Bis­(penta­chloro­phenyl) di­sulfide

The mol­ecule of bis­(penta­chloro­phenyl) di­sulfide, (Cl₅C₆)₂S₂, lies on a twofold axis; the phenyl rings are twisted by 19.2 (1)° and the C—S—S—C torsion angle is −82.8 (2)°. The crystal packing is dominated by weak Cl...Cl contacts of 3.5–3.7 Å.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.099
• Data-to-parameter ratio = 16.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.459     0.767
          Tmin' and Tmax expected:      0.528     0.767
          RR' =      0.869
          Please check that your absorption correction is appropriate.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

Polychloroaromatic hydrocarbons undergo nucleophilic substitution with thiolate ions in polar aprotic solution (Baird et al., 1988), as exemplified by the reaction of perchlorocoronene, C₂₄Cl₁₂, with CH₃O-4-C₆H₄S, in which all Cl atoms are replaced by the CH₃O-4-C₆H₄S groups. On the other hand, hexachlorobenzene reacts with sodium phenylthiolate to form hexa(phenylsulfido)benzene (MacNicol et al., 1982). In the present study, the reaction of C₆Cl₆ with (O₂CCH₂S)²⁻ in DMF afforded a disulfide, C₆Cl₅SSC₆Cl₅ (Fig. 1), (I) instead.

The molecule of (I) occupies a special position on the twofold axis. The S1—S1ⁱ bond distance of 2.063 (2) Å is similar to that found in 2-nitrophenyl 4-nitrophenyl disulfide (Glidewell et al., 2002). The aromatic ring is planar, and the Cl substituents lie close to its plane, the largest deviation being 0.085 (4) Å. The two rings are twisted by 19.2 (1)° and the C1—S1—S1ⁱ—C1ⁱ torsion angle is −82.8 (2)°. The crystal packing is dominated by Cl···Cl contacts of 3.5–3.7 Å.

S2. Experimental

Hexachlorobenzene (0.28 g, 1 mmol) and an excess of disodium thioglycollate (1.34 g, 10 mmol) were refluxed in a DMF–water (1/1) mixture for 5 h. The reaction mixture was cooled, and the product was extracted with toluene. The toluene solution was washed with water and then dried over magnesium sulfate. Evaporation of the solvent afforded the crude product, which was then recrystallized from toluene.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with ellipsoids drawn at the 50% probability level. [Symmetry code: (i) 1 − x, y, 1/2 − z.]

Bis(pentachlorophenyl) disulfide

Crystal data

C12Cl10S2	F(000) = 1096
Mr = 562.74	Dx = 2.074 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.188 (4) Å	Cell parameters from 25 reflections
b = 8.685 (3) Å	θ = 13.0–15.0°
c = 14.645 (3) Å	µ = 1.77 mm^−1
β = 111.12 (1)°	T = 298 K
V = 1802.1 (8) Å^3	Block, yellow
Z = 4	0.35 × 0.33 × 0.15 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	1469 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.0°, θmin = 2.8°
ω scans	h = −18→18
Absorption correction: empirical (using intensity measurements) ψ scan (North et al., 1968)	k = −10→0
Tmin = 0.459, Tmax = 0.767	l = −18→18
3538 measured reflections	2 standard reflections every 60 min
1774 independent reflections	intensity decay: none

