Literature DB >> 23476222

(1S,3R,8R)-2,2-Dibromo-10-bromo-methyl-3,7,7-trimethyl-tricyclo-[6.4.0.0(1,3)]dodec-9-ene.

Abdelouahd Oukhrib¹, Ahmed Benharref, Mohamed Saadi, Jean-Claude Daran, Moha Berraho.

Abstract

The title compound, C16H23Br3, 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 the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an additional three-membered ring from the reaction of himachalene with dibromo-carbene. The six-membered ring has an envelope conformation (the flap atom being the C atom shared with the three-membered ring, whereas the seven-membered ring displays a screw boat conformation; the dihedral angle between the rings (defined by the near coplanar atoms) is 56.5 (2)°.

Entities: CellLine Chemical Disease Species

Year: 2012 PMID： 23476222 PMCID： PMC3588986 DOI： 10.1107/S1600536812046430

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the isolation of β-himachalene, see: Joseph & Dev (1968 ▶); Plattier & Teiseire (1974 ▶). For the reactivity of this sesquiterpene, see: Lassaba et al. (1997 ▶); Chekroun et al. (2000 ▶); El Jamili et al. (2002 ▶); Sbai et al. (2002 ▶); Dakir et al. (2004 ▶); Benharref et al. (2010 ▶). For its biological activity, see: Daoubi et al. (2004 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H23Br3 M = 455.07 Orthorhombic, a = 9.2614 (5) Å b = 12.8215 (8) Å c = 14.3966 (11) Å V = 1709.52 (19) Å3 Z = 4 Mo Kα radiation μ = 7.07 mm−1 T = 180 K 0.49 × 0.31 × 0.08 mm

Data collection

Agilent Xcalibur (Sapphire1, long nozzle) diffractometer Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.135, T max = 1.000 9721 measured reflections 3461 independent reflections 3121 reflections with I > 2σ(I) R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.034 wR(F 2) = 0.075 S = 1.04 3461 reflections 176 parameters H-atom parameters constrained Δρmax = 0.66 e Å−3 Δρmin = −0.55 e Å−3 Absolute structure: Flack (1983 ▶), 1460 Friedel pairs Flack parameter: 0.012 (16) Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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 ▶). Click here for additional data file. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046430/im2411sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046430/im2411Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536812046430/im2411Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₆H₂₃Br₃	F(000) = 896
M_r = 455.07	D_x = 1.768 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3461 reflections
a = 9.2614 (5) Å	θ = 3.1–26.4°
b = 12.8215 (8) Å	µ = 7.07 mm⁻¹
c = 14.3966 (11) Å	T = 180 K
V = 1709.52 (19) Å³	Prism, colourless
Z = 4	0.49 × 0.31 × 0.08 mm

Agilent Xcalibur (Sapphire1, long nozzle) diffractometer	3461 independent reflections
Graphite monochromator	3121 reflections with I > 2σ(I)
Detector resolution: 8.2632 pixels mm^-1	R_int = 0.049
ω scans	θ_max = 26.4°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	h = −11→11
T_min = 0.135, T_max = 1.000	k = −16→15
9721 measured reflections	l = −15→17

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0387P)² + 0.0947P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.075	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.66 e Å⁻³
3461 reflections	Δρ_min = −0.55 e Å⁻³
176 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0034 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1460 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.012 (16)

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent, 2010)

