(1S*,3R*,5S*,7S*)-4,4,8,8-Tetra­chloro-1-isopropyl-5-methyl­tri­cyclo­[5.1.0.03,5]octa­ne

Turdybekov, K.M.; Ryazantsev, O.G.; Atazhanova, G.A.; Adekenov, S.M.

doi:10.1107/S1600536814004826

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o417

doi:10.1107/S1600536814004826

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(1S,3R,5S,7S)-4,4,8,8-Tetrachloro-1-isopropyl-5-methyltricyclo[5.1.0.0^3,5]octane

Koblandy M. Turdybekov,^a ^* Oleg G. Ryazantsev,^a Gayane A. Atazhanova ^a and Sergazy M. Adekenov ^a

^aInternational Reseach and Production Holding "Phytochemistry", Gazaliev St 4, 100009 Karaganda, Kazakhstan
^*Correspondence e-mail: xray-phyto@yandex.kz

(Received 13 February 2014; accepted 3 March 2014; online 12 March 2014)

The title compound, C₁₂H₁₆Cl₄, is a derivative of the natural product 1-isopropyl-4-methylcyclohexa-1,4-diene, and represents a diastereomer with two trans-fused cyclopropane rings. Both enantiomers are present in the non-centrosymmetric polar space group Pna2₁. The central cyclohexane ring is planar within 0.02 (1) Å. The C atoms of dichloromethylene groups deviate from this plane by 1.19 (1) and −1.26 (1) Å, whereas the isopropyl and methyl groups are oriented more equatorially, deviating by 0.71 (1) and −0.87 (1) Å, respectively.

CCDC reference: 989552

Related literature

For the isolation of 1-isopropyl-4-methylcyclohexa-1,4-diene, see: Jamali et al. (2013 ). For the crystal structure of a related compound, see: Lynch et al. (1994 ).

Experimental

Crystal data

C₁₂H₁₆Cl₄
M_r = 302.05
Orthorhombic, P n a 2₁
a = 10.9480 (3) Å
b = 11.8207 (3) Å
c = 10.5027 (4) Å
V = 1359.19 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 150 K
0.30 × 0.26 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.786, T_max = 0.988
9762 measured reflections
3130 independent reflections
2973 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.05
3130 reflections
148 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1313 Friedel pairs
Absolute structure parameter: 0.09 (4)

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 989552

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814004826/ld2121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004826/ld2121Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814004826/ld2121Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536814004826/ld2121Isup4.cml

checkCIF report

Comment top

The molecule of the title compound, (I) (Fig.1) is an enantiomeric pair of diastereomers. The relative configuration at positions 1, 3, 5 and 7 was established as S, R, S, and S, respectively. The cyclohexane ring is approximately planar, the maximum deviation from the mean plane being 0.02 (1) Å. The atoms C4 and C8 of cyclopentane rings deviate from this plane on 1.19 (1) and -1.26 (1) Å, atom C9 of isopropyl and atom C12 of methyl groups deviate on 0.71 (1) and -0.87 (1) Å, respectively.

Related literature top

For the isolation of 1-isopropyl-4-methylcyclohexa-1,4-diene, see: Jamali et al. (2013). For the crystal structure of a related compound, see: Lynch et al. (1994).

Experimental top

The title compound was synthesized by interaction of /g-terpinene 1-isopropyl-4-methylcyclohexa-1,4-diene, which was isolated from the essential oil of above aerial part of Juniperus sabina L., with NaOH in CHCl₃ in presence of triethylbenzylammonium chloride with yield 72% and with melting point 80–84°C.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

(1S*,3R*,5S*,7S*)-4,4,8,8-Tetrachloro-1-isopropyl-5-methyltricyclo[5.1.0.0^3,5]octane top

Crystal data top

C₁₂H₁₆Cl₄	D_x = 1.476 Mg m⁻³
M_r = 302.05	Melting point = 357–353 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5371 reflections
a = 10.9480 (3) Å	θ = 2.5–29.2°
b = 11.8207 (3) Å	µ = 0.84 mm⁻¹
c = 10.5027 (4) Å	T = 150 K
V = 1359.19 (7) Å³	Irregular, colourless
Z = 4	0.30 × 0.26 × 0.02 mm
F(000) = 624

Data collection top

Bruker APEXII CCD diffractometer	3130 independent reflections
Radiation source: fine-focus sealed tube	2973 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 7.11 pixels mm^-1	θ_max = 29.7°, θ_min = 2.6°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −13→15
T_min = 0.786, T_max = 0.988	l = −14→13
9762 measured 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)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0259P)² + 0.1704P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3130 reflections	Δρ_max = 0.23 e Å⁻³
148 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1313 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (4)

