Decachloro­hexa-1,5-diene

Abstract

The title compound, C₆Cl₁₀, cystallizes in a nearly C2-symmetrical gauche conformation. Both trichloro­vinyl groups are nearly planar [Cl—C—C—Cl torsion angles = −178.47 (12) and −179.93 (11)°] and the lengths of their C—Cl bonds increase from the terminal trans and cis C—Cl bonds to the inter­nal bonds. The Cl—C—Cl bond angles of the terminal dichloro­methyl­ene units are compressed to 111.75 (11) and 111.40 (11)°.

Related literature  

For the synthesis of perchloro­alkenes, see: Prins (1949 ▶); Roedig et al. (1963 ▶). For structures of perchloro­alkenes, see: Herbstein (1979 ▶); Rao & Livingston (1958 ▶); Hopf et al. (1991 ▶); Detert et al. (2009 ▶). For rearrangements of highly halogenated alkenes, see: Maahs (1963 ▶); Herges et al. (2005 ▶). For recent reactions of perchloro­alkenes, see: Schmidt et al. (2009 ▶); Rahimi & Schmidt (2010 ▶).

Experimental  

Crystal data  

• C₆Cl₁₀

• M _r = 426.56

• Monoclinic,

• a = 12.8936 (5) Å

• b = 6.7051 (2) Å

• c = 15.3753 (5) Å

• β = 93.858 (3)°

• V = 1326.23 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 2.07 mm⁻¹

• T = 193 K

• 0.15 × 0.15 × 0.15 mm

Data collection  

• Stoe IPDS 2T diffractometer

• Absorption correction: multi-scan (PLATON; Spek, 2009 ▶) T _min = 0.747, T _max = 0.747

• 18142 measured reflections

• 3181 independent reflections

• 2991 reflections with I > 2σ(I)

• R _int = 0.044

Refinement  

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.075

• S = 1.06

• 3181 reflections

• 145 parameters

• Δρ_max = 0.94 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2011 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2011 ▶); program(s) used to solve structure: SIR97 (Altomare et al. 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812019769/bt5907Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

In the monoclinic crystal, decachlorohexadiene adopts a gauche conformation [C2—C3—C4—C5: 60.4 (2)°] with a non-perfect C2-symmetry. With torsion angles of -178.47 (12)° (Cl2—C1—C2—Cl3) and -179.93 (11)° (Cl8—C5—C6—Cl9) both trichorovinyl groups are nearly planar. The C—Cl bonds of these units are significantly different. The bond lengths C2—Cl3 [1.736 (2) Å] and C5—Cl8 [1.737 (2) Å] are sligthly longer than the corresponding bonds (1.731 Å) in trans-octachloro-1,3,5-hexatriene (Detert et al., 2009). The bonds to the cis-chlorine atoms are shorter: C1—Cl1: 1.721 (2) Å and C6—Cl10: 1.718 (2) Å and those to the trans-chlorine atoms are reduced to C1—Cl2: 1.700 (2) Å and C6—Cl9: 1.702 (2). The same bond length variations, but to a lower degree, were found in the triene. With 111.40 (11)° and 111.74 (11)° the bond angles of the terminal dichloromethylene units are smaller than in the reference compound (115.5°).

Experimental

1,5-Decachlorohexadiene: The diene was prepared from hexachloropropene with cuprous chloride as the coupling agent according the procedure given by Prins. (Prins, 1949) Single crystals were obtained by slow evaporation of a solution of perchlorohexadiene in dichloromethane/methanol.

Refinement

All atoms were refined with anisotropic displacement parameters.

Figures

Fig. 1.

