Di­chloro­methyl phenyl sulfone

The unequivocal structure of di­chloro­methyl phenyl sulfone, C₇H₆Cl₂O₂S, (I), via X-ray analysis is reported for the first time. Prepared from the reaction of sodium benzene­sulfinate with chloro­form in KOH, (I) exhibited a sharp melting point, 331.5–332.0 K. Several different melting points have been reported. We find that (I) crystallizes as two chemically identical mol­ecules in the asymmetric unit, but with a number of small geometric differences between the two mol­ecules. Intermolecular Cl₂C—H...O—S(O)—Ph hydrogen bonding between the two geometrically different mol­ecules produces infinite molecular chains, which may induce the small geometric differences exhibited in the two mol­ecules of (I).

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.088
• Data-to-parameter ratio = 15.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: PROCESS in TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON.

dichloromethyl phenyl sulfone

Crystal data

C7H6Cl2O2S	Dx = 1.604 Mg m^−3
Mr = 225.09	Melting point = 331.5–332 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 10.353 (3) Å	Cell parameters from 25 reflections
b = 9.5269 (10) Å	θ = 13.7–16.2°
c = 18.9124 (18) Å	µ = 0.87 mm^−1
β = 91.541 (14)°	T = 296 K
V = 1864.6 (7) Å^3	Prism, colorless
Z = 8	0.41 × 0.35 × 0.30 mm
F(000) = 912

Data collection

Rigaku AFC-5S diffractometer	2137 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 25.1°, θmin = 2.0°
ω scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
Tmin = 0.723, Tmax = 0.769	l = −22→22
3501 measured reflections	3 standard reflections every 100 reflections
3305 independent reflections	intensity decay: 0.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0253P)^2 + 0.876P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3305 reflections	Δρmax = 0.21 e Å^−3
218 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0119 (5)

