6-Bromo-2-(1,4-di­bromo-4-methyl­cyclo­hex­yl)-6-methyl­heptan-4-one

Benharref, A.; Mazoir, N.; Ait Elhad, M.; Daran, J.-C.; Berraho, M.

doi:10.1107/S2414314617015966

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171596

https://doi.org/10.1107/S2414314617015966

Open

access

6-Bromo-2-(1,4-dibromo-4-methylcyclohexyl)-6-methylheptan-4-one

Ahmed Benharref,^a Noureddine Mazoir,^a ^* Mustapha Ait Elhad,^a Jean-Claude Daran ^b and Moha Berraho ^a

^aLaboratoire de Chimie des Substances Naturelles, "Unité Associé au CNRST (URAC16)", Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, Université Cadi Ayyad, 40000 Marrakech, Morocco, and ^bLaboratoire de Chimie de Coordination, 205 Route de Narbone, 31077 Toulouse, Cedex 04, France
^*Correspondence e-mail: mazoir17@gmail.com

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 16 October 2017; accepted 2 November 2017; online 7 November 2017)

The title compound, C₁₅H₂₅Br₃O, was synthesized in one step from a mixture of α-atlantone [2-methyl-6-(4-methylcyclohex-3-en-1-yl)hepta-2,5-dien-4-one] and γ-atlantone [2-methyl-6-(4-methylcyclohex-3-en-1-ylidene)hept-2-en-4-one], which were isolated from an essential oil of the Atlas cedar (Cedrus Atlantica). The molecule is built up from the bromo ethyl cyclohexane ring, which has a substituent bromomethylhexanone group. The cyclohexane ring adopts a chair conformation. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains parallel to [100].

Keywords: crystal structure; α-atlantone and γ-atlantone; Atlas cedar (Cedrus Atlantica); C—H⋯O hydrogen bonding.

CCDC reference: 1583652

Structure description

α-Atlantone and γ-atlantone are constituents (5–6%) of the essential oil of the Atlas cedar (Cedrus Atlantica) (Plattier & Teisseire,1974 ; Mazoir et al., 2016 ). The reactivity of these sesquiterpenes and their derivatives has been studied by our team (Loughzail et al., 2009 ; Mazoir et al., 2009 , 2016) in order to prepare new products with biological properties. Indeed, these compounds have been tested for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al.,2004 ).

Herein, we report on the synthesis and crystal structure of the title compound, 6-bromo-2-(1,4-dibromo-4-methylcyclohexyl)-6-methylheptan-4-one. The bromo ethyl cyclohexane ring has a bromomethylhexanone group as a substituent (Fig. 1). The cyclohexane ring has a chair conformation as indicated by the total puckering amplitude Q_T = 0.486 (10) Å and spherical polar angle θ = 1.6 (12)° with φ = 105 (27)°.

Figure 1
A view of the molecular structure of the molecule of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, the molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains parallel to [100] (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱ	0.97	2.43 (1)	3.377 (12)	167
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
A partial view down [010] of the crystal packing of the title compound, showing the C—H⋯O hydrogen bonds as blue lines (see Table 1

Synthesis and crystallization

In a 100 ml reactor equipped with a magnetic stirrer, dichloromethane (40 ml) was added to 2 g (9 mmol) of a mixture of α- and γ-atlantone. 15 ml of 33% bromohydric acid in acetic acid were then added dropwise with stirring. The reaction mixture was stirred for 1 h, then the solvent was removed and the residue obtained was chromatographed on silica, eluting with petroleum ether, which allowed the isolation of the title compound (yield 1.5 g, 73%). The title compound was recrystallized from pentane at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. With the Flack parameter (Flack & Bernardinelli, 2000 ) close to 0.5, we can not determine the absolute structure. The synthesis leads to a racemic compound. Most likely, we have an inversion twin, with two enantiomers present in the crystal.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₂₅Br₃O
M_r	461.08
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	9.2060 (11), 9.6974 (12), 19.605 (3)
V (Å³)	1750.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.91
Crystal size (mm)	0.37 × 0.25 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008 )
T_min, T_max	0.245, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	8603, 2872, 2532
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.581

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.090, 1.08
No. of reflections	2872
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.15, −0.55
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.52 (3)
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1583652

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617015966/ff4021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617015966/ff4021Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

