—C23—C22 | 121.8 (3) |
C8—C7—C9 | 60.1 (2) | C24—C23—C25 | 59.7 (2) |
C6—C7—C9 | 118.2 (3) | C22—C23—C25 | 118.1 (3) |
C8—C7—H7 | 114.8 | C24—C23—H23 | 115.3 |
C6—C7—H7 | 114.8 | C22—C23—H23 | 115.3 |
C9—C7—H7 | 114.8 | C25—C23—H23 | 115.3 |
C7—C8—C9 | 61.0 (2) | C23—C24—C25 | 61.0 (2) |
C7—C8—Br2 | 117.2 (2) | C23—C24—Br4 | 117.3 (2) |
C9—C8—Br2 | 119.8 (2) | C25—C24—Br4 | 119.5 (2) |
C7—C8—Br1 | 120.9 (2) | C23—C24—Br3 | 121.5 (2) |
C9—C8—Br1 | 121.0 (2) | C25—C24—Br3 | 121.0 (2) |
Br2—C8—Br1 | 109.63 (15) | Br4—C24—Br3 | 109.45 (15) |
C16—C9—C10 | 115.4 (3) | C24—C25—C26 | 120.9 (3) |
C16—C9—C8 | 119.4 (3) | C24—C25—C23 | 59.4 (2) |
C10—C9—C8 | 119.5 (3) | C26—C25—C23 | 111.6 (3) |
C16—C9—C7 | 120.0 (3) | C24—C25—C32 | 119.4 (3) |
C10—C9—C7 | 111.4 (3) | C26—C25—C32 | 114.5 (3) |
C8—C9—C7 | 58.8 (2) | C23—C25—C32 | 119.3 (3) |
C9—C10—C11 | 108.6 (3) | C25—C26—C27 | 108.7 (3) |
C9—C10—H10A | 110.0 | C25—C26—H26A | 110.0 |
C11—C10—H10A | 110.0 | C27—C26—H26A | 110.0 |
C9—C10—H10B | 110.0 | C25—C26—H26B | 110.0 |
C11—C10—H10B | 110.0 | C27—C26—H26B | 110.0 |
H10A—C10—H10B | 108.3 | H26A—C26—H26B | 108.3 |
C10—C11—C1 | 115.9 (3) | C26—C27—C17 | 114.6 (3) |
C10—C11—H11A | 108.3 | C26—C27—H27A | 108.6 |
C1—C11—H11A | 108.3 | C17—C27—H27A | 108.6 |
C10—C11—H11B | 108.3 | C26—C27—H27B | 108.6 |
C1—C11—H11B | 108.3 | C17—C27—H27B | 108.6 |
H11A—C11—H11B | 107.4 | H27A—C27—H27B | 107.6 |
O1—C12—C13 | 120.5 (4) | O2—C28—C29 | 119.4 (4) |
O1—C12—C1 | 120.9 (4) | O2—C28—C17 | 121.5 (4) |
C13—C12—C1 | 118.4 (3) | C29—C28—C17 | 118.9 (3) |
C12—C13—H13A | 109.5 | C28—C29—H29A | 109.5 |
C12—C13—H13B | 109.5 | C28—C29—H29B | 109.5 |
H13A—C13—H13B | 109.5 | H29A—C29—H29B | 109.5 |
C12—C13—H13C | 109.5 | C28—C29—H29C | 109.5 |
H13A—C13—H13C | 109.5 | H29A—C29—H29C | 109.5 |
H13B—C13—H13C | 109.5 | H29B—C29—H29C | 109.5 |
C5—C14—H14A | 109.5 | C21—C30—H30A | 109.5 |
C5—C14—H14B | 109.5 | C21—C30—H30B | 109.5 |
H14A—C14—H14B | 109.5 | H30A—C30—H30B | 109.5 |
C5—C14—H14C | 109.5 | C21—C30—H30C | 109.5 |
H14A—C14—H14C | 109.5 | H30A—C30—H30C | 109.5 |
H14B—C14—H14C | 109.5 | H30B—C30—H30C | 109.5 |
C5—C15—H15A | 109.5 | C21—C31—H31A | 109.5 |
C5—C15—H15B | 109.5 | C21—C31—H31B | 109.5 |
H15A—C15—H15B | 109.5 | H31A—C31—H31B | 109.5 |
C5—C15—H15C | 109.5 | C21—C31—H31C | 109.5 |
H15A—C15—H15C | 109.5 | H31A—C31—H31C | 109.5 |
H15B—C15—H15C | 109.5 | H31B—C31—H31C | 109.5 |
C9—C16—H16A | 109.5 | C25—C32—H32A | 109.5 |
C9—C16—H16B | 109.5 | C25—C32—H32B | 109.5 |
H16A—C16—H16B | 109.5 | H32A—C32—H32B | 109.5 |
C9—C16—H16C | 109.5 | C25—C32—H32C | 109.5 |
H16A—C16—H16C | 109.5 | H32A—C32—H32C | 109.5 |
H16B—C16—H16C | 109.5 | H32B—C32—H32C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C16H24Br2O |
Mr | 392.17 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 13.5013 (19), 14.042 (2), 17.213 (3) |
V (Å3) | 3263.3 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.96 |
Crystal size (mm) | 0.5 × 0.03 × 0.03 |
Data collection | |
Diffractometer | Bruker X8 APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.557, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22468, 6542, 5262 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.060, 1.02 |
No. of reflections | 6540 |
No. of parameters | 351 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.39 |
Absolute structure | Flack & Bernardinelli (2000) |
Absolute structure parameter | −0.005 (8) |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).
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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The bicyclic sesquiterpene β-himachalene is the main constituent of the essential oil of the Atlas cedar (Cedrus atlantica) (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). 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 paper we present the crystal structure of the title compound, (1S, 6R,7S, 9R)-1-acetyl-8,8-dibromo-5,5,9- trimethyltricyclo[4.4.0,17,9]decane. The asymmetric unit of the title compound contains two independent molecules of similar geometry (Fig. 1). Each molecule contains two fused six-membered rings, which are fused to a three-membered ring as shown in Fig.1. In both molecules, one of the six-membered ring has a chair conformation as indicated by the total puckering amplitude QT = 0.543 (4) Å and spherical polar angle θ2 = 177.7 (4)° with ϕ2 = 1(11)°, whereas the other six-membered ring displays a boat conformation with QT = 0.725 (3) Å, θ2 = 92.2 (2)° (Cremer & Pople, 1975). Owing to the presence of Br atoms, the absolute configuration could be fully confirmed, by refining the Flack parameter as C1(S), C6(R), C7(S) and C9(R).