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	U_iso*/U_eq
C13	0.9676 (5)	0.5913 (4)	0.4115 (3)	0.0283 (12)
H13A	0.9119	0.6220	0.4606	0.042*
H13B	0.9989	0.5230	0.4299	0.042*
H13C	0.9093	0.5861	0.3565	0.042*
C1	1.1613 (4)	0.6641 (3)	0.2929 (3)	0.0110 (8)
C2	1.0820 (5)	0.7571 (3)	0.3330 (3)	0.0164 (9)
C3	1.0980 (5)	0.6589 (3)	0.3916 (3)	0.0160 (9)
C4	1.2066 (6)	0.6600 (3)	0.4707 (3)	0.0251 (11)
H4A	1.1567	0.6746	0.5285	0.030*
H4B	1.2760	0.7154	0.4602	0.030*
C5	1.2867 (6)	0.5560 (4)	0.4793 (3)	0.0280 (12)
H5A	1.2275	0.5082	0.5151	0.034*
H5B	1.3752	0.5675	0.5139	0.034*
C6	1.3251 (5)	0.5037 (3)	0.3864 (3)	0.0233 (10)
H6A	1.2356	0.4818	0.3573	0.028*
H6B	1.3798	0.4410	0.4001	0.028*
C7	1.4112 (5)	0.5671 (3)	0.3143 (3)	0.0196 (10)
C8	1.3273 (4)	0.6703 (3)	0.2837 (3)	0.0146 (8)
H8	1.3594	0.7261	0.3254	0.018*
C9	1.3668 (4)	0.7037 (3)	0.1861 (3)	0.0186 (10)
H9	1.4614	0.7250	0.1756	0.022*
C10	1.2776 (5)	0.7050 (3)	0.1147 (3)	0.0158 (9)
C11	1.1229 (5)	0.6707 (3)	0.1223 (3)	0.0161 (9)
H11A	1.0988	0.6284	0.0687	0.019*
H11B	1.0611	0.7318	0.1214	0.019*
C12	1.0923 (4)	0.6086 (3)	0.2101 (3)	0.0139 (8)
H12A	1.1318	0.5389	0.2041	0.017*
H12B	0.9889	0.6028	0.2195	0.017*
C14	1.5566 (5)	0.6008 (4)	0.3559 (4)	0.0427 (15)
H14A	1.6119	0.5401	0.3719	0.064*
H14B	1.5400	0.6419	0.4106	0.064*
H14C	1.6088	0.6415	0.3111	0.064*
C15	1.4416 (6)	0.4939 (4)	0.2310 (3)	0.0328 (13)
H15A	1.4933	0.4336	0.2521	0.049*
H15B	1.4985	0.5303	0.1856	0.049*
H15C	1.3518	0.4727	0.2036	0.049*
C16	1.3330 (6)	0.7378 (4)	0.0200 (3)	0.0286 (11)
H16A	1.3172	0.6817	−0.0241	0.034*
H16B	1.4361	0.7506	0.0236	0.034*
Br1	0.89111 (5)	0.79294 (4)	0.28578 (3)	0.02481 (13)
Br2	1.17768 (6)	0.88596 (3)	0.36490 (3)	0.02729 (14)
Br3	1.23443 (7)	0.86490 (4)	−0.02407 (4)	0.04212 (18)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C13	0.030 (3)	0.028 (3)	0.027 (3)	−0.002 (2)	0.016 (2)	0.009 (2)
C1	0.0118 (18)	0.0124 (18)	0.0088 (19)	−0.0009 (16)	0.0025 (16)	0.0028 (17)
C2	0.016 (2)	0.018 (2)	0.015 (2)	−0.0061 (18)	0.0004 (17)	−0.0025 (18)
C3	0.020 (2)	0.015 (2)	0.013 (2)	0.0007 (19)	0.0037 (18)	−0.0005 (17)
C4	0.047 (3)	0.021 (2)	0.007 (2)	0.003 (2)	−0.005 (2)	−0.0004 (18)
C5	0.046 (3)	0.026 (2)	0.013 (2)	0.008 (2)	−0.005 (2)	0.004 (2)
C6	0.032 (3)	0.019 (2)	0.020 (3)	0.007 (2)	−0.001 (2)	0.0051 (18)
C7	0.012 (2)	0.021 (2)	0.026 (3)	0.0040 (19)	−0.0045 (18)	0.0045 (19)
C8	0.0139 (19)	0.015 (2)	0.015 (2)	−0.0022 (17)	−0.0019 (19)	0.0036 (18)
C9	0.010 (2)	0.019 (2)	0.026 (3)	−0.0017 (18)	0.0026 (16)	0.007 (2)
C10	0.021 (2)	0.0145 (19)	0.012 (2)	0.0047 (19)	0.0061 (17)	0.0031 (17)
C11	0.020 (2)	0.018 (2)	0.010 (2)	−0.0006 (18)	−0.0006 (17)	−0.0011 (17)
C12	0.0130 (19)	0.0158 (19)	0.013 (2)	0.0010 (18)	0.0010 (18)	−0.0032 (18)
C14	0.020 (3)	0.042 (3)	0.066 (4)	−0.003 (2)	−0.022 (3)	0.018 (3)
C15	0.029 (3)	0.030 (3)	0.040 (3)	0.015 (2)	0.009 (2)	0.010 (2)
C16	0.033 (3)	0.030 (3)	0.023 (3)	0.010 (2)	0.011 (2)	0.012 (2)
Br1	0.0178 (2)	0.0254 (2)	0.0312 (3)	0.0070 (2)	0.0019 (2)	−0.0009 (2)
Br2	0.0377 (3)	0.0147 (2)	0.0295 (3)	−0.0026 (2)	−0.0072 (2)	−0.0044 (2)
Br3	0.0431 (3)	0.0365 (3)	0.0467 (4)	0.0046 (3)	0.0065 (3)	0.0243 (3)

