2-Chloro­phenyl 4-toluene­sulfonate: molecular aggregration through weak C—H...O interactions

The title mol­ecule, C₁₃H₁₁ClO₃S, is stabilized by weak C—H...O interactions. The dihedral angle between the mean planes of the 4-tolyl and the 2-chloro­phenyl rings is 51.47 (9)°. Both the sulfonyl O atoms form a three-centred symmetrical hydrogen-bonded chelate motif with an H atom of the neighbouring 2-chloro­phenyl ring. In addition, two of the sulfonyl O atoms form two other weak hydrogen bonds with the H atoms of the 4-tolyl rings of two different neighbouring mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.096
• Data-to-parameter ratio = 10.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

p-Toluene sulfonates are used in monitoring the merging of lipids (Yachi et al., 1989), studying membrane fusion during acrosome reaction (Spungin et al., 1992), development of immunoaffinity chromatography for the purification of human coagulation factor (Tharakan et al., 1992), chemical studies on viruses (Alford et al., 1991), development of technology for linking photosensitizer to model monoclonal antibody (Jiang et al., 1990) and chemical modification of σ subunits of the E. coli RNA polymerase (Narayanan & Krakow, 1983). An X-ray study of the title compound, (I), was undertaken in order to determine its crystal and molecular structure owing to the biological importance of its analogues. A search of Version 5.23 of the Cambridge Structural Database (Allen, 2002) revealed 16 structures (refcodes: KAWDAN, FIXCAQ, NEDXUP, NEDYAW, NEDYIE, NUNCII, RASSOT, RELVUZ, SIMVUF, TCPTOS, TEBFOV, TMPDTS, TSMIPH, WOHCUR, ZZZBDA10 and MIWHIJ) that are closely related to the title compound. The S—C, S—O and S═O bond lengths (Table 1) are comparable to those found in these structures. The Cl atom lies almost in the plane of the phenyl ring to which it is bonded. The dihedral angle between the 2-chlorophenyl and the 4-tolyl rings is found to be 51.47 (9)° thereby confirming their non-coplanar orientation. This is in contrast to the near coplanar orientation of the 4-tolyl and 2,4-dinitrophenyl rings in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu et al., 2003).

The crystal structure of (I) is stabilized by weak C—H···O interactions. The range for H···O distances (Table 2) found in (I) agree with those found for weak C—H···O bonds (Desiraju & Steiner, 1999). Both O1 and O2 of the sulfonyl group act as acceptors, forming weak hydrogen bonds with the CH group of the 2-chlorophenyl ring of a neighbouring molecule (Fig. 3). The H12···O1 and H12···O2 distances differ by only 0.12 Å. The resulting configuration is best regarded as a three-centre symmetrical hydrogen-bonded chelate (Desiraju, 1989) and observed in molecules containing fewer functional H atoms and several acceptors. The O1···H12···O2 bite angle is 55.2 (3)° and the sum of angles around H12, 352.4 (2)°, indicates the configuration around it to be almost planar, as observed for many molecules with such hydrogen bonds (Jeffrey & Mitra, 1984). One of the sulfonyl O atoms, O1, acts as an acceptor, forming a weak hydrogen bond with H4 of the 4-tolyl ring of a neighbouring molecule. The other sulfonyl O atom, O2, acts as an acceptor to form another weak hydrogen bond with H6 of the 4-tolyl ring of another neighbouring molecule (Fig. 3). The above intermolecular C—H···O interactions contribute to the molecular aggregation of the title molecule.

S2. Experimental

p-Toluenesulfonyl chloride (0.9 g, 4.7 mmol), dissolved in acetone (4 ml) was added dropwise to 2-chlorophenol (0.5 g, 3.9 mmol) in aqueous NaOH (2.5 ml, 10%) with constant shaking. The precipitated 2-chlorophenyl 4-toluenesulfonate (0.9 g, 3.2 mmol, yield: 82%) was filtered off and recrystallized from aqueous ethanol.

