(1S,3R,8R)-2,2-Di­chloro-3,7,7,10-tetra­methyl-11-methyl­enetri­cyclo­[6.4.0.01,3]dodec-9-ene

Benharref, A.; El Ammari, L.; Saadi, M.; Mazoir, N.; Berraho, M.

doi:10.1107/S2414314617004217

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170421

https://doi.org/10.1107/S2414314617004217

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(1S,3R,8R)-2,2-Dichloro-3,7,7,10-tetramethyl-11-methylenetricyclo[6.4.0.0^1,3]dodec-9-ene

Ahmed Benharref,^a ^* Lahcen El Ammari,^b Mohamed Saadi,^b Noureddine Mazoir ^a 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 du Solide Appliquée, Faculté des Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta BP 1014 Rabat, Morocco
^*Correspondence e-mail: benharref@uca.ac.ma

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 10 March 2017; accepted 15 March 2017; online 21 March 2017)

The title compound, C₁₇H₂₄Cl₂, was synthesized in four steps from β-himachalene (3,5,5,9-tetramethyl-2,4a,5,6,7,8-hexahydro-1H-benzocycloheptene), which was isolated from an essential oil of the Atlas cedar (Cedrus atlantica). The molecule is built from fused six- and seven-membered rings, and an additional three-membered ring. The dihedral angle between the mean planes of the cyclohexene and cycloheptane rings is 58.37 (19)°. There is an intramolecular C—H⋯Cl hydrogen bond present involving a Cl atom and the H atom of the unique methine C atom, forming an S(5) ring motif. There are no significant intermolecular interactions present.

Keywords: crystal structure; β-himachalene; three fused rings.

CCDC reference: 1538178

Structure description

The essential oil of Atlas cedar(Cedrus atlantica) consists mainly (50%) of a hydrocarbon sesquiterpene called β-himachalene (El Haib et al., 2011 ). The reactivity of these sesquiterpenes and their derivatives have been studied extensively by our team in order to prepare new products having biological properties (El Haib et al., 2011; Benharref et al., 2015 , 2016 ; Ait Elhad et al., 2017 ). These compounds have been tested, using the food poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004 ). Herein, we report on the crystal structure of the title compound.

The molecular structure is illustrated in Fig. 1. The molecule is built up from a seven-membered ring, which is fused to a six-membered ring and a three-membered ring. The six-membered ring shows a half-chair conformation, as indicated by the total puckering amplitude Q_T of 0.457 (3) Å and spherical polar angle θ = 127.5 (5)° and φ2 = 165.3 (7)°, whereas the seven-membered ring displays a boat conformation with Q_T = 1.121 (4) Å and spherical polar angle θ = 87.59 (26)°, φ2 = 311.0 (2)° and φ3 = 247 (5)°. The mean planes of the six- and seven-membered rings are inclined to one another by 58.37 (19)°. The three-membered ring (C1–C3) is nearly perpendicular to the six-membered ring (C1/C8–C12) mean plane, making a dihedral angle of 86.1 (3)°. There is an intramolecular C—H⋯Cl hydrogen bond present involving a chlorine Cl atom, Cl1 and the H atom of atom C8 common to both rings, forming an S(5) ring motif (Table 1 and Fig. 1). There are no significant intermolecular interactions present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cl1	0.98	2.60	3.174 (3)	117

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular C—H⋯O hydrogen bond is shown as a dashed line (see Table 1

Synthesis and crystallization

In a 250 ml reactor equipped with a condenser, dropping funnel and a magnetic stirrer, was introduced 20 ml of anhydrous ether and 1 g of magnesium, and then via the dropping funnel, 2 ml of methyl iodide dissolved in 20 ml of ether were added dropwise. Thereafter, 6 g (20 mmol) of (1S,3R,8R)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0¹,³] dodecan-11-one (Ourhriss et al., 2013 ) solubilized in 60 ml of ether were added dropwise. At the end of the addition, the mixture was stirred for 4 h at ambient temperature. After addition of 50 ml water, the reaction mixture was extracted three times with 20 ml of dichloromethane. The organic phases were combined, dried over sodium sulfate and then concentrated in vacuo. The residue obtained was chromatographed on silica eluting with hexane, which allowed the isolation of the title compound (yield 1.5 g, 25%). It was recrystallized from petroleum ether, yielding colourless prismatic crystals on slow evaporation of the solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Owing to the presence of Cl atoms, the absolute configuration could be fully confirmed from anomalous dispersion effects [Flack parameter = −0.02 (4)], as C1(S), C3(R) and C8(R).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₄Cl₂
M_r	299.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.5995 (3), 13.4865 (4), 18.2435 (7)
V (Å³)	1623.75 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.24 × 0.2 × 0.15