C13—C3	1.514 (6)	C7—C15	1.549 (6)
C13—H13A	0.9600	C7—C8	1.596 (6)
C13—H13B	0.9600	C8—C9	1.515 (6)
C13—H13C	0.9600	C8—H8	0.9800
C1—C2	1.516 (6)	C9—C10	1.318 (6)
C1—C12	1.528 (5)	C9—H9	0.9300
C1—C3	1.540 (6)	C10—C11	1.503 (6)
C1—C8	1.544 (5)	C10—C16	1.517 (6)
C2—C3	1.523 (6)	C11—C12	1.520 (6)
C2—Br2	1.930 (4)	C11—H11A	0.9700
C2—Br1	1.949 (4)	C11—H11B	0.9700
C3—C4	1.519 (6)	C12—H12A	0.9700
C4—C5	1.532 (6)	C12—H12B	0.9700
C4—H4A	0.9700	C14—H14A	0.9600
C4—H4B	0.9700	C14—H14B	0.9600
C5—C6	1.538 (6)	C14—H14C	0.9600
C5—H5A	0.9700	C15—H15A	0.9600
C5—H5B	0.9700	C15—H15B	0.9600
C6—C7	1.541 (6)	C15—H15C	0.9600
C6—H6A	0.9700	C16—Br3	1.973 (4)
C6—H6B	0.9700	C16—H16A	0.9700
C7—C14	1.535 (6)	C16—H16B	0.9700