S3. Refinement

All the H atoms were located in a difference Fourier map and their positional and isotropic displacement paramaters were refined. The C—H bond lengths are in the range 0.88 (3)–1.02 (3) Å. The H—C—H angles for the methyl group are in the range 102 (3)—111 (3)°. The C—C—H angles for the phenyl groups are in the range 119 (1)–124 (1)°.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title molecule, showing 50% probablity displacement ellipsoids.
	Fig. 2. Diagram showing the potential C—H···O interactions in the title molecule.

2-chlorophenyl 4-toluenesulfonate

Crystal data

C13H11ClO3S	F(000) = 292
Mr = 282.73	Dx = 1.438 Mg m^−3
Triclinic, P1	Melting point = 72–73 K
a = 7.487 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.675 (4) Å	Cell parameters from 1959 reflections
c = 10.277 (4) Å	θ = 2.4–26.7°
α = 95.378 (6)°	µ = 0.45 mm^−1
β = 97.886 (6)°	T = 100 K
γ = 96.404 (6)°	Needle, colorless
V = 653.0 (5) Å^3	0.40 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2227 independent reflections
Radiation source: fine-focus sealed tube	1762 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −8→8
Tmin = 0.841, Tmax = 0.957	k = −10→10
4385 measured reflections	l = −12→12

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0594P)^2] where P = (Fo^2 + 2Fc^2)/3
2227 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.34 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
S	0.33885 (7)	0.50916 (6)	0.19595 (5)	0.02342 (18)
Cl	0.51020 (8)	0.96080 (6)	0.32565 (5)	0.03011 (19)
O1	0.2264 (2)	0.42744 (16)	0.07871 (15)	0.0290 (4)
O2	0.4723 (2)	0.43083 (17)	0.27041 (15)	0.0299 (4)
O3	0.46129 (19)	0.65838 (17)	0.15408 (14)	0.0247 (4)
C1	−0.1413 (4)	0.8042 (3)	0.5581 (3)	0.0342 (6)
C2	−0.0217 (3)	0.7296 (2)	0.4682 (2)	0.0241 (5)
C3	−0.0817 (3)	0.6964 (3)	0.3311 (2)	0.0260 (5)
C4	0.0267 (3)	0.6280 (2)	0.2466 (2)	0.0237 (5)
C5	0.1981 (3)	0.5938 (2)	0.3013 (2)	0.0213 (5)
C6	0.2619 (3)	0.6262 (2)	0.4372 (2)	0.0243 (5)
C7	0.1507 (3)	0.6940 (2)	0.5196 (2)	0.0262 (5)
C8	0.3708 (3)	0.7764 (2)	0.0934 (2)	0.0207 (5)
C9	0.2782 (3)	0.7476 (3)	−0.0355 (2)	0.0264 (5)