6-Bromo-2-(1,4-dibromo-4-methylcyclohexyl)-6-methylheptan-4-one top

Crystal data top

C₁₅H₂₅Br₃O	D_x = 1.750 Mg m⁻³
M_r = 461.08	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 4050 reflections
a = 9.2060 (11) Å	θ = 2.3–24.3°
b = 9.6974 (12) Å	µ = 6.91 mm⁻¹
c = 19.605 (3) Å	T = 173 K
V = 1750.2 (4) Å³	Fragment, colourless
Z = 4	0.37 × 0.25 × 0.07 mm
F(000) = 912

Data collection top

Bruker APEXII CCD diffractometer	2872 independent reflections
Radiation source: fine-focus sealed tube	2532 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
φ and ω scans	θ_max = 24.4°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −10→10
T_min = 0.245, T_max = 0.745	k = −11→11
8603 measured reflections	l = −22→22

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0404P)² + 1.8613P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.090	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 1.15 e Å⁻³
2872 reflections	Δρ_min = −0.55 e Å⁻³
177 parameters	Absolute structure: Refined as an inversion twin
0 restraints	Absolute structure parameter: 0.52 (3)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0606 (13)	−0.0653 (10)	0.3905 (6)	0.046 (3)
H1A	−0.0342	−0.0762	0.3707	0.069*
H1B	0.0515	−0.0516	0.4388	0.069*
H1C	0.1172	−0.1466	0.3819	0.069*
C2	0.1345 (10)	0.0577 (9)	0.3591 (5)	0.032 (2)
H2	0.2285	0.0654	0.3822	0.038*
C3	0.0507 (12)	0.1918 (9)	0.3770 (5)	0.037 (3)
H3A	0.0492	0.2508	0.3370	0.045*
H3B	−0.0490	0.1679	0.3876	0.045*
C4	0.1123 (10)	0.2716 (9)	0.4353 (5)	0.024 (2)
C5	0.0179 (10)	0.3905 (8)	0.4577 (5)	0.025 (2)
H5A	−0.0736	0.3531	0.4739	0.030*
H5B	−0.0035	0.4463	0.4179	0.030*
C6	0.0783 (9)	0.4849 (7)	0.5129 (5)	0.027 (2)
C7	0.2130 (11)	0.5610 (10)	0.4895 (7)	0.047 (3)
H7A	0.2900	0.4962	0.4817	0.071*
H7B	0.2421	0.6256	0.5240	0.071*
H7C	0.1922	0.6096	0.4479	0.071*
C8	0.0986 (10)	0.4182 (9)	0.5837 (5)	0.024 (2)
H8A	0.0081	0.3793	0.5986	0.036*
H8B	0.1297	0.4870	0.6158	0.036*
H8C	0.1706	0.3468	0.5809	0.036*
C1'	0.1698 (9)	0.0440 (8)	0.2835 (5)	0.024 (2)
C7'	0.2495 (9)	−0.0911 (8)	0.2673 (6)	0.025 (2)
H7'1	0.3321	−0.0992	0.2978	0.030*
H7'2	0.1846	−0.1674	0.2770	0.030*
C6'	0.3031 (10)	−0.1052 (8)	0.1948 (5)	0.023 (2)
H6'1	0.2200	−0.1216	0.1655	0.028*
H6'2	0.3650	−0.1859	0.1922	0.028*
C5'	0.3866 (9)	0.0173 (9)	0.1670 (5)	0.028 (2)
C3'	0.3048 (11)	0.1524 (9)	0.1821 (6)	0.033 (3)
H3'1	0.3676	0.2296	0.1710	0.040*
H3'2	0.2204	0.1577	0.1525	0.040*
C2'	0.2560 (10)	0.1661 (8)	0.2548 (6)	0.032 (3)
H2'1	0.1966	0.2483	0.2586	0.039*
H2'2	0.3412	0.1798	0.2831	0.039*
C15	0.4196 (11)	0.0017 (9)	0.0926 (5)	0.030 (2)
H15A	0.4814	−0.0769	0.0859	0.045*
H15B	0.4679	0.0831	0.0763	0.045*
H15C	0.3307	−0.0111	0.0678	0.045*
O1	0.2291 (8)	0.2476 (7)	0.4609 (5)	0.050 (2)
Br1	−0.02173 (9)	0.03945 (9)	0.23253 (5)	0.0297 (2)
Br2	0.57752 (10)	0.02694 (9)	0.21677 (6)	0.0367 (3)
Br3	−0.07495 (12)	0.62940 (9)	0.52607 (6)	0.0417 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.052 (7)	0.051 (6)	0.036 (7)	0.014 (5)	0.007 (6)	0.002 (5)
C2	0.025 (5)	0.032 (5)	0.039 (7)	0.009 (4)	−0.005 (4)	−0.011 (5)
C3	0.038 (7)	0.042 (5)	0.031 (7)	0.016 (5)	−0.004 (5)	−0.012 (5)
C4	0.026 (6)	0.025 (4)	0.019 (6)	0.001 (4)	0.003 (4)	0.001 (4)
C5	0.022 (5)	0.026 (4)	0.026 (6)	0.003 (4)	0.004 (4)	0.002 (4)
C6	0.021 (4)	0.016 (4)	0.043 (7)	0.000 (4)	−0.001 (4)	−0.006 (4)
C7	0.031 (6)	0.033 (5)	0.078 (10)	−0.007 (4)	0.008 (6)	−0.004 (6)
C8	0.027 (5)	0.028 (4)	0.018 (6)	0.003 (4)	−0.006 (4)	0.007 (4)
C1'	0.021 (4)	0.023 (4)	0.028 (6)	0.002 (4)	−0.003 (4)	−0.004 (5)
C7'	0.023 (5)	0.020 (4)	0.032 (7)	−0.002 (3)	0.002 (5)	0.001 (4)
C6'	0.026 (6)	0.021 (4)	0.022 (6)	0.001 (4)	0.001 (4)	−0.005 (4)
C5'	0.020 (5)	0.028 (5)	0.035 (7)	−0.001 (4)	−0.002 (4)	0.000 (4)
C3'	0.026 (6)	0.023 (5)	0.050 (8)	0.006 (4)	0.001 (5)	0.007 (5)
C2'	0.027 (5)	0.016 (4)	0.053 (9)	0.004 (4)	−0.007 (5)	−0.004 (4)
C15	0.034 (5)	0.032 (5)	0.024 (6)	−0.002 (4)	0.005 (5)	0.005 (4)
O1	0.041 (5)	0.043 (4)	0.065 (7)	0.023 (4)	−0.027 (4)	−0.022 (4)
Br1	0.0244 (5)	0.0343 (4)	0.0305 (6)	0.0016 (4)	−0.0050 (4)	−0.0067 (5)
Br2	0.0239 (5)	0.0375 (5)	0.0488 (8)	−0.0001 (4)	−0.0044 (5)	−0.0034 (5)
Br3	0.0411 (6)	0.0266 (4)	0.0575 (8)	0.0071 (4)	0.0018 (6)	−0.0087 (5)