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

	x	y	z	Uiso*/Ueq
Cl1	0.66005 (9)	0.57739 (10)	0.46637 (5)	0.0732 (3)
Cl2	0.58109 (10)	0.43312 (10)	0.33756 (6)	0.0848 (3)
S1	0.67094 (7)	0.71983 (8)	0.32793 (4)	0.0485 (2)
O1	0.5951 (2)	0.7304 (2)	0.26412 (11)	0.0693 (6)
O2	0.80360 (19)	0.6788 (2)	0.32532 (11)	0.0615 (6)
C1	0.6578 (3)	0.8747 (3)	0.37739 (15)	0.0469 (7)
C2	0.5494 (3)	0.9579 (3)	0.36768 (17)	0.0605 (9)
C3	0.5393 (4)	1.0783 (4)	0.4078 (2)	0.0755 (10)
C4	0.6349 (4)	1.1127 (4)	0.4562 (2)	0.0767 (11)
C5	0.7418 (4)	1.0299 (4)	0.46509 (18)	0.0704 (10)
C6	0.7553 (3)	0.9104 (3)	0.42558 (17)	0.0594 (8)
C7	0.5861 (3)	0.5934 (3)	0.38229 (16)	0.0520 (8)
Cl1a	0.20410 (11)	0.63129 (11)	0.22819 (5)	0.0842 (3)
Cl2a	0.12902 (11)	0.90469 (10)	0.27820 (6)	0.0883 (3)
S1a	0.15960 (7)	0.67724 (9)	0.37831 (4)	0.0509 (2)
O1a	0.0773 (2)	0.7571 (2)	0.42241 (10)	0.0649 (6)
O2a	0.2965 (2)	0.6945 (3)	0.38559 (13)	0.0725 (7)
C1a	0.1210 (3)	0.4986 (3)	0.38389 (14)	0.0489 (7)
C2a	0.0006 (3)	0.4623 (4)	0.40854 (15)	0.0582 (8)
C3a	−0.0311 (4)	0.3218 (4)	0.41355 (18)	0.0705 (10)
C4a	0.0552 (4)	0.2210 (4)	0.39426 (18)	0.0751 (10)
C5a	0.1738 (4)	0.2579 (4)	0.3692 (2)	0.0755 (10)
C6a	0.2082 (3)	0.3969 (4)	0.36406 (17)	0.0630 (9)
C7a	0.1111 (3)	0.7233 (3)	0.28827 (15)	0.0533 (8)
H2	0.4847	0.9334	0.3349	0.073*
H3	0.4675	1.1361	0.4020	0.091*
H4	0.6270	1.1935	0.4834	0.092*
H5	0.8059	1.0547	0.4982	0.084*
H6	0.8285	0.8545	0.4311	0.071*
H7	0.4973	0.6263	0.3879	0.062*
H2a	−0.0578	0.5313	0.4215	0.070*
H3a	−0.1114	0.2956	0.4301	0.085*
H4a	0.0334	0.1267	0.3981	0.090*
H5a	0.2311	0.1884	0.3557	0.091*
H6a	0.2887	0.4221	0.3475	0.076*
H7a	0.0200	0.6985	0.2804	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0758 (6)	0.0843 (7)	0.0593 (5)	−0.0112 (5)	−0.0031 (4)	0.0180 (5)
Cl2	0.1002 (8)	0.0528 (5)	0.1018 (8)	−0.0144 (5)	0.0109 (6)	−0.0181 (5)
S1	0.0493 (4)	0.0500 (4)	0.0461 (4)	−0.0005 (4)	−0.0010 (3)	−0.0006 (4)
O1	0.0840 (16)	0.0756 (16)	0.0474 (12)	0.0067 (13)	−0.0149 (11)	−0.0021 (11)
O2	0.0462 (12)	0.0671 (15)	0.0715 (14)	0.0024 (11)	0.0107 (10)	−0.0023 (12)
C1	0.0481 (17)	0.0435 (17)	0.0491 (17)	−0.0056 (14)	0.0013 (13)	0.0028 (14)
C2	0.057 (2)	0.057 (2)	0.067 (2)	0.0013 (17)	−0.0032 (16)	0.0032 (17)
C3	0.075 (2)	0.052 (2)	0.100 (3)	0.0071 (19)	0.011 (2)	−0.003 (2)
C4	0.108 (3)	0.049 (2)	0.074 (2)	−0.012 (2)	0.016 (2)	−0.0108 (18)
C5	0.092 (3)	0.056 (2)	0.063 (2)	−0.022 (2)	−0.0102 (19)	−0.0045 (18)
C6	0.059 (2)	0.054 (2)	0.065 (2)	−0.0089 (16)	−0.0082 (16)	0.0028 (16)
C7	0.0425 (17)	0.0509 (18)	0.0625 (19)	−0.0045 (14)	0.0013 (14)	−0.0017 (15)
Cl1a	0.1148 (8)	0.0822 (7)	0.0569 (5)	0.0216 (6)	0.0302 (5)	−0.0024 (5)
Cl2a	0.1195 (9)	0.0564 (6)	0.0896 (7)	0.0057 (5)	0.0115 (6)	0.0075 (5)
S1a	0.0448 (4)	0.0604 (5)	0.0472 (4)	−0.0025 (4)	−0.0034 (3)	−0.0085 (4)
O1a	0.0683 (14)	0.0765 (16)	0.0502 (12)	0.0007 (12)	0.0076 (11)	−0.0200 (11)
O2a	0.0441 (12)	0.0804 (17)	0.0923 (17)	−0.0070 (12)	−0.0118 (11)	−0.0081 (14)
C1a	0.0485 (17)	0.061 (2)	0.0370 (15)	−0.0021 (15)	−0.0081 (13)	0.0007 (14)
C2a	0.063 (2)	0.069 (2)	0.0430 (17)	−0.0009 (18)	0.0048 (15)	0.0024 (16)
C3a	0.074 (2)	0.078 (3)	0.060 (2)	−0.013 (2)	0.0097 (18)	0.0068 (19)
C4a	0.097 (3)	0.060 (2)	0.068 (2)	−0.009 (2)	−0.006 (2)	0.0087 (19)
C5a	0.078 (3)	0.065 (3)	0.082 (3)	0.011 (2)	−0.012 (2)	−0.002 (2)
C6a	0.054 (2)	0.067 (2)	0.067 (2)	0.0019 (18)	−0.0037 (16)	−0.0027 (18)
C7a	0.0588 (19)	0.0525 (18)	0.0488 (17)	−0.0007 (16)	0.0048 (14)	−0.0029 (15)

Geometric parameters (Å, º)