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.661, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22208, 3322, 2402
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.102, 1.02
No. of reflections	3322
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18
Absolute structure	Flack x determined using 811 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.02 (4)
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1538178

Crystal structure: contains datablocks I, block. DOI: https://doi.org/10.1107/S2414314617004217/ff4014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004217/ff4014Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617004217/ff4014Isup3.cml

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); software used to prepare material for publication: publCIF (Westrip, 2010).

(1S,3R,8R)-2,2-Dichloro-3,7,7,10-tetramethyl-11-methylenetricyclo[6.4.0.0^1,3]dodec-9-ene top

Crystal data top

C₁₇H₂₄Cl₂	D_x = 1.224 Mg m⁻³
M_r = 299.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3322 reflections
a = 6.5995 (3) Å	θ = 2.7–26.4°
b = 13.4865 (4) Å	µ = 0.39 mm⁻¹
c = 18.2435 (7) Å	T = 296 K
V = 1623.75 (11) Å³	Prismatic, colourless
Z = 4	0.24 × 0.2 × 0.15 mm
F(000) = 640

Data collection top

Bruker X8 APEX diffractometer	2402 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
φ and ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.661, T_max = 0.746	k = −14→16
22208 measured reflections	l = −22→22
3322 independent reflections

Refinement top

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0405P)² + 0.3683P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3322 reflections	Δρ_max = 0.22 e Å⁻³
176 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 811 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (4)