Crystal data top

C₁₂H₁₆Cl₄	V = 1359.19 (7) Å³
M_r = 302.05	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 10.9480 (3) Å	µ = 0.84 mm⁻¹
b = 11.8207 (3) Å	T = 150 K
c = 10.5027 (4) Å	0.30 × 0.26 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	3130 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2973 reflections with I > 2σ(I)
T_min = 0.786, T_max = 0.988	R_int = 0.021
9762 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	Δρ_max = 0.23 e Å⁻³
S = 1.05	Δρ_min = −0.16 e Å⁻³
3130 reflections	Absolute structure: Flack (1983), 1313 Friedel pairs
148 parameters	Absolute structure parameter: 0.09 (4)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cl1	0.57150 (4)	−0.08034 (4)	1.00600 (5)	0.03549 (12)
Cl2	0.38725 (4)	0.05915 (4)	1.12573 (5)	0.03067 (11)
Cl3	−0.09617 (3)	0.02606 (4)	0.84836 (4)	0.02866 (11)
Cl4	0.10624 (4)	−0.10256 (4)	0.74584 (4)	0.02984 (11)
C1	0.15053 (13)	0.08350 (13)	0.90807 (15)	0.0188 (3)
C2	0.27707 (13)	0.08167 (13)	0.84709 (17)	0.0232 (3)
H2A	0.2665	0.0869	0.7537	0.028*
H2B	0.3213	0.1504	0.8748	0.028*
C3	0.35723 (14)	−0.01975 (14)	0.87507 (16)	0.0228 (3)
H3	0.4093	−0.0434	0.8015	0.027*
C4	0.41698 (13)	−0.03625 (14)	1.00155 (18)	0.0240 (3)
C5	0.31894 (14)	−0.11786 (14)	0.96113 (17)	0.0223 (3)
C6	0.19710 (14)	−0.11148 (14)	1.03019 (16)	0.0223 (3)
H6A	0.1526	−0.1831	1.0148	0.027*
H6B	0.2136	−0.1068	1.1227	0.027*
C7	0.11359 (13)	−0.01439 (13)	0.99450 (16)	0.0186 (3)
H7	0.0555	0.0077	1.0636	0.022*
C8	0.06109 (13)	−0.00524 (14)	0.86426 (16)	0.0204 (3)
C9	0.10022 (14)	0.20144 (15)	0.93809 (17)	0.0230 (4)
H9	0.0144	0.1915	0.9687	0.028*
C10	0.17182 (18)	0.25947 (16)	1.04511 (19)	0.0333 (4)
H10A	0.2567	0.2704	1.0183	0.050*
H10B	0.1698	0.2120	1.1216	0.050*
H10C	0.1348	0.3331	1.0639	0.050*
C11	0.09512 (18)	0.27444 (16)	0.8189 (2)	0.0338 (4)
H11A	0.0558	0.3467	0.8390	0.051*
H11B	0.0481	0.2353	0.7529	0.051*
H11C	0.1782	0.2883	0.7880	0.051*
C12	0.35564 (17)	−0.23654 (15)	0.92405 (19)	0.0303 (4)
H12A	0.4327	−0.2342	0.8766	0.045*
H12B	0.2918	−0.2700	0.8706	0.045*
H12C	0.3662	−0.2824	1.0010	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01859 (18)	0.0338 (2)	0.0541 (3)	0.00717 (17)	−0.0056 (2)	0.0017 (2)
Cl2	0.0291 (2)	0.0298 (2)	0.0332 (2)	0.00478 (17)	−0.00942 (19)	−0.00751 (19)
Cl3	0.01775 (18)	0.0357 (3)	0.0325 (2)	0.00250 (16)	−0.00432 (19)	0.00241 (19)
Cl4	0.0297 (2)	0.0359 (3)	0.0239 (2)	0.00577 (17)	−0.00508 (17)	−0.00837 (18)
C1	0.0177 (7)	0.0225 (8)	0.0161 (8)	0.0025 (6)	0.0012 (6)	0.0021 (6)
C2	0.0202 (8)	0.0252 (8)	0.0241 (9)	0.0021 (6)	0.0043 (7)	0.0065 (7)
C3	0.0183 (7)	0.0276 (9)	0.0227 (9)	0.0034 (6)	0.0030 (6)	0.0003 (7)
C4	0.0166 (7)	0.0250 (9)	0.0304 (10)	0.0056 (6)	−0.0019 (7)	−0.0004 (8)
C5	0.0203 (7)	0.0220 (8)	0.0247 (8)	0.0039 (6)	−0.0024 (6)	−0.0004 (7)
C6	0.0209 (7)	0.0241 (9)	0.0220 (8)	0.0006 (6)	−0.0001 (6)	0.0028 (7)
C7	0.0171 (7)	0.0214 (8)	0.0173 (8)	0.0004 (5)	0.0001 (6)	0.0008 (6)
C8	0.0166 (7)	0.0249 (8)	0.0198 (9)	0.0030 (6)	−0.0007 (6)	−0.0003 (7)
C9	0.0197 (7)	0.0236 (9)	0.0256 (9)	0.0049 (7)	0.0014 (6)	0.0022 (7)
C10	0.0332 (10)	0.0255 (9)	0.0411 (12)	0.0068 (8)	−0.0033 (8)	−0.0080 (8)
C11	0.0317 (10)	0.0299 (10)	0.0399 (12)	0.0072 (8)	0.0031 (7)	0.0124 (9)
C12	0.0295 (9)	0.0254 (10)	0.0359 (11)	0.0061 (7)	−0.0030 (8)	−0.0046 (8)

