3-Nitro­benzene­sulfonyl chloride: molecular aggregation through C—H...O interactions

In the title compound, C₆H₄ClNO₄S, the molecular structure and molecular packing in the crystal are stabilized by C—H...O interactions. The C—H...O interactions form S(5) and R¹₂ ring motifs.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.106
• Data-to-parameter ratio = 14.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Structural studies on aryl sulfonyl chlorides are essential for understanding the mechanisms of nucleophilic substitution reactions at the sulfonyl reaction center (Kislov & Ivanov, 2000). Substitution reactions of sulfonyl chlorides bridge inorganic and organic chemistry (Koo et al., 2000). The complex of 4-toluenesulfonyl chloride with protein had been reported as a ruminant feed material (Miller, US patent No. 3711289). Sulfonyl halides are used as initiators in the metal catalyzed living radical polymerization of acrylonitrile (Barboiu & Percec, 2002). Arene sulfonyl halides were reported to be the universal class of functional initiators for metal catalyzed living radical polymerization of styrenes, methacrylates and acrylates (Percec et al., 1998). The present crystal structure determination of the title compound, (I), is undertaken owing to the biological activity and synthetic utility of its analogues.

A search of the July 2002 release of Cambridge Structural Database (Allen, 2002) revealed 11 structures (with the following refcodes: COKCOU, FAQJOW, FOHYAC, KADZOE, NAQLUM, NAXFEX, NAXFIB, NBZSOC, QQQHJA, QQQHJA01 and SUTYAH) that are closely related to the title compound. The S═O, S—C and S—Cl bond lengths (Table 1) are comparable to those found in these structures. The crystal structure of (I) is stabilized by weak C—H···O interactions. The range of H···O distances (Table 2) found in (I) agrees with those found for weak C—H···O bonds (Desiraju & Steiner, 1999). The C6—H6···O4 and C6—H6···O2 (Fig. 1) interactions constitute a pair of bifurcated donor bonds generating two rings fused to each other each of graph set (Etter, 1990; Bernstein et al., 1995) motif S(5). Each of the C4—H4···O3 and C2—H2···O1 (Fig. 2) interactions generate S(5) motif. The C3—H3···O2ⁱⁱⁱ and C2—H2···O2ⁱⁱⁱ (Fig. 2 and Table 2 for symmetry codes) interactions constitute a pair of bifurcated acceptor bonds generating a ring of graph set R¹₂(5). The molecular aggregation is completed by several other weak C—H···O interactions (Table 2 and Fig. 2). Other short intermolecular contacts are Cl1···O1(1 − x, −y, 1 − z) of 3.231 (2) Å and Cl1···Cl1(1 − x, 1 − y, 1 − z) of 3.437 (1) Å.

S2. Experimental

The title compound was purchased from National Chemicals, Vadodara, Gujarat, India. Diffraction quality crystals were obtained by recrystallizing the sample from a 1:1 mixture of petroleum ether and acetone.

S3. Refinement

H atoms were located from a difference Fourier map and both positional and isotropic displacement paramaters were refined. The C—H bond lengths are in the range 0.90 (3)–0.95 (3) Å and the C—C—H angles for the aromatic ring are in the range 118 (2)–123 (2)°. The highest peak in the difference Fourier map lies close to the Cl atom (0.84 Å).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing 50% probablity displacement ellipsoids and intramolecular C—H···O interactions.
	Fig. 2. Part of the molecular network, showing intermolecular C—H···O interactions and also Cl···Cl and Cl···O contacts. [Symmetry codes: (v) 1 − x, 1 − y, 1 − z; (vi) 1 − x, −y, 1 − z; other codes are given in Table 2.]