C10	0.1998 (3)	0.8697 (3)	−0.0928 (2)	0.0301 (6)
C11	0.2183 (3)	1.0190 (3)	−0.0221 (2)	0.0301 (6)
C12	0.3130 (3)	1.0465 (3)	0.1056 (2)	0.0270 (5)
C13	0.3888 (3)	0.9243 (3)	0.1646 (2)	0.0235 (5)
H1A	−0.130 (4)	0.764 (3)	0.647 (3)	0.057 (9)*
H1B	−0.276 (4)	0.774 (3)	0.524 (3)	0.065 (9)*
H1C	−0.113 (4)	0.906 (4)	0.571 (3)	0.061 (10)*
H3	−0.201 (3)	0.719 (2)	0.294 (2)	0.023 (6)*
H4	−0.015 (3)	0.609 (3)	0.160 (2)	0.025 (6)*
H6	0.378 (3)	0.605 (2)	0.475 (2)	0.018 (5)*
H7	0.203 (3)	0.714 (3)	0.613 (2)	0.025 (6)*
H9	0.268 (3)	0.642 (3)	−0.087 (2)	0.027 (6)*
H10	0.129 (3)	0.849 (3)	−0.181 (2)	0.025 (6)*
H11	0.164 (3)	1.098 (3)	−0.063 (2)	0.030 (6)*
H12	0.335 (3)	1.149 (3)	0.152 (2)	0.034 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0263 (3)	0.0142 (3)	0.0299 (3)	0.0068 (2)	0.0057 (2)	−0.0042 (2)
Cl	0.0373 (4)	0.0229 (3)	0.0275 (3)	0.0019 (2)	0.0036 (2)	−0.0074 (2)
O1	0.0341 (9)	0.0152 (8)	0.0353 (9)	0.0029 (7)	0.0041 (7)	−0.0074 (7)
O2	0.0332 (9)	0.0222 (8)	0.0359 (9)	0.0140 (7)	0.0054 (7)	−0.0013 (7)
O3	0.0239 (8)	0.0187 (8)	0.0323 (9)	0.0078 (6)	0.0066 (7)	−0.0031 (7)
C1	0.0337 (16)	0.0323 (16)	0.0383 (16)	0.0104 (12)	0.0120 (12)	−0.0039 (12)
C2	0.0242 (12)	0.0178 (12)	0.0307 (13)	0.0032 (9)	0.0076 (10)	−0.0006 (10)
C3	0.0205 (12)	0.0253 (13)	0.0322 (13)	0.0060 (10)	0.0024 (10)	0.0021 (10)
C4	0.0266 (13)	0.0193 (12)	0.0239 (13)	0.0026 (10)	0.0028 (10)	−0.0014 (9)
C5	0.0229 (11)	0.0135 (11)	0.0278 (12)	0.0037 (9)	0.0072 (9)	−0.0029 (9)
C6	0.0217 (12)	0.0202 (12)	0.0306 (13)	0.0062 (10)	0.0013 (10)	0.0004 (10)
C7	0.0301 (13)	0.0210 (12)	0.0266 (13)	0.0046 (10)	0.0035 (11)	−0.0024 (10)
C8	0.0180 (11)	0.0164 (11)	0.0276 (12)	0.0034 (9)	0.0061 (9)	−0.0027 (9)
C9	0.0255 (12)	0.0230 (13)	0.0302 (13)	0.0014 (10)	0.0095 (10)	−0.0060 (10)
C10	0.0267 (13)	0.0373 (15)	0.0267 (13)	0.0039 (11)	0.0070 (11)	0.0014 (11)
C11	0.0270 (13)	0.0306 (14)	0.0375 (15)	0.0092 (11)	0.0120 (11)	0.0116 (12)
C12	0.0289 (13)	0.0169 (12)	0.0381 (14)	0.0047 (10)	0.0157 (11)	0.0000 (10)
C13	0.0229 (11)	0.0224 (12)	0.0256 (12)	0.0012 (9)	0.0097 (9)	−0.0030 (9)

