Literature DB >> 23723876

(1S,3R,8R,9S,11R)-2,2-Di-bromo-10,10-di-chloro-3,7,7,11-tetra-methyl-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

Najia Ourhriss¹, Ahmed Benharref, Mohamed Saadi, Moha Berraho, Lahcen El Ammari.

Abstract

The title compound, C17H24Br2Cl2, was synthesized 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 the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule contains fused six-, seven- and two three-membered rings. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a boat conformation. The absolute structure was unambiguously established from anomalous dispersion effects. The crystal packing exhibits no short inter-molecular contacts.

Entities: Chemical Disease Species

Year: 2013 PMID： 23723876 PMCID： PMC3648256 DOI： 10.1107/S1600536813009070

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

Related literature

For the crystal structures of related compounds, see: Ourhriss et al. (2013 ▶); Oukhrib et al. (2013a ▶,b ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C17H24Br2Cl2 M = 459.08 Monoclinic, a = 9.0112 (6) Å b = 11.6772 (8) Å c = 9.0849 (6) Å β = 108.045 (5)° V = 908.94 (11) Å3 Z = 2 Mo Kα radiation μ = 4.75 mm−1 T = 296 K 0.45 × 0.34 × 0.29 mm

Data collection

Bruker X8 APEX diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.739, T max = 0.867 6676 measured reflections 3720 independent reflections 2910 reflections with I > 2σ(I) R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.038 wR(F 2) = 0.092 S = 1.03 3720 reflections 190 parameters 1 restraint H-atom parameters constrained Δρmax = 0.64 e Å−3 Δρmin = −0.79 e Å−3 Absolute structure: Flack & Bernardinelli (2000 ▶), 1096 Friedel pairs Flack parameter: 0.039 (10) 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, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶). Click here for additional data file. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009070/cv5397sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009070/cv5397Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536813009070/cv5397Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₇H₂₄Br₂Cl₂	F(000) = 460
M_r = 459.08	D_x = 1.677 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3720 reflections
a = 9.0112 (6) Å	θ = 2.8–29.6°
b = 11.6772 (8) Å	µ = 4.75 mm⁻¹
c = 9.0849 (6) Å	T = 296 K
β = 108.045 (5)°	Block, colourless
V = 908.94 (11) Å³	0.45 × 0.34 × 0.29 mm
Z = 2

Bruker X8 APEX diffractometer	3720 independent reflections
Radiation source: fine-focus sealed tube	2910 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 29.6°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −12→12
T_min = 0.739, T_max = 0.867	k = −16→15
6676 measured reflections	l = −12→12

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0333P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3720 reflections	Δρ_max = 0.64 e Å⁻³
190 parameters	Δρ_min = −0.79 e Å⁻³
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 1096 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.039 (10)