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.74059 (16)	0.48733 (7)	0.22743 (5)	0.0593 (3)
Cl2	0.31946 (19)	0.46806 (9)	0.19407 (6)	0.0729 (4)
C8	0.6086 (5)	0.4877 (2)	0.39470 (17)	0.0373 (8)
H8	0.7361	0.5033	0.3697	0.045*
C1	0.4414 (5)	0.5081 (2)	0.34001 (19)	0.0393 (8)
C10	0.4643 (8)	0.3142 (3)	0.3983 (2)	0.0558 (12)
C7	0.6048 (6)	0.5533 (3)	0.4665 (2)	0.0472 (9)
C9	0.6143 (7)	0.3785 (3)	0.4108 (2)	0.0504 (10)
H9	0.7326	0.3534	0.4314	0.060*
C3	0.4449 (6)	0.6081 (3)	0.2991 (2)	0.0469 (9)
C2	0.4937 (6)	0.5133 (3)	0.25931 (19)	0.0448 (9)
C12	0.2456 (6)	0.4582 (3)	0.3607 (2)	0.0566 (10)
H12A	0.1445	0.4717	0.3234	0.068*
H12B	0.1971	0.4855	0.4067	0.068*
C11	0.2719 (7)	0.3478 (3)	0.3686 (2)	0.0574 (11)
C4	0.6192 (7)	0.6770 (3)	0.3179 (2)	0.0587 (12)
H4A	0.6261	0.7295	0.2816	0.070*
H4B	0.7454	0.6401	0.3158	0.070*
C6	0.5094 (9)	0.6556 (3)	0.4524 (2)	0.0707 (14)
H6A	0.3678	0.6449	0.4405	0.085*
H6B	0.5128	0.6918	0.4983	0.085*
C5	0.5962 (9)	0.7228 (3)	0.3940 (2)	0.0722 (15)
H5A	0.7284	0.7454	0.4102	0.087*
H5B	0.5099	0.7808	0.3899	0.087*
C15	0.4846 (8)	0.5050 (4)	0.5288 (2)	0.0763 (14)
H15A	0.4894	0.5469	0.5714	0.115*
H15B	0.5428	0.4417	0.5404	0.115*
H15C	0.3463	0.4963	0.5139	0.115*
C16	0.8238 (8)	0.5643 (4)	0.4931 (3)	0.0816 (16)
H16A	0.8256	0.6009	0.5382	0.122*
H16B	0.9016	0.5991	0.4568	0.122*
H16C	0.8815	0.4998	0.5009	0.122*
C17	0.2504 (8)	0.6630 (3)	0.2818 (3)	0.0804 (15)
H17A	0.2037	0.6968	0.3250	0.121*
H17B	0.1493	0.6165	0.2660	0.121*
H17C	0.2750	0.7104	0.2436	0.121*
C14	0.4937 (10)	0.2054 (3)	0.4160 (3)	0.095 (2)
H14A	0.6291	0.1949	0.4336	0.142*
H14B	0.4721	0.1666	0.3726	0.142*
H14C	0.3984	0.1858	0.4530	0.142*
C13	0.1223 (9)	0.2868 (4)	0.3491 (3)	0.0899 (17)
H13A	0.1381	0.2186	0.3542	0.108*
H13B	0.0021	0.3124	0.3304	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0631 (6)	0.0683 (6)	0.0464 (5)	0.0108 (6)	0.0118 (5)	−0.0042 (5)
Cl2	0.0833 (9)	0.0790 (8)	0.0562 (6)	−0.0033 (6)	−0.0283 (6)	−0.0072 (6)
C8	0.0356 (19)	0.0390 (19)	0.0374 (18)	0.0032 (16)	0.0009 (15)	−0.0028 (15)
C1	0.0363 (19)	0.0397 (19)	0.0418 (19)	0.0008 (16)	−0.0006 (15)	−0.0043 (16)
C10	0.088 (4)	0.040 (2)	0.040 (2)	−0.004 (2)	0.013 (2)	−0.0014 (17)
C7	0.049 (2)	0.051 (2)	0.041 (2)	−0.0043 (18)	0.0038 (18)	−0.0052 (17)
C9	0.059 (3)	0.052 (2)	0.040 (2)	0.016 (2)	0.000 (2)	0.0029 (17)
C3	0.054 (3)	0.045 (2)	0.042 (2)	0.0128 (19)	−0.0034 (19)	0.0017 (17)
C2	0.049 (2)	0.048 (2)	0.038 (2)	0.0028 (19)	−0.0072 (15)	−0.0032 (17)
C12	0.045 (2)	0.068 (3)	0.057 (2)	−0.003 (2)	−0.002 (2)	−0.0041 (19)
C11	0.060 (3)	0.062 (3)	0.050 (2)	−0.019 (2)	0.015 (2)	−0.0069 (18)
C4	0.078 (3)	0.042 (2)	0.056 (3)	−0.006 (2)	0.009 (2)	0.0001 (18)
C6	0.096 (4)	0.060 (3)	0.056 (3)	0.010 (3)	0.012 (3)	−0.019 (2)
C5	0.109 (4)	0.043 (2)	0.064 (3)	−0.008 (2)	0.007 (3)	−0.011 (2)
C15	0.092 (3)	0.089 (3)	0.048 (3)	−0.003 (3)	0.017 (2)	−0.008 (3)
C16	0.074 (3)	0.100 (4)	0.071 (3)	−0.010 (3)	−0.015 (3)	−0.024 (3)
C17	0.081 (4)	0.074 (3)	0.087 (4)	0.038 (3)	−0.003 (3)	0.006 (2)
C14	0.160 (6)	0.043 (2)	0.080 (4)	−0.005 (3)	0.017 (4)	0.008 (2)
C13	0.083 (4)	0.090 (4)	0.097 (4)	−0.041 (3)	0.015 (3)	−0.018 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.765 (4)	C4—C5	1.528 (5)
Cl2—C2	1.764 (4)	C4—H4A	0.9700
C8—C9	1.503 (5)	C4—H4B	0.9700
C8—C1	1.513 (5)	C6—C5	1.511 (6)
C8—C7	1.580 (5)	C6—H6A	0.9700
C8—H8	0.9800	C6—H6B	0.9700
C1—C12	1.505 (5)	C5—H5A	0.9700
C1—C2	1.514 (5)	C5—H5B	0.9700
C1—C3	1.542 (5)	C15—H15A	0.9600
C10—C9	1.335 (6)	C15—H15B	0.9600
C10—C11	1.453 (6)	C15—H15C	0.9600
C10—C14	1.515 (6)	C16—H16A	0.9600
C7—C15	1.532 (5)	C16—H16B	0.9600
C7—C16	1.532 (6)	C16—H16C	0.9600
C7—C6	1.539 (6)	C17—H17A	0.9600
C9—H9	0.9300	C17—H17B	0.9600
C3—C2	1.506 (5)	C17—H17C	0.9600
C3—C17	1.514 (5)	C14—H14A	0.9600
C3—C4	1.518 (6)	C14—H14B	0.9600
C12—C11	1.507 (5)	C14—H14C	0.9600
C12—H12A	0.9700	C13—H13A	0.9300
C12—H12B	0.9700	C13—H13B	0.9300
C11—C13	1.333 (6)