Geometric parameters (Å, º) top

Cl1—C4	1.7707 (15)	C6—C7	1.514 (2)
Cl2—C4	1.7547 (19)	C6—H6A	0.9900
Cl3—C8	1.7689 (14)	C6—H6B	0.9900
Cl4—C8	1.7648 (17)	C7—C8	1.488 (2)
C1—C8	1.507 (2)	C7—H7	1.0000
C1—C7	1.525 (2)	C9—C11	1.522 (2)
C1—C2	1.526 (2)	C9—C10	1.532 (3)
C1—C9	1.532 (2)	C9—H9	1.0000
C2—C3	1.515 (2)	C10—H10A	0.9800
C2—H2A	0.9900	C10—H10B	0.9800
C2—H2B	0.9900	C10—H10C	0.9800
C3—C4	1.493 (2)	C11—H11A	0.9800
C3—C5	1.529 (2)	C11—H11B	0.9800
C3—H3	1.0000	C11—H11C	0.9800
C4—C5	1.504 (2)	C12—H12A	0.9800
C5—C12	1.510 (2)	C12—H12B	0.9800
C5—C6	1.520 (2)	C12—H12C	0.9800

C8—C1—C7	58.76 (10)	C8—C7—C6	121.06 (14)
C8—C1—C2	116.86 (14)	C8—C7—C1	60.00 (11)
C7—C1—C2	118.66 (13)	C6—C7—C1	124.20 (13)
C8—C1—C9	117.56 (13)	C8—C7—H7	113.7
C7—C1—C9	118.21 (13)	C6—C7—H7	113.7
C2—C1—C9	115.19 (13)	C1—C7—H7	113.7
C3—C2—C1	117.11 (13)	C7—C8—C1	61.24 (11)
C3—C2—H2A	108.0	C7—C8—Cl4	119.49 (11)
C1—C2—H2A	108.0	C1—C8—Cl4	119.14 (11)
C3—C2—H2B	108.0	C7—C8—Cl3	118.56 (11)
C1—C2—H2B	108.0	C1—C8—Cl3	121.04 (11)
H2A—C2—H2B	107.3	Cl4—C8—Cl3	110.02 (9)
C4—C3—C2	121.99 (14)	C11—C9—C1	111.10 (14)
C4—C3—C5	59.69 (11)	C11—C9—C10	111.62 (16)
C2—C3—C5	123.80 (13)	C1—C9—C10	111.99 (13)
C4—C3—H3	113.7	C11—C9—H9	107.3
C2—C3—H3	113.7	C1—C9—H9	107.3
C5—C3—H3	113.7	C10—C9—H9	107.3
C3—C4—C5	61.33 (11)	C9—C10—H10A	109.5
C3—C4—Cl2	119.73 (11)	C9—C10—H10B	109.5
C5—C4—Cl2	119.31 (12)	H10A—C10—H10B	109.5
C3—C4—Cl1	118.71 (12)	C9—C10—H10C	109.5
C5—C4—Cl1	120.02 (12)	H10A—C10—H10C	109.5
Cl2—C4—Cl1	110.29 (9)	H10B—C10—H10C	109.5
C4—C5—C12	118.59 (14)	C9—C11—H11A	109.5
C4—C5—C6	117.36 (14)	C9—C11—H11B	109.5
C12—C5—C6	113.74 (14)	H11A—C11—H11B	109.5
C4—C5—C3	58.98 (11)	C9—C11—H11C	109.5
C12—C5—C3	118.63 (15)	H11A—C11—H11C	109.5
C6—C5—C3	119.01 (13)	H11B—C11—H11C	109.5
C7—C6—C5	116.70 (14)	C5—C12—H12A	109.5
C7—C6—H6A	108.1	C5—C12—H12B	109.5
C5—C6—H6A	108.1	H12A—C12—H12B	109.5
C7—C6—H6B	108.1	C5—C12—H12C	109.5
C5—C6—H6B	108.1	H12A—C12—H12C	109.5
H6A—C6—H6B	107.3	H12B—C12—H12C	109.5