Geometric parameters (Å, º)

S—O2	1.4439 (16)	C4—H4	0.89 (2)
S—O1	1.4460 (16)	C5—C6	1.403 (3)
S—O3	1.6276 (16)	C6—C7	1.403 (3)
S—C5	1.777 (2)	C6—H6	0.95 (2)
Cl—C13	1.758 (2)	C7—H7	0.98 (2)
O3—C8	1.433 (3)	C8—C9	1.395 (3)
C1—C2	1.524 (3)	C8—C13	1.399 (3)
C1—H1A	1.01 (3)	C9—C10	1.406 (3)
C1—H1B	1.02 (3)	C9—H9	1.00 (2)
C1—H1C	0.88 (3)	C10—C11	1.407 (3)
C2—C7	1.404 (3)	C10—H10	0.98 (2)
C2—C3	1.411 (3)	C11—C12	1.390 (3)
C3—C4	1.403 (3)	C11—H11	0.94 (2)
C3—H3	0.97 (2)	C12—C13	1.405 (3)
C4—C5	1.404 (3)	C12—H12	0.96 (3)
O2—S—O1	119.82 (9)	C7—C6—C5	118.8 (2)
O2—S—O3	102.91 (9)	C7—C6—H6	118.9 (13)
O1—S—O3	108.77 (9)	C5—C6—H6	122.2 (13)
O2—S—C5	110.68 (10)	C6—C7—C2	121.1 (2)
O1—S—C5	109.25 (10)	C6—C7—H7	115.1 (13)
O3—S—C5	104.10 (9)	C2—C7—H7	123.9 (13)
C8—O3—S	118.70 (13)	C9—C8—C13	121.1 (2)
C2—C1—H1A	112.2 (16)	C9—C8—O3	121.04 (18)
C2—C1—H1B	112.1 (17)	C13—C8—O3	117.68 (19)
H1A—C1—H1B	102 (2)	C8—C9—C10	118.8 (2)
C2—C1—H1C	111 (2)	C8—C9—H9	120.9 (13)
H1A—C1—H1C	108 (3)	C10—C9—H9	120.4 (13)
H1B—C1—H1C	111 (3)	C9—C10—C11	120.4 (2)
C7—C2—C3	118.80 (19)	C9—C10—H10	119.3 (13)
C7—C2—C1	120.8 (2)	C11—C10—H10	120.3 (13)
C3—C2—C1	120.4 (2)	C12—C11—C10	120.2 (2)
C4—C3—C2	121.3 (2)	C12—C11—H11	121.3 (14)
C4—C3—H3	119.1 (13)	C10—C11—H11	118.5 (14)
C2—C3—H3	119.6 (13)	C11—C12—C13	119.7 (2)
C3—C4—C5	118.4 (2)	C11—C12—H12	121.2 (14)
C3—C4—H4	119.2 (14)	C13—C12—H12	118.9 (14)
C5—C4—H4	122.4 (14)	C8—C13—C12	119.7 (2)
C4—C5—C6	121.63 (19)	C8—C13—Cl	120.87 (17)
C4—C5—S	119.23 (16)	C12—C13—Cl	119.38 (17)
C6—C5—S	119.14 (16)
O2—S—O3—C8	−171.50 (14)	C5—C6—C7—C2	−0.2 (3)
O1—S—O3—C8	60.44 (16)	C3—C2—C7—C6	−0.1 (3)
C5—S—O3—C8	−55.94 (16)	C1—C2—C7—C6	−179.6 (2)
C7—C2—C3—C4	0.4 (3)	S—O3—C8—C13	112.90 (19)
C1—C2—C3—C4	179.9 (2)	S—O3—C8—C9	−71.2 (2)
C2—C3—C4—C5	−0.4 (3)	C13—C8—C9—C10	−1.1 (3)
C3—C4—C5—C6	0.1 (3)	O3—C8—C9—C10	−176.79 (19)
C3—C4—C5—S	−179.28 (16)	C8—C9—C10—C11	1.5 (3)
O2—S—C5—C6	22.0 (2)	C9—C10—C11—C12	−0.7 (4)
O1—S—C5—C6	155.95 (17)	C10—C11—C12—C13	−0.6 (3)
O3—S—C5—C6	−87.96 (18)	C9—C8—C13—C12	−0.2 (3)
O2—S—C5—C4	−158.63 (17)	O3—C8—C13—C12	175.67 (18)
O1—S—C5—C4	−24.7 (2)	C9—C8—C13—Cl	−178.50 (16)
O3—S—C5—C4	91.41 (18)	O3—C8—C13—Cl	−2.6 (3)
C4—C5—C6—C7	0.2 (3)	C11—C12—C13—C8	1.0 (3)
S—C5—C6—C7	179.55 (17)	C11—C12—C13—Cl	179.34 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl^i	1.02 (3)	3.11 (3)	3.748 (3)	122 (2)
C3—H3···Cl^i	0.97 (2)	3.20 (2)	4.017 (3)	143.0 (16)
C3—H3···O3^i	0.97 (2)	2.70 (2)	3.613 (3)	156.2 (17)
C4—H4···O1^ii	0.89 (2)	2.70 (2)	3.571 (3)	164.1 (19)
C6—H6···O2^iii	0.95 (2)	2.76 (2)	3.477 (3)	132.9 (16)
C7—H7···Cl^iv	0.98 (2)	3.30 (2)	3.774 (2)	111.8 (15)
C9—H9···O2^v	1.00 (2)	2.97 (2)	3.591 (3)	121.2 (15)
C12—H12···O1^vi	0.96 (3)	2.77 (2)	3.466 (3)	130.2 (17)
C12—H12···O2^vi	0.96 (3)	2.65 (3)	3.592 (3)	167.2 (19)

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