4-Chloro­phenyl 4-toluene­sulfonate: supramolecular aggregation through C—H...O, C–H...Cl and C—H...π interactions

In the crystal structure of the title mol­ecule, C₁₃H₁₁ClO₃S, the dihedral angle between the mean planes of the 4-tolyl and 4-chloro­phenyl rings is 64.95 (6)°. There are weak C—H...O hydrogen bonds which generate rings of motifs S(5), S(6), R¹₂(9), R²₁(4), R¹₂(6) and R²₂(8). The supramolecular aggregation is completed by the presence of C—H...Cl and C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.094
• Data-to-parameter ratio = 15.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.31
         From the CIF: _reflns_number_total               3099
         Count of symmetry unique reflns         1715
         Completeness (_total/calc)            180.70%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1384
         Fraction of Friedel pairs measured     0.807
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

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 sigma sub units 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.

The dihedral angle between the mean planes of the 4-tolyl and 4-chlorophenyl rings is 64.95 (6)°. This shows their non-coplanar orientation similar to that found in 2-chlorophenyl 4-toluenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003b), 8-tosyloxyquinoline (Vembu, Nallu, Garrison & Youngs, 2003c) and in contrast to the near coplanar orientation observed in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003a) and 4-methoxyphenyl 4-toluenesulfonate (Vembu, Nallu, Garrison, Hindi & Youngs, 2003).

The crystal structure of (I) is stabilized by weak C—H···O interactions. The range for the H···O distances (Table 2) agree with those found for weak C—H···O bonds (Desiraju & Steiner, 1999). The C4—H4···O1 and C4—H4···O3 interactions constitute a pair of bifurcated donor bonds, each of them generating a S(5) graph set (Etter, 1990; Bernstein et al., 1995) motif which are fused to each other. The C6—H6···O2 and C13—H13···O2 interactions constitute a pair of bifurcated acceptor bonds. They generate rings of graph-set motifs S(5) and S(6), respectively, which are fused to each other. The C9—H9···O2^v and C4—H4···O2^v (Table 2 and Fig. 4) interactions form a pair of bifurcated acceptor bonds, generating a ring of graph set R¹₂(9). The C7—H7···O3ⁱⁱⁱ and C7—H7···O1ⁱⁱⁱ(Fig. 3) interactions form a pair of bifurcated donor bonds generating a ring of graph set R²₁(4). The H7···O3ⁱⁱⁱ and H7···O1ⁱⁱⁱ distances differ by 0.18 (3) Å. The resulting configuration can be regarded as a three-centered hygrogen-bonded chelate (Desiraju, 1989) and observed in similar structures (Vembu, Nallu, Garrison & Youngs, 2003b and 2003c; Vembu, Nallu, Garrison, Hindi & Youngs, 2003). The C7—H7···O3ⁱⁱⁱ (Fig. 3) and C1—H1C···O3ⁱⁱⁱ (Fig. 2) interactions constitute a pair of bifurcated acceptor bonds, generating a ring of graph set R¹₂(6). The C1—H1C···O3ⁱⁱⁱ (Fig. 2) and C7—H7···O1ⁱⁱⁱ (Fig. 3) interactions generate a R²₂(8) motif which consists of R²₁(4) chelate and R¹₂(6) ring motifs.

There are several other C—H···O (Figs. 3 and 4) and a C—H···Cl (Fig. 2) interactions which contribute for the supramolecular aggregation (Table 2). The supramolecular aggregation is completed by the presence of two C—H···π interactions (Table 2). The geometry of the C—H···π interaction was obtained from PLATON (Spek, 1998); Cg1 and Cg2 are the centroids of 4-tolyl and 4-chlorophenyl rings, respectively. Molecular packing in the unit cell is shown in Fig. 5.

S2. Experimental

4-Toluenesulfonyl chloride (4.7 mmol), dissolved in actone (4 ml), was added dropwise to 4-chlorophenol (5 mmol) in aqueous NaOH (2.5 ml, 10%) with constant shaking. The precipitated title compound (3.5 mmol, yield 74%) was filtered off and recrystallized from a 1:1 mixture of petroleum ether and acetone.

S3. Refinement

All hydrogen atoms were located from a difference Fourier map and their positional coordinates and isotropic displacement paramaters were refined. The C—H bond lengths are in the range 0.82 (4)–1.00 (3) Å, the H—C—H angles for the methyl group are in the range 101 (3)–108 (3)° and the C—C—H angles for the aromatic rings are in the range 115 (2)–130 (3)°.