Cl1—C7	1.753 (3)	C3—C4	1.370 (5)
Cl1a—C7a	1.745 (3)	C3a—C4a	1.367 (5)
Cl2—C7	1.746 (3)	C4—C5	1.366 (5)
Cl2a—C7a	1.749 (3)	C4a—C5a	1.373 (5)
S1—O1	1.425 (2)	C5—C6	1.370 (4)
S1a—O1a	1.428 (2)	C5a—C6a	1.376 (5)
S1—O2	1.430 (2)	C2—H2	0.9300
S1a—O2a	1.429 (2)	C2a—H2a	0.9300
S1—C1	1.754 (3)	C3—H3	0.9300
S1a—C1a	1.752 (3)	C3a—H3a	0.9300
S1—C7	1.824 (3)	C4—H4	0.9300
S1a—C7a	1.816 (3)	C4a—H4a	0.9300
C1—C2	1.382 (4)	C5—H5	0.9300
C1a—C2a	1.386 (4)	C5a—H5a	0.9300
C1—C6	1.384 (4)	C6—H6	0.9300
C1a—C6a	1.383 (4)	C6a—H6a	0.9300
C2—C3	1.381 (5)	C7—H7	0.9800
C2a—C3a	1.383 (5)	C7a—H7a	0.9800
O1—S1—O2	119.83 (14)	Cl2—C7—S1	108.24 (16)
O1a—S1a—O2a	119.20 (14)	Cl2a—C7a—S1a	108.26 (16)
O1—S1—C1	110.07 (14)	Cl1—C7—S1	111.31 (16)
O1a—S1a—C1a	109.97 (14)	Cl1a—C7a—S1a	110.25 (17)
O2—S1—C1	109.68 (14)	C3—C2—H2	120.8
O2a—S1a—C1a	109.47 (15)	C1—C2—H2	120.8
O1—S1—C7	105.14 (14)	C3a—C2a—H2a	120.6
O1a—S1a—C7a	105.37 (14)	C1a—C2a—H2a	120.6
O2—S1—C7	108.45 (14)	C4—C3—H3	119.9
O2a—S1a—C7a	108.09 (15)	C2—C3—H3	119.9
C1—S1—C7	102.10 (13)	C4a—C3a—H3a	119.9
C1a—S1a—C7a	103.49 (14)	C2a—C3a—H3a	119.9
C2—C1—C6	121.4 (3)	C5—C4—H4	119.6
C2a—C1a—C6a	121.0 (3)	C3—C4—H4	119.6
C2—C1—S1	119.1 (2)	C3a—C4a—H4a	119.7
C2a—C1a—S1a	118.1 (3)	C5a—C4a—H4a	119.7
C6—C1—S1	119.5 (2)	C4—C5—H5	119.8
C6a—C1a—S1a	120.8 (2)	C6—C5—H5	119.8
C3—C2—C1	118.4 (3)	C4a—C5a—H5a	119.8
C3a—C2a—C1a	118.8 (3)	C6a—C5a—H5a	119.8
C4—C3—C2	120.2 (4)	C5—C6—H6	120.6
C4a—C3a—C2a	120.2 (3)	C1—C6—H6	120.6
C5—C4—C3	120.8 (3)	C5a—C6a—H6a	120.6
C5a—C4a—C3a	120.6 (4)	C1a—C6a—H6a	120.6
C4—C5—C6	120.4 (3)	Cl2—C7—H7	108.5
C4a—C5a—C6a	120.4 (4)	Cl1—C7—H7	108.5
C5—C6—C1	118.7 (3)	S1—C7—H7	108.5
C5a—C6a—C1a	118.9 (3)	Cl1a—C7a—H7a	109.0
Cl2—C7—Cl1	111.72 (17)	Cl2a—C7a—H7a	109.0
Cl2a—C7a—Cl1a	111.32 (17)	S1a—C7a—H7a	109.0
O1—S1—C1—C2	24.6 (3)	C3—C4—C5—C6	0.0 (6)
O1a—S1a—C1a—C2a	19.7 (3)	C3a—C4a—C5a—C6a	0.9 (6)
O2—S1—C1—C2	158.5 (2)	C4—C5—C6—C1	−0.8 (5)
O2a—S1a—C1a—C2a	152.4 (2)	C4a—C5a—C6a—C1a	−0.6 (5)
C7—S1—C1—C2	−86.6 (3)	C2—C1—C6—C5	1.1 (5)
C7a—S1a—C1a—C2a	−92.5 (2)	C2a—C1a—C6a—C5a	−0.1 (5)
O1—S1—C1—C6	−155.9 (2)	S1—C1—C6—C5	−178.3 (2)
O1a—S1a—C1a—C6a	−160.5 (2)	S1a—C1a—C6a—C5a	−179.9 (3)
O2—S1—C1—C6	−22.1 (3)	O1—S1—C7—Cl2	61.40 (19)
O2a—S1a—C1a—C6a	−27.7 (3)	O1a—S1a—C7a—Cl2a	58.43 (19)
C7—S1—C1—C6	92.8 (3)	O2—S1—C7—Cl2	−67.91 (18)
C7a—S1a—C1a—C6a	87.3 (3)	O2a—S1a—C7a—Cl2a	−70.04 (19)
C6—C1—C2—C3	−0.5 (5)	C1—S1—C7—Cl2	176.34 (16)
C6a—C1a—C2a—C3a	0.4 (4)	C1a—S1a—C7a—Cl2a	173.91 (16)
S1—C1—C2—C3	178.9 (3)	O1—S1—C7—Cl1	−175.45 (16)
S1a—C1a—C2a—C3a	−179.7 (2)	O1a—S1a—C7a—Cl1a	−179.58 (16)
C1—C2—C3—C4	−0.4 (5)	O2—S1—C7—Cl1	55.2 (2)
C1a—C2a—C3a—C4a	−0.2 (5)	O2a—S1a—C7a—Cl1a	51.9 (2)
C2—C3—C4—C5	0.7 (6)	C1—S1—C7—Cl1	−60.51 (19)
C2a—C3a—C4a—C5a	−0.5 (5)	C1a—S1a—C7a—Cl1a	−64.10 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O2a	0.98	2.18	3.151 (4)	172
C7a—H7a···O2^i	0.98	2.42	3.305 (4)	149

Symmetry code: (i) x−1, y, z.