3-Nitrobenzenesulfonyl chloride

Crystal data

C6H4ClNO4S	F(000) = 448
Mr = 221.61	Dx = 1.745 Mg m^−3
Monoclinic, P21/n	Melting point: 333-335 K K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.8868 (4) Å	Cell parameters from 823 reflections
b = 9.4298 (4) Å	θ = 2.8–27.5°
c = 11.8789 (5) Å	µ = 0.68 mm^−1
β = 107.318 (2)°	T = 120 K
V = 843.40 (7) Å^3	Block, colourless
Z = 4	0.39 × 0.24 × 0.13 mm

Data collection

Bruker SMART CCD 6K area-detector diffractometer	1928 independent reflections
Radiation source: fine-focus sealed tube	1667 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 8 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −12→12
Tmin = 0.822, Tmax = 0.916	l = −15→15
9420 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.106	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.872P] where P = (Fo^2 + 2Fc^2)/3
1928 reflections	(Δ/σ)max < 0.001
134 parameters	Δρmax = 1.26 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

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	0.32306 (8)	0.43025 (6)	0.53772 (6)	0.03728 (19)
S1	0.10523 (7)	0.30523 (5)	0.49511 (4)	0.02122 (16)
O1	0.3023 (3)	−0.28186 (18)	0.32733 (16)	0.0359 (4)
O2	0.1028 (3)	−0.13592 (19)	0.22689 (15)	0.0386 (4)
O3	0.0254 (2)	0.32696 (18)	0.58608 (16)	0.0316 (4)
O4	0.0094 (3)	0.3315 (2)	0.37543 (16)	0.0410 (5)
N1	0.2148 (3)	−0.17316 (19)	0.31766 (16)	0.0248 (4)
C1	0.2439 (3)	−0.0821 (2)	0.42233 (18)	0.0203 (4)
C2	0.3410 (3)	−0.1353 (2)	0.5311 (2)	0.0244 (4)
C3	0.3635 (3)	−0.0513 (2)	0.6308 (2)	0.0271 (5)
C4	0.2911 (3)	0.0838 (2)	0.61985 (19)	0.0247 (5)
C5	0.1983 (3)	0.1340 (2)	0.50833 (18)	0.0190 (4)
C6	0.1716 (3)	0.0529 (2)	0.40713 (18)	0.0194 (4)
H2	0.386 (4)	−0.224 (3)	0.540 (2)	0.026 (6)*
H3	0.429 (4)	−0.082 (3)	0.706 (3)	0.040 (8)*
H4	0.303 (3)	0.139 (3)	0.685 (2)	0.025 (6)*
H6	0.108 (4)	0.086 (3)	0.330 (2)	0.026 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0286 (3)	0.0218 (3)	0.0638 (4)	−0.0036 (2)	0.0174 (3)	−0.0001 (3)
S1	0.0207 (3)	0.0197 (3)	0.0215 (3)	0.00173 (19)	0.0036 (2)	−0.00229 (18)
O1	0.0443 (10)	0.0287 (9)	0.0386 (10)	0.0089 (8)	0.0183 (8)	−0.0060 (7)
O2	0.0581 (12)	0.0280 (9)	0.0229 (8)	0.0007 (8)	0.0015 (8)	−0.0050 (7)
O3	0.0325 (9)	0.0284 (9)	0.0398 (10)	−0.0031 (7)	0.0194 (8)	−0.0083 (7)
O4	0.0527 (12)	0.0318 (9)	0.0266 (9)	0.0173 (8)	−0.0064 (8)	−0.0034 (7)
N1	0.0318 (10)	0.0220 (9)	0.0230 (9)	−0.0032 (7)	0.0117 (8)	−0.0015 (7)
C1	0.0210 (10)	0.0192 (10)	0.0216 (10)	−0.0028 (8)	0.0077 (8)	−0.0022 (8)
C2	0.0245 (10)	0.0192 (11)	0.0286 (11)	0.0008 (8)	0.0067 (9)	0.0028 (8)
C3	0.0310 (12)	0.0247 (11)	0.0210 (10)	0.0008 (9)	0.0010 (9)	0.0034 (8)
C4	0.0279 (11)	0.0249 (11)	0.0186 (10)	−0.0009 (8)	0.0027 (8)	−0.0015 (8)
C5	0.0189 (9)	0.0172 (10)	0.0200 (9)	0.0004 (7)	0.0043 (7)	0.0008 (7)
C6	0.0189 (10)	0.0211 (10)	0.0174 (9)	−0.0015 (8)	0.0044 (8)	0.0016 (7)