View of compound I. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C6Cl10	F(000) = 824
Mr = 426.56	Dx = 2.136 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 28472 reflections
a = 12.8936 (5) Å	θ = 2.6–32.4°
b = 6.7051 (2) Å	µ = 2.07 mm−1
c = 15.3753 (5) Å	T = 193 K
β = 93.858 (3)°	Block, colourless
V = 1326.23 (8) Å3	0.15 × 0.15 × 0.15 mm
Z = 4

Data collection

Stoe IPDS 2T diffractometer	3181 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2991 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 6.67 pixels mm-1	θmax = 28.0°, θmin = 3.0°
rotation method scans	h = −17→17
Absorption correction: multi-scan (PLATON; Spek, 2009)	k = −8→8
Tmin = 0.747, Tmax = 0.747	l = −20→19
18142 measured reflections

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.030	Secondary atom site location: difference Fourier map
wR(F2) = 0.075	w = 1/[σ2(Fo2) + (0.0314P)2 + 1.2539P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3181 reflections	Δρmax = 0.94 e Å−3
145 parameters	Δρmin = −0.44 e Å−3

Special details

Experimental. 13C-NMR (75 MHz, CDCl3): δ = 94.5 (C-3,4), 128.1 (C-1,6), 131.2 (C-2,5)MS (FD): 426 (100%, Cl10 pattern) [M]+.C6Cl10 (426.596): calcd. C 16.89%; found C 17.06%.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.07308 (4)	0.63553 (10)	0.19647 (4)	0.04455 (14)
Cl2	0.28741 (4)	0.54432 (8)	0.22272 (3)	0.03407 (12)
Cl3	0.03427 (4)	0.60643 (9)	0.38657 (4)	0.04477 (14)
Cl4	0.20468 (5)	0.63372 (9)	0.52864 (4)	0.04909 (16)
Cl5	0.36486 (4)	0.62962 (8)	0.41150 (3)	0.03657 (12)
Cl6	0.13705 (5)	0.18663 (9)	0.47450 (4)	0.04778 (15)
Cl7	0.34462 (5)	0.25344 (10)	0.54017 (3)	0.04564 (15)
Cl8	0.19658 (4)	0.09671 (7)	0.29308 (4)	0.03836 (13)
Cl9	0.50500 (4)	0.20720 (9)	0.40404 (3)	0.03898 (13)
Cl10	0.41762 (4)	0.02630 (8)	0.25017 (4)	0.04048 (13)
C1	0.17431 (15)	0.5804 (3)	0.27135 (13)	0.0302 (4)
C2	0.16004 (15)	0.5674 (3)	0.35642 (13)	0.0290 (4)
C3	0.24229 (15)	0.5212 (3)	0.43068 (12)	0.0287 (4)
C4	0.25883 (15)	0.2894 (3)	0.44660 (12)	0.0294 (4)
C5	0.29541 (15)	0.1796 (3)	0.36660 (12)	0.0281 (4)
C6	0.39289 (15)	0.1447 (3)	0.34565 (12)	0.0289 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0363 (3)	0.0573 (3)	0.0386 (3)	0.0024 (2)	−0.0082 (2)	0.0092 (2)
Cl2	0.0338 (2)	0.0402 (3)	0.0291 (2)	0.00294 (19)	0.00900 (17)	0.00380 (18)
Cl3	0.0355 (3)	0.0501 (3)	0.0508 (3)	0.0077 (2)	0.0182 (2)	0.0015 (2)
Cl4	0.0693 (4)	0.0454 (3)	0.0335 (3)	0.0115 (3)	0.0101 (2)	−0.0131 (2)
Cl5	0.0408 (3)	0.0329 (2)	0.0352 (2)	−0.00885 (19)	−0.00350 (19)	0.00085 (19)
Cl6	0.0460 (3)	0.0377 (3)	0.0628 (4)	−0.0004 (2)	0.0267 (3)	0.0081 (3)
Cl7	0.0566 (3)	0.0565 (3)	0.0241 (2)	0.0145 (3)	0.0046 (2)	0.0129 (2)
Cl8	0.0339 (2)	0.0287 (2)	0.0518 (3)	−0.00371 (18)	−0.0026 (2)	−0.0083 (2)
Cl9	0.0299 (2)	0.0521 (3)	0.0345 (2)	0.0026 (2)	−0.00126 (18)	0.0047 (2)
Cl10	0.0467 (3)	0.0384 (3)	0.0377 (3)	0.0036 (2)	0.0133 (2)	−0.0090 (2)
C1	0.0304 (9)	0.0270 (9)	0.0333 (9)	0.0010 (7)	0.0030 (7)	0.0006 (7)
C2	0.0299 (9)	0.0239 (8)	0.0335 (9)	0.0010 (7)	0.0051 (7)	−0.0005 (7)
C3	0.0372 (9)	0.0256 (9)	0.0235 (8)	0.0017 (7)	0.0031 (7)	−0.0025 (7)
C4	0.0339 (9)	0.0281 (9)	0.0271 (8)	0.0043 (7)	0.0079 (7)	0.0055 (7)
C5	0.0347 (9)	0.0214 (8)	0.0284 (8)	0.0004 (7)	0.0037 (7)	0.0014 (7)
C6	0.0328 (9)	0.0260 (9)	0.0280 (8)	0.0015 (7)	0.0030 (7)	0.0026 (7)