C9—C8—C1	109.0 (3)	C3—C4—C5	112.2 (4)
C9—C8—C7	112.8 (3)	C3—C4—H4A	109.2
C1—C8—C7	115.6 (3)	C5—C4—H4A	109.2
C9—C8—H8	106.3	C3—C4—H4B	109.2
C1—C8—H8	106.3	C5—C4—H4B	109.2
C7—C8—H8	106.3	H4A—C4—H4B	107.9
C12—C1—C8	112.3 (3)	C5—C6—C7	120.0 (4)
C12—C1—C2	117.4 (3)	C5—C6—H6A	107.3
C8—C1—C2	118.9 (3)	C7—C6—H6A	107.3
C12—C1—C3	121.7 (3)	C5—C6—H6B	107.3
C8—C1—C3	117.8 (3)	C7—C6—H6B	107.3
C2—C1—C3	59.0 (2)	H6A—C6—H6B	106.9
C9—C10—C11	120.6 (4)	C6—C5—C4	115.8 (3)
C9—C10—C14	119.8 (5)	C6—C5—H5A	108.3
C11—C10—C14	119.5 (4)	C4—C5—H5A	108.3
C15—C7—C16	107.1 (4)	C6—C5—H5B	108.3
C15—C7—C6	107.1 (4)	C4—C5—H5B	108.3
C16—C7—C6	110.6 (4)	H5A—C5—H5B	107.4
C15—C7—C8	112.7 (3)	C7—C15—H15A	109.5
C16—C7—C8	107.6 (3)	C7—C15—H15B	109.5
C6—C7—C8	111.7 (3)	H15A—C15—H15B	109.5
C10—C9—C8	125.8 (4)	C7—C15—H15C	109.5
C10—C9—H9	117.1	H15A—C15—H15C	109.5
C8—C9—H9	117.1	H15B—C15—H15C	109.5
C2—C3—C17	119.7 (3)	C7—C16—H16A	109.5
C2—C3—C4	117.8 (3)	C7—C16—H16B	109.5
C17—C3—C4	113.0 (3)	H16A—C16—H16B	109.5
C2—C3—C1	59.6 (2)	C7—C16—H16C	109.5
C17—C3—C1	121.0 (3)	H16A—C16—H16C	109.5
C4—C3—C1	116.0 (3)	H16B—C16—H16C	109.5
C3—C2—C1	61.4 (2)	C3—C17—H17A	109.5
C3—C2—Cl2	118.7 (3)	C3—C17—H17B	109.5
C1—C2—Cl2	119.4 (3)	H17A—C17—H17B	109.5
C3—C2—Cl1	121.7 (3)	C3—C17—H17C	109.5
C1—C2—Cl1	121.5 (3)	H17A—C17—H17C	109.5
Cl2—C2—Cl1	108.11 (19)	H17B—C17—H17C	109.5
C1—C12—C11	111.5 (3)	C10—C14—H14A	109.5
C1—C12—H12A	109.3	C10—C14—H14B	109.5
C11—C12—H12A	109.3	H14A—C14—H14B	109.5
C1—C12—H12B	109.3	C10—C14—H14C	109.5
C11—C12—H12B	109.3	H14A—C14—H14C	109.5
H12A—C12—H12B	108.0	H14B—C14—H14C	109.5
C13—C11—C10	123.7 (4)	C11—C13—H13A	120.0
C13—C11—C12	120.0 (5)	C11—C13—H13B	120.0
C10—C11—C12	116.4 (4)	H13A—C13—H13B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cl1	0.98	2.60	3.174 (3)	117

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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