C8—C1—C2—C3	−66.2 (2)	C5—C6—C7—C8	64.6 (2)
C7—C1—C2—C3	1.2 (2)	C5—C6—C7—C1	−8.1 (2)
C9—C1—C2—C3	149.62 (15)	C2—C1—C7—C8	−105.70 (16)
C1—C2—C3—C4	−73.4 (2)	C9—C1—C7—C8	106.78 (15)
C1—C2—C3—C5	−0.8 (2)	C8—C1—C7—C6	109.15 (17)
C2—C3—C4—C5	113.23 (16)	C2—C1—C7—C6	3.4 (2)
C2—C3—C4—Cl2	3.9 (2)	C9—C1—C7—C6	−144.07 (16)
C5—C3—C4—Cl2	−109.28 (14)	C6—C7—C8—C1	−114.21 (16)
C2—C3—C4—Cl1	−136.23 (13)	C6—C7—C8—Cl4	−5.1 (2)
C5—C3—C4—Cl1	110.53 (15)	C1—C7—C8—Cl4	109.13 (13)
C3—C4—C5—C12	108.00 (18)	C6—C7—C8—Cl3	134.01 (13)
Cl2—C4—C5—C12	−142.04 (15)	C1—C7—C8—Cl3	−111.78 (14)
Cl1—C4—C5—C12	−0.4 (2)	C2—C1—C8—C7	108.76 (15)
C3—C4—C5—C6	−109.03 (16)	C9—C1—C8—C7	−107.88 (16)
Cl2—C4—C5—C6	0.9 (2)	C7—C1—C8—Cl4	−109.69 (14)
Cl1—C4—C5—C6	142.53 (14)	C2—C1—C8—Cl4	−0.9 (2)
Cl2—C4—C5—C3	109.95 (14)	C9—C1—C8—Cl4	142.43 (13)
Cl1—C4—C5—C3	−108.44 (15)	C7—C1—C8—Cl3	107.83 (14)
C2—C3—C5—C4	−110.31 (18)	C2—C1—C8—Cl3	−143.41 (13)
C4—C3—C5—C12	−107.94 (17)	C9—C1—C8—Cl3	0.0 (2)
C2—C3—C5—C12	141.75 (17)	C8—C1—C9—C11	−86.75 (17)
C4—C3—C5—C6	106.25 (17)	C7—C1—C9—C11	−154.17 (14)
C2—C3—C5—C6	−4.1 (2)	C2—C1—C9—C11	57.21 (19)
C4—C5—C6—C7	76.0 (2)	C8—C1—C9—C10	147.68 (16)
C12—C5—C6—C7	−139.28 (15)	C7—C1—C9—C10	80.26 (18)
C3—C5—C6—C7	8.1 (2)	C2—C1—C9—C10	−68.36 (19)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆Cl₄
M_r	302.05
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	10.9480 (3), 11.8207 (3), 10.5027 (4)
V (Å³)	1359.19 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.30 × 0.26 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.786, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	9762, 3130, 2973
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.698

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.05
No. of reflections	3130
No. of parameters	148
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.16
Absolute structure	Flack (1983), 1313 Friedel pairs
Absolute structure parameter	0.09 (4)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank Professor Yurii V. Gatilov (Institute of Organic Chemistry, Novosibirsk, Russia) for the data collection.

References

Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jamali, C. A., Kasrat, A., Bekkouche, K., Hassani, L., Wohlmuth, H., Leach, D. & Abbad, A. (2013). Ind. Crops Prod. 49, 366–372. Web of Science CrossRef CAS Google Scholar
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