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.036	Secondary atom site location: difference Fourier map
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 1.1173P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1774 reflections	Δρmax = 0.43 e Å^−3
109 parameters	Δρmin = −0.32 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.5320 (1)	0.8684 (1)	0.1269 (1)	0.0474 (2)
Cl2	0.3923 (1)	1.1376 (1)	0.1012 (1)	0.0560 (3)
Cl3	0.1879 (1)	1.0737 (1)	0.0895 (1)	0.0547 (3)
Cl4	0.1272 (1)	0.7427 (1)	0.1203 (1)	0.0476 (2)
Cl5	0.2686 (1)	0.4736 (1)	0.1554 (1)	0.0451 (2)
S1	0.4798 (1)	0.5319 (1)	0.1748 (1)	0.0421 (2)
C1	0.3955 (2)	0.6824 (3)	0.1443 (2)	0.0318 (6)
C2	0.4210 (2)	0.8316 (3)	0.1283 (2)	0.0344 (6)
C3	0.3582 (2)	0.9531 (3)	0.1128 (2)	0.0351 (7)
C4	0.2668 (2)	0.9252 (3)	0.1107 (2)	0.0359 (7)
C5	0.2397 (2)	0.7770 (3)	0.1239 (2)	0.0316 (6)
C6	0.3033 (2)	0.6567 (3)	0.1404 (2)	0.0317 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0323 (4)	0.0505 (5)	0.0628 (6)	−0.0076 (3)	0.0214 (4)	0.0030 (4)
Cl2	0.0584 (5)	0.0324 (4)	0.0817 (7)	−0.0042 (3)	0.0307 (5)	0.0109 (4)
Cl3	0.0510 (5)	0.0423 (5)	0.0751 (6)	0.0179 (4)	0.0281 (5)	0.0133 (4)
Cl4	0.0301 (4)	0.0510 (5)	0.0665 (6)	−0.0022 (3)	0.0233 (4)	−0.0025 (4)
Cl5	0.0410 (4)	0.0313 (4)	0.0638 (5)	−0.0067 (3)	0.0200 (4)	0.0021 (4)
S1	0.0317 (4)	0.0335 (4)	0.0589 (5)	0.0032 (3)	0.0137 (4)	−0.0085 (3)
C1	0.030 (1)	0.031 (1)	0.036 (2)	0.003 (1)	0.012 (1)	−0.001 (1)
C2	0.029 (1)	0.039 (2)	0.036 (2)	−0.004 (1)	0.013 (1)	−0.003 (1)
C3	0.039 (2)	0.030 (1)	0.038 (2)	−0.005 (1)	0.014 (1)	0.001 (1)
C4	0.038 (2)	0.034 (2)	0.037 (2)	0.008 (1)	0.016 (1)	0.003 (1)
C5	0.024 (1)	0.036 (1)	0.036 (2)	−0.001 (1)	0.011 (1)	−0.001 (1)
C6	0.033 (2)	0.029 (1)	0.033 (2)	−0.004 (1)	0.010 (1)	−0.002 (1)

Geometric parameters (Å, º)

Cl1—C2	1.722 (3)	C1—C2	1.397 (4)
Cl2—C3	1.712 (3)	C1—C6	1.398 (4)
Cl3—C4	1.710 (3)	C2—C3	1.385 (4)
Cl4—C5	1.717 (3)	C3—C4	1.398 (4)
Cl5—C6	1.715 (3)	C4—C5	1.386 (4)
S1—C1	1.771 (3)	C5—C6	1.384 (4)
S1—S1^i	2.063 (2)
C1—S1—S1^i	100.3 (1)	C5—C4—C3	120.0 (3)
C2—C1—C6	118.4 (3)	C5—C4—Cl3	120.1 (2)
C2—C1—S1	120.5 (2)	C3—C4—Cl3	119.9 (2)
C6—C1—S1	121.0 (2)	C6—C5—C4	120.1 (3)
C3—C2—C1	121.1 (3)	C6—C5—Cl4	119.9 (2)
C3—C2—Cl1	118.4 (2)	C4—C5—Cl4	119.9 (2)
C1—C2—Cl1	120.4 (2)	C5—C6—C1	120.8 (3)
C2—C3—C4	119.5 (3)	C5—C6—Cl5	119.7 (2)
C2—C3—Cl2	120.9 (2)	C1—C6—Cl5	119.5 (2)
C4—C3—Cl2	119.6 (2)
S1^i—S1—C1—C2	96.5 (3)	Cl2—C3—C4—Cl3	3.7 (4)
S1^i—S1—C1—C6	−80.5 (3)	C3—C4—C5—C6	0.8 (5)
C6—C1—C2—C3	2.6 (5)	Cl3—C4—C5—C6	179.6 (2)
S1—C1—C2—C3	−174.4 (2)	C3—C4—C5—Cl4	−179.5 (2)
C6—C1—C2—Cl1	−177.1 (2)	Cl3—C4—C5—Cl4	−0.7 (4)
S1—C1—C2—Cl1	5.9 (4)	C4—C5—C6—C1	0.2 (5)
C1—C2—C3—C4	−1.7 (5)	Cl4—C5—C6—C1	−179.5 (2)
Cl1—C2—C3—C4	178.1 (2)	C4—C5—C6—Cl5	−179.3 (2)
C1—C2—C3—Cl2	175.7 (2)	Cl4—C5—C6—Cl5	0.9 (4)
Cl1—C2—C3—Cl2	−4.5 (4)	C2—C1—C6—C5	−1.9 (4)
C2—C3—C4—C5	−0.1 (5)	S1—C1—C6—C5	175.1 (2)
Cl2—C3—C4—C5	−177.4 (2)	C2—C1—C6—Cl5	177.6 (2)
C2—C3—C4—Cl3	−178.9 (2)	S1—C1—C6—Cl5	−5.4 (4)

Symmetry code: (i) −x+1, y, −z+1/2.