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	U_iso*/U_eq
C1	0.8734 (5)	0.4080 (3)	0.7265 (5)	0.0211 (8)
C2	0.9989 (5)	0.3302 (4)	0.6990 (6)	0.0288 (10)
C3	1.0234 (4)	0.3775 (4)	0.8568 (5)	0.0275 (9)
C4	1.0081 (6)	0.2965 (4)	0.9812 (5)	0.0357 (11)
H4A	1.1102	0.2657	1.0363	0.043*
H4B	0.9413	0.2330	0.9329	0.043*
C5	0.9408 (6)	0.3542 (5)	1.0962 (6)	0.0442 (13)
H5A	1.0232	0.3954	1.1721	0.053*
H5B	0.9014	0.2960	1.1507	0.053*
C6	0.8095 (6)	0.4372 (5)	1.0187 (5)	0.0387 (12)
H6A	0.8567	0.5027	0.9849	0.046*
H6B	0.7670	0.4645	1.0981	0.046*
C7	0.6702 (5)	0.3992 (4)	0.8798 (5)	0.0301 (9)
C8	0.7181 (4)	0.3573 (3)	0.7345 (5)	0.0206 (8)
H8	0.7319	0.2741	0.7439	0.025*
C9	0.5812 (4)	0.3798 (4)	0.5883 (4)	0.0224 (8)
H9	0.4807	0.3749	0.6086	0.027*
C10	0.5657 (5)	0.3530 (4)	0.4239 (5)	0.0261 (9)
C11	0.5826 (5)	0.4755 (4)	0.4748 (5)	0.0278 (9)
C12	0.7378 (6)	0.5328 (4)	0.4939 (6)	0.0373 (11)
H12A	0.7190	0.6125	0.4639	0.045*
H12B	0.7856	0.4970	0.4234	0.045*
C13	0.8528 (5)	0.5277 (3)	0.6570 (5)	0.0277 (9)
H13A	0.9534	0.5556	0.6546	0.033*
H13B	0.8168	0.5784	0.7235	0.033*
C14	1.1485 (6)	0.4682 (5)	0.9207 (7)	0.0432 (13)
H14A	1.1495	0.4896	1.0230	0.065*
H14B	1.1262	0.5343	0.8546	0.065*
H14C	1.2486	0.4377	0.9247	0.065*
C15	0.5843 (6)	0.2992 (5)	0.9266 (6)	0.0453 (13)
H15A	0.4981	0.2763	0.8394	0.068*
H15B	0.5463	0.3228	1.0096	0.068*
H15C	0.6547	0.2360	0.9601	0.068*
C16	0.5593 (6)	0.5035 (5)	0.8432 (6)	0.0419 (12)
H16A	0.6113	0.5673	0.8140	0.063*
H16B	0.5305	0.5232	0.9333	0.063*
H16C	0.4673	0.4849	0.7596	0.063*
C17	0.4417 (7)	0.5546 (4)	0.4175 (7)	0.0479 (14)
H17A	0.4693	0.6299	0.4593	0.072*
H17B	0.3576	0.5255	0.4506	0.072*
H17C	0.4095	0.5581	0.3065	0.072*
Cl1	0.37818 (14)	0.30587 (10)	0.30591 (14)	0.0415 (3)
Cl2	0.70977 (16)	0.28463 (12)	0.36234 (14)	0.0429 (3)
Br1	1.11977 (6)	0.38295 (6)	0.57096 (7)	0.05382 (18)
Br2	0.97449 (6)	0.16666 (4)	0.66883 (6)	0.04537 (16)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0167 (18)	0.022 (2)	0.023 (2)	−0.0038 (15)	0.0039 (16)	−0.0013 (15)
C2	0.019 (2)	0.034 (2)	0.033 (3)	−0.0019 (17)	0.0085 (19)	−0.0011 (18)
C3	0.0185 (18)	0.035 (2)	0.028 (2)	0.005 (2)	0.0054 (17)	0.004 (2)
C4	0.028 (2)	0.049 (3)	0.024 (2)	0.003 (2)	−0.0001 (19)	0.003 (2)
C5	0.044 (3)	0.066 (4)	0.021 (3)	−0.004 (3)	0.007 (2)	−0.002 (2)
C6	0.038 (3)	0.057 (3)	0.023 (3)	−0.001 (2)	0.013 (2)	−0.010 (2)
C7	0.029 (2)	0.038 (2)	0.028 (2)	0.0027 (19)	0.0153 (19)	−0.004 (2)
C8	0.0199 (18)	0.0217 (19)	0.022 (2)	0.0009 (15)	0.0096 (17)	0.0021 (15)
C9	0.0205 (18)	0.0241 (18)	0.024 (2)	−0.0013 (18)	0.0093 (16)	0.0001 (18)
C10	0.022 (2)	0.035 (2)	0.019 (2)	0.0020 (17)	0.0027 (17)	0.0016 (16)
C11	0.029 (2)	0.028 (2)	0.023 (2)	0.0031 (18)	0.0021 (19)	0.0076 (17)
C12	0.035 (3)	0.030 (2)	0.043 (3)	−0.006 (2)	0.007 (2)	0.011 (2)
C13	0.022 (2)	0.022 (2)	0.037 (3)	−0.0034 (17)	0.0067 (19)	0.0028 (18)
C14	0.023 (2)	0.054 (3)	0.047 (3)	−0.008 (2)	0.004 (2)	−0.005 (2)
C15	0.043 (3)	0.068 (3)	0.033 (3)	−0.005 (3)	0.024 (3)	0.004 (3)
C16	0.036 (3)	0.051 (3)	0.044 (3)	0.011 (2)	0.019 (3)	−0.008 (2)
C17	0.042 (3)	0.038 (3)	0.053 (3)	0.012 (2)	−0.001 (3)	0.003 (2)
Cl1	0.0330 (6)	0.0449 (7)	0.0341 (7)	−0.0066 (5)	−0.0077 (5)	−0.0011 (5)
Cl2	0.0438 (7)	0.0613 (8)	0.0262 (6)	0.0125 (6)	0.0144 (5)	−0.0040 (5)
Br1	0.0336 (3)	0.0840 (4)	0.0516 (3)	−0.0014 (3)	0.0244 (3)	0.0083 (3)
Br2	0.0452 (3)	0.0386 (2)	0.0525 (3)	0.0134 (3)	0.0156 (3)	−0.0033 (3)

C1—C13	1.522 (6)	C9—C11	1.524 (6)
C1—C2	1.530 (6)	C9—H9	0.9800
C1—C3	1.537 (5)	C10—C11	1.496 (6)
C1—C8	1.542 (5)	C10—Cl2	1.756 (4)
C2—C3	1.488 (6)	C10—Cl1	1.785 (4)
C2—Br1	1.924 (4)	C11—C12	1.511 (6)
C2—Br2	1.932 (4)	C11—C17	1.525 (7)
C3—C4	1.513 (6)	C12—C13	1.524 (7)
C3—C14	1.524 (7)	C12—H12A	0.9700
C4—C5	1.519 (7)	C12—H12B	0.9700
C4—H4A	0.9700	C13—H13A	0.9700
C4—H4B	0.9700	C13—H13B	0.9700
C5—C6	1.523 (7)	C14—H14A	0.9600
C5—H5A	0.9700	C14—H14B	0.9600
C5—H5B	0.9700	C14—H14C	0.9600
C6—C7	1.544 (6)	C15—H15A	0.9600
C6—H6A	0.9700	C15—H15B	0.9600
C6—H6B	0.9700	C15—H15C	0.9600
C7—C15	1.531 (7)	C16—H16A	0.9600
C7—C16	1.545 (7)	C16—H16B	0.9600
C7—C8	1.587 (5)	C16—H16C	0.9600
C8—C9	1.529 (6)	C17—H17A	0.9600
C8—H8	0.9800	C17—H17B	0.9600
C9—C10	1.490 (6)	C17—H17C	0.9600