C3—C13—H13A	109.5	C14—C7—C8	107.5 (4)
C3—C13—H13B	109.5	C6—C7—C8	111.8 (3)
H13A—C13—H13B	109.5	C15—C7—C8	112.1 (4)
C3—C13—H13C	109.5	C9—C8—C1	109.5 (3)
H13A—C13—H13C	109.5	C9—C8—C7	111.9 (3)
H13B—C13—H13C	109.5	C1—C8—C7	114.7 (3)
C2—C1—C12	117.5 (3)	C9—C8—H8	106.7
C2—C1—C3	59.8 (3)	C1—C8—H8	106.7
C12—C1—C3	122.7 (3)	C7—C8—H8	106.7
C2—C1—C8	118.3 (4)	C10—C9—C8	125.1 (4)
C12—C1—C8	112.0 (3)	C10—C9—H9	117.4
C3—C1—C8	117.4 (4)	C8—C9—H9	117.4
C1—C2—C3	60.9 (3)	C9—C10—C11	122.5 (4)
C1—C2—Br2	122.8 (3)	C9—C10—C16	119.5 (4)
C3—C2—Br2	122.1 (3)	C11—C10—C16	118.0 (4)
C1—C2—Br1	119.5 (3)	C10—C11—C12	113.0 (3)
C3—C2—Br1	118.5 (3)	C10—C11—H11A	109.0
Br2—C2—Br1	107.3 (2)	C12—C11—H11A	109.0
C13—C3—C4	113.1 (4)	C10—C11—H11B	109.0
C13—C3—C2	120.0 (4)	C12—C11—H11B	109.0
C4—C3—C2	118.1 (4)	H11A—C11—H11B	107.8
C13—C3—C1	120.2 (4)	C11—C12—C1	109.1 (3)
C4—C3—C1	116.1 (4)	C11—C12—H12A	109.9
C2—C3—C1	59.3 (3)	C1—C12—H12A	109.9
C3—C4—C5	111.9 (4)	C11—C12—H12B	109.9
C3—C4—H4A	109.2	C1—C12—H12B	109.9
C5—C4—H4A	109.2	H12A—C12—H12B	108.3
C3—C4—H4B	109.2	C7—C14—H14A	109.5
C5—C4—H4B	109.2	C7—C14—H14B	109.5
H4A—C4—H4B	107.9	H14A—C14—H14B	109.5
C4—C5—C6	114.9 (4)	C7—C14—H14C	109.5
C4—C5—H5A	108.5	H14A—C14—H14C	109.5
C6—C5—H5A	108.5	H14B—C14—H14C	109.5
C4—C5—H5B	108.5	C7—C15—H15A	109.5
C6—C5—H5B	108.5	C7—C15—H15B	109.5
H5A—C5—H5B	107.5	H15A—C15—H15B	109.5
C5—C6—C7	118.4 (4)	C7—C15—H15C	109.5
C5—C6—H6A	107.7	H15A—C15—H15C	109.5
C7—C6—H6A	107.7	H15B—C15—H15C	109.5
C5—C6—H6B	107.7	C10—C16—Br3	111.2 (3)
C7—C6—H6B	107.7	C10—C16—H16A	109.4
H6A—C6—H6B	107.1	Br3—C16—H16A	109.4
C14—C7—C6	109.9 (4)	C10—C16—H16B	109.4
C14—C7—C15	108.2 (4)	Br3—C16—H16B	109.4
C6—C7—C15	107.2 (4)	H16A—C16—H16B	108.0

5 in total

1. Regio- and stereoselectivity of beta-himachalene epoxidation by m-CPBA. A theoretical study.

Authors: A Chekroun; A Jarid; A Benharref; A Boutalib
Journal: J Org Chem Date: 2000-07-14 Impact factor: 4.354

2. Screening study for potential lead compounds for natural product-based fungicides: I. Synthesis and in vitro evaluation of coumarins against Botrytis cinerea.

Authors: Mourad Daoubi; Rosa Durán-Patrón; Mohamed Hmamouchi; Rosario Hernández-Galán; Ahmed Benharref; Isidro G Collado
Journal: Pest Manag Sci Date: 2004-09 Impact factor: 4.845

3. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

4. (1S,3R,8S,9S,10R)-2,2-Dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.0(1,3)]dodecane and (1S,3R,8S,10R)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0(1,3)]dodecan-9-one.

Authors: F Sbai; M Dakir; A Auhmani; H El Jamili; M Akssira; A Benharref; A Kenz; M Pierrot
Journal: Acta Crystallogr C Date: 2002-07-31 Impact factor: 1.172

5. (1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetra-methyltricyclo-[6.4.0.0]dodec-10-en-9-one.

Authors: Ahmed Benharref; Lahcen El Ammari; Moha Berraho
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2010-10-23

5 in total