Geometric parameters (Å, º)

Cl1—C1	1.721 (2)	Cl9—C6	1.702 (2)
Cl2—C1	1.700 (2)	Cl10—C6	1.718 (2)
Cl3—C2	1.736 (2)	C1—C2	1.336 (3)
Cl4—C3	1.7806 (19)	C2—C3	1.536 (3)
Cl5—C3	1.782 (2)	C3—C4	1.586 (3)
Cl6—C4	1.793 (2)	C4—C5	1.535 (3)
Cl7—C4	1.771 (2)	C5—C6	1.339 (3)
Cl8—C5	1.737 (2)
C2—C1—Cl2	126.87 (16)	C5—C4—C3	113.08 (15)
C2—C1—Cl1	121.38 (16)	C5—C4—Cl7	112.13 (13)
Cl2—C1—Cl1	111.75 (11)	C3—C4—Cl7	109.21 (14)
C1—C2—C3	127.38 (18)	C5—C4—Cl6	109.18 (14)
C1—C2—Cl3	116.37 (15)	C3—C4—Cl6	107.63 (13)
C3—C2—Cl3	116.25 (14)	Cl7—C4—Cl6	105.21 (10)
C2—C3—C4	113.02 (15)	C6—C5—C4	128.36 (18)
C2—C3—Cl4	109.25 (13)	C6—C5—Cl8	116.56 (15)
C4—C3—Cl4	109.03 (13)	C4—C5—Cl8	115.05 (14)
C2—C3—Cl5	111.74 (13)	C5—C6—Cl9	127.43 (16)
C4—C3—Cl5	108.28 (13)	C5—C6—Cl10	121.17 (16)
Cl4—C3—Cl5	105.21 (10)	Cl9—C6—Cl10	111.40 (11)
Cl2—C1—C2—C3	1.4 (3)	Cl5—C3—C4—Cl7	61.66 (14)
Cl1—C1—C2—C3	−179.52 (15)	C2—C3—C4—Cl6	−60.28 (18)
Cl2—C1—C2—Cl3	−178.47 (12)	Cl4—C3—C4—Cl6	61.42 (15)
Cl1—C1—C2—Cl3	0.7 (2)	Cl5—C3—C4—Cl6	175.38 (9)
C1—C2—C3—C4	−86.2 (2)	C3—C4—C5—C6	90.7 (2)
Cl3—C2—C3—C4	93.61 (17)	Cl7—C4—C5—C6	−33.3 (3)
C1—C2—C3—Cl4	152.21 (18)	Cl6—C4—C5—C6	−149.47 (18)
Cl3—C2—C3—Cl4	−27.96 (18)	C3—C4—C5—Cl8	−87.37 (18)
C1—C2—C3—Cl5	36.2 (3)	Cl7—C4—C5—Cl8	148.61 (11)
Cl3—C2—C3—Cl5	−143.95 (11)	Cl6—C4—C5—Cl8	32.41 (17)
C2—C3—C4—C5	60.4 (2)	C4—C5—C6—Cl9	2.0 (3)
Cl4—C3—C4—C5	−177.90 (14)	Cl8—C5—C6—Cl9	−179.93 (11)
Cl5—C3—C4—C5	−63.94 (18)	C4—C5—C6—Cl10	−177.43 (15)
C2—C3—C4—Cl7	−174.00 (13)	Cl8—C5—C6—Cl10	0.7 (2)
Cl4—C3—C4—Cl7	−52.30 (16)