C13—C1—C2	118.6 (3)	C10—C9—H9	111.8
C13—C1—C3	119.8 (3)	C11—C9—H9	111.8
C2—C1—C3	58.1 (3)	C8—C9—H9	111.8
C13—C1—C8	112.1 (3)	C9—C10—C11	61.4 (3)
C2—C1—C8	120.5 (3)	C9—C10—Cl2	124.4 (3)
C3—C1—C8	118.0 (3)	C11—C10—Cl2	121.3 (3)
C3—C2—C1	61.2 (3)	C9—C10—Cl1	116.4 (3)
C3—C2—Br1	121.4 (3)	C11—C10—Cl1	117.8 (3)
C1—C2—Br1	119.6 (3)	Cl2—C10—Cl1	108.9 (2)
C3—C2—Br2	118.7 (3)	C10—C11—C12	117.4 (4)
C1—C2—Br2	123.5 (3)	C10—C11—C9	59.1 (3)
Br1—C2—Br2	106.9 (2)	C12—C11—C9	116.6 (4)
C2—C3—C4	117.9 (4)	C10—C11—C17	118.6 (4)
C2—C3—C14	119.7 (4)	C12—C11—C17	114.5 (4)
C4—C3—C14	112.2 (4)	C9—C11—C17	119.7 (4)
C2—C3—C1	60.7 (3)	C11—C12—C13	114.9 (4)
C4—C3—C1	117.3 (3)	C11—C12—H12A	108.5
C14—C3—C1	120.2 (4)	C13—C12—H12A	108.5
C3—C4—C5	112.6 (4)	C11—C12—H12B	108.5
C3—C4—H4A	109.1	C13—C12—H12B	108.5
C5—C4—H4A	109.1	H12A—C12—H12B	107.5
C3—C4—H4B	109.1	C1—C13—C12	113.5 (4)
C5—C4—H4B	109.1	C1—C13—H13A	108.9
H4A—C4—H4B	107.8	C12—C13—H13A	108.9
C4—C5—C6	112.5 (4)	C1—C13—H13B	108.9
C4—C5—H5A	109.1	C12—C13—H13B	108.9
C6—C5—H5A	109.1	H13A—C13—H13B	107.7
C4—C5—H5B	109.1	C3—C14—H14A	109.5
C6—C5—H5B	109.1	C3—C14—H14B	109.5
H5A—C5—H5B	107.8	H14A—C14—H14B	109.5
C5—C6—C7	120.9 (4)	C3—C14—H14C	109.5
C5—C6—H6A	107.1	H14A—C14—H14C	109.5
C7—C6—H6A	107.1	H14B—C14—H14C	109.5
C5—C6—H6B	107.1	C7—C15—H15A	109.5
C7—C6—H6B	107.1	C7—C15—H15B	109.5
H6A—C6—H6B	106.8	H15A—C15—H15B	109.5
C15—C7—C6	110.2 (4)	C7—C15—H15C	109.5
C15—C7—C16	108.2 (4)	H15A—C15—H15C	109.5
C6—C7—C16	104.9 (4)	H15B—C15—H15C	109.5
C15—C7—C8	106.7 (4)	C7—C16—H16A	109.5
C6—C7—C8	114.0 (3)	C7—C16—H16B	109.5
C16—C7—C8	112.8 (4)	H16A—C16—H16B	109.5
C9—C8—C1	113.2 (3)	C7—C16—H16C	109.5
C9—C8—C7	108.4 (3)	H16A—C16—H16C	109.5
C1—C8—C7	113.9 (3)	H16B—C16—H16C	109.5
C9—C8—H8	107.0	C11—C17—H17A	109.5
C1—C8—H8	107.0	C11—C17—H17B	109.5
C7—C8—H8	107.0	H17A—C17—H17B	109.5
C10—C9—C11	59.5 (3)	C11—C17—H17C	109.5
C10—C9—C8	129.4 (3)	H17A—C17—H17C	109.5
C11—C9—C8	122.7 (3)	H17B—C17—H17C	109.5

5 in total

1. A short history of SHELX.

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

2. (1S,3R,8R,9R,10S)-2,2-Dibromo-3,7,7,10-tetra-methyl-9β,10β-ep-oxy-3,7,7,10-tetra-methyl-tricyclo-[6.4.0.0(1,3)]dodeca-ne.

Authors: Abdelouahd Oukhrib; Ahmed Benharref; Mohamed Saadi; Moha Berraho; Lahcen El Ammari
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2013-03-09