Geometric parameters (Å, º)

S1—O3	1.4182 (17)	C1—C6	1.384 (3)
S1—O4	1.4193 (18)	C1—C2	1.385 (3)
S1—C5	1.761 (2)	C6—H6	0.95 (3)
S1—Cl1	2.0198 (8)	C3—C4	1.386 (3)
O1—N1	1.222 (3)	C3—C2	1.391 (3)
N1—O2	1.224 (3)	C3—H3	0.93 (3)
N1—C1	1.472 (3)	C4—H4	0.91 (3)
C5—C6	1.387 (3)	C2—H2	0.90 (3)
C5—C4	1.392 (3)
O3—S1—O4	120.87 (12)	C2—C1—N1	118.73 (19)
O3—S1—C5	109.41 (10)	C1—C6—C5	116.33 (19)
O4—S1—C5	109.45 (10)	C1—C6—H6	120.5 (16)
O3—S1—Cl1	105.20 (8)	C5—C6—H6	123.2 (16)
O4—S1—Cl1	107.98 (10)	C4—C3—C2	119.9 (2)
C5—S1—Cl1	102.24 (7)	C4—C3—H3	118.2 (19)
O1—N1—O2	124.23 (19)	C2—C3—H3	121.9 (19)
O1—N1—C1	117.94 (18)	C3—C4—C5	119.2 (2)
O2—N1—C1	117.83 (18)	C3—C4—H4	120.6 (16)
C6—C5—C4	122.58 (19)	C5—C4—H4	120.2 (16)
C6—C5—S1	118.46 (15)	C1—C2—C3	118.9 (2)
C4—C5—S1	118.93 (16)	C1—C2—H2	122.4 (18)
C6—C1—C2	123.1 (2)	C3—C2—H2	118.6 (17)
C6—C1—N1	118.14 (18)
O3—S1—C5—C6	135.78 (17)	C2—C1—C6—C5	−1.1 (3)
O4—S1—C5—C6	1.2 (2)	N1—C1—C6—C5	178.45 (18)
Cl1—S1—C5—C6	−113.06 (16)	C4—C5—C6—C1	−0.6 (3)
O3—S1—C5—C4	−42.4 (2)	S1—C5—C6—C1	−178.63 (15)
O4—S1—C5—C4	−176.90 (18)	C2—C3—C4—C5	−0.7 (3)
Cl1—S1—C5—C4	68.79 (18)	C6—C5—C4—C3	1.5 (3)
O1—N1—C1—C6	167.96 (19)	S1—C5—C4—C3	179.53 (17)
O2—N1—C1—C6	−12.9 (3)	C6—C1—C2—C3	1.8 (3)
O1—N1—C1—C2	−12.5 (3)	N1—C1—C2—C3	−177.8 (2)
O2—N1—C1—C2	166.6 (2)	C4—C3—C2—C1	−0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O4	0.95 (3)	2.55 (3)	2.897 (3)	101.9 (18)
C6—H6···O2	0.95 (3)	2.42 (3)	2.712 (3)	97.1 (18)
C4—H4···O3	0.91 (3)	2.79 (3)	3.051 (3)	97.8 (18)
C2—H2···O1	0.90 (3)	2.48 (3)	2.725 (3)	96.0 (19)
C4—H4···O4^i	0.91 (3)	2.38 (3)	3.116 (3)	138 (2)
C6—H6···O1^ii	0.95 (3)	2.52 (3)	3.251 (3)	134 (2)
C3—H3···O2^iii	0.93 (3)	2.97 (3)	3.504 (3)	118 (2)
C2—H2···O2^iii	0.90 (3)	2.71 (3)	3.387 (3)	133 (2)
C3—H3···O3^iv	0.93 (3)	2.54 (3)	3.412 (3)	156 (3)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y−1/2, z+1/2; (iv) −x+1/2, y−1/2, −z+3/2.