Geometric parameters (Å, º) top

C1—C2	1.505 (14)	C8—H8B	0.9600
C1—H1A	0.9600	C8—H8C	0.9600
C1—H1B	0.9600	C1'—C2'	1.532 (12)
C1—H1C	0.9600	C1'—C7'	1.535 (11)
C2—C1'	1.523 (14)	C1'—Br1	2.027 (9)
C2—C3	1.552 (12)	C7'—C6'	1.511 (14)
C2—H2	0.9800	C7'—H7'1	0.9700
C3—C4	1.492 (13)	C7'—H7'2	0.9700
C3—H3A	0.9700	C6'—C5'	1.517 (12)
C3—H3B	0.9700	C6'—H6'1	0.9700
C4—O1	1.209 (11)	C6'—H6'2	0.9700
C4—C5	1.509 (12)	C5'—C15	1.498 (14)
C5—C6	1.522 (12)	C5'—C3'	1.540 (12)
C5—H5A	0.9700	C5'—Br2	2.012 (9)
C5—H5B	0.9700	C3'—C2'	1.501 (15)
C6—C7	1.515 (13)	C3'—H3'1	0.9700
C6—C8	1.544 (13)	C3'—H3'2	0.9700
C6—Br3	2.005 (8)	C2'—H2'1	0.9700
C7—H7A	0.9600	C2'—H2'2	0.9700
C7—H7B	0.9600	C15—H15A	0.9600
C7—H7C	0.9600	C15—H15B	0.9600
C8—H8A	0.9600	C15—H15C	0.9600

C2—C1—H1A	109.5	H8B—C8—H8C	109.5
C2—C1—H1B	109.5	C2—C1'—C2'	113.6 (8)
H1A—C1—H1B	109.5	C2—C1'—C7'	112.2 (8)
C2—C1—H1C	109.5	C2'—C1'—C7'	109.6 (7)
H1A—C1—H1C	109.5	C2—C1'—Br1	107.2 (6)
H1B—C1—H1C	109.5	C2'—C1'—Br1	106.7 (6)
C1—C2—C1'	115.2 (8)	C7'—C1'—Br1	107.2 (6)
C1—C2—C3	110.3 (8)	C6'—C7'—C1'	115.3 (8)
C1'—C2—C3	113.6 (8)	C6'—C7'—H7'1	108.5
C1—C2—H2	105.7	C1'—C7'—H7'1	108.5
C1'—C2—H2	105.7	C6'—C7'—H7'2	108.5
C3—C2—H2	105.7	C1'—C7'—H7'2	108.5
C4—C3—C2	114.8 (8)	H7'1—C7'—H7'2	107.5
C4—C3—H3A	108.6	C7'—C6'—C5'	115.7 (7)
C2—C3—H3A	108.6	C7'—C6'—H6'1	108.4
C4—C3—H3B	108.6	C5'—C6'—H6'1	108.4
C2—C3—H3B	108.6	C7'—C6'—H6'2	108.4
H3A—C3—H3B	107.5	C5'—C6'—H6'2	108.4
O1—C4—C3	123.8 (8)	H6'1—C6'—H6'2	107.4
O1—C4—C5	122.6 (9)	C15—C5'—C6'	112.0 (8)
C3—C4—C5	113.6 (8)	C15—C5'—C3'	111.8 (8)
C4—C5—C6	117.1 (8)	C6'—C5'—C3'	110.5 (7)
C4—C5—H5A	108.0	C15—C5'—Br2	107.5 (6)
C6—C5—H5A	108.0	C6'—C5'—Br2	107.8 (6)
C4—C5—H5B	108.0	C3'—C5'—Br2	107.1 (6)
C6—C5—H5B	108.0	C2'—C3'—C5'	113.8 (8)
H5A—C5—H5B	107.3	C2'—C3'—H3'1	108.8
C7—C6—C5	112.2 (9)	C5'—C3'—H3'1	108.8
C7—C6—C8	112.2 (8)	C2'—C3'—H3'2	108.8
C5—C6—C8	115.6 (7)	C5'—C3'—H3'2	108.8
C7—C6—Br3	105.9 (5)	H3'1—C3'—H3'2	107.7
C5—C6—Br3	104.8 (6)	C3'—C2'—C1'	115.8 (8)
C8—C6—Br3	105.2 (6)	C3'—C2'—H2'1	108.3
C6—C7—H7A	109.5	C1'—C2'—H2'1	108.3
C6—C7—H7B	109.5	C3'—C2'—H2'2	108.3
H7A—C7—H7B	109.5	C1'—C2'—H2'2	108.3
C6—C7—H7C	109.5	H2'1—C2'—H2'2	107.4
H7A—C7—H7C	109.5	C5'—C15—H15A	109.5
H7B—C7—H7C	109.5	C5'—C15—H15B	109.5
C6—C8—H8A	109.5	H15A—C15—H15B	109.5
C6—C8—H8B	109.5	C5'—C15—H15C	109.5
H8A—C8—H8B	109.5	H15A—C15—H15C	109.5
C6—C8—H8C	109.5	H15B—C15—H15C	109.5
H8A—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.97	2.43 (1)	3.377 (12)	167

Symmetry code: (i) x−1/2, −y+1/2, −z+1.

Acknowledgements

The authors thank the Laboratoire de Chimie de Coordination, UPR-CNRS 8241 Toulouse for the X-ray measurements.

References

Bruker (2009). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Daoubi, M., Durán-Patrón, R., Hmamouchi, M., Hernández-Galán, R., Benharref, A. & Collado, I. G. (2004). Pest Manag. Sci. 60, 927–932. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143–1148. Web of Science CrossRef CAS IUCr Journals Google Scholar
Loughzail, M., Mazoir, N., Maya, C. M., Berraho, M., Benharref, A. & Bouhmaida, N. (2009). Acta Cryst. E65, o4. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mazoir, N., Dakir, M., Tebbaa, M., Loughzail, M. & Benharref, A. (2016). Tetrahedron Lett. 57, 278–280. Web of Science CrossRef CAS Google Scholar
Mazoir, N., El Ammari, L., Bouhmaida, N., Dahaoui, S., Benharref, A. & Berraho, M. (2009). Acta Cryst. E65, o1269–o1270. Web of Science CSD CrossRef IUCr Journals Google Scholar
Plattier, M. & Teisseire, P. (1974). Recherches, 19, 131–144. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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.