Computing details

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

Figures

	Fig. 1. The Molecular Structure of the title molecule, with displacement ellipsoids drawn at the 50% probablity level.
	Fig. 2. Diagram showing hydrogen bonds 3 and 9 (the numbering relates to sequence of entries in Table 2).
	Fig. 3. Diagram showing hydrogen bonds 1, 4, 6 and 7 (the numbering relates to sequence of entries in Table 2).
	Fig. 4. Diagram showing hydrogen bonds 4 and 5 (the numbering relates to sequence of entries in Table 2).
	Fig. 5. Packing of the molecule in the unit cell.

4-chlorophenyl 4-toluenesulfonate

Crystal data

C13H11ClO3S	Dx = 1.456 Mg m^−3
Mr = 282.73	Melting point = 343–344 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 5.8937 (6) Å	Cell parameters from 8098 reflections
b = 27.647 (3) Å	θ = 2.6–28.3°
c = 7.9171 (8) Å	µ = 0.45 mm^−1
V = 1290.1 (2) Å^3	T = 100 K
Z = 4	Plate, colorless
F(000) = 584	0.50 × 0.30 × 0.10 mm

Data collection

CCD area detector diffractometer	3099 independent reflections
Radiation source: fine-focus sealed tube	2964 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.805, Tmax = 0.956	k = −35→36
10721 measured reflections	l = −10→10

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)] = 0.039	All H-atom parameters refined
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0579P)^2 + 0.1095P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
3099 reflections	Δρmax = 0.77 e Å^−3
207 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack(1983), 1384 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

Special details

Experimental. The Tmin and Tmax values obtained from the SIZE instruction are listed above. The absorption correction was applied using SADABS and it gives 0.741957 ratio of min/max transmission"

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	0.95291 (9)	0.341051 (17)	0.34256 (7)	0.01823 (13)
Cl	0.66184 (12)	0.58207 (2)	0.42087 (9)	0.03484 (17)
O1	0.9539 (3)	0.29973 (6)	0.2359 (2)	0.0283 (4)
O2	1.1589 (3)	0.36511 (6)	0.3842 (2)	0.0253 (4)
O3	0.7930 (3)	0.37809 (6)	0.24118 (19)	0.0208 (3)
C1	0.4324 (5)	0.29812 (10)	0.9804 (3)	0.0248 (5)
C2	0.5629 (4)	0.30854 (7)	0.8206 (3)	0.0179 (4)
C3	0.4808 (4)	0.29391 (8)	0.6642 (3)	0.0192 (4)
C4	0.5981 (4)	0.30353 (7)	0.5161 (3)	0.0175 (4)
C5	0.8018 (4)	0.32878 (7)	0.5269 (3)	0.0156 (4)
C6	0.8879 (4)	0.34391 (8)	0.6817 (3)	0.0188 (4)
C7	0.7687 (4)	0.33351 (7)	0.8276 (3)	0.0205 (4)
C8	0.7729 (4)	0.42636 (8)	0.2969 (3)	0.0182 (4)
C9	0.5813 (4)	0.43951 (9)	0.3845 (3)	0.0251 (5)
C10	0.5498 (4)	0.48784 (9)	0.4244 (3)	0.0263 (5)
C11	0.7085 (4)	0.52104 (8)	0.3763 (3)	0.0225 (5)
C12	0.9036 (4)	0.50791 (9)	0.2922 (3)	0.0263 (5)
C13	0.9367 (4)	0.45969 (9)	0.2512 (3)	0.0250 (5)
H1A	0.452 (7)	0.2673 (16)	1.014 (6)	0.066 (12)*
H1B	0.269 (5)	0.2998 (10)	0.969 (4)	0.025 (7)*
H1C	0.473 (6)	0.3176 (13)	1.070 (5)	0.046 (10)*
H3	0.343 (5)	0.2793 (10)	0.656 (4)	0.022 (7)*
H4	0.537 (5)	0.2974 (9)	0.406 (4)	0.019 (7)*
H6	1.029 (7)	0.3621 (14)	0.669 (6)	0.066 (12)*
H7	0.815 (4)	0.3432 (9)	0.940 (4)	0.016 (6)*
H9	0.489 (6)	0.4189 (12)	0.411 (5)	0.040 (9)*
H10	0.431 (6)	0.4953 (12)	0.476 (5)	0.044 (10)*
H12	1.014 (6)	0.5315 (13)	0.256 (5)	0.040 (9)*
H13	1.072 (5)	0.4479 (10)	0.191 (4)	0.023 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0191 (2)	0.0207 (2)	0.0149 (2)	0.00053 (18)	0.0032 (2)	0.0006 (2)
Cl	0.0418 (4)	0.0205 (3)	0.0423 (4)	0.0069 (2)	0.0021 (3)	0.0025 (2)
O1	0.0384 (10)	0.0253 (8)	0.0213 (8)	0.0038 (7)	0.0102 (8)	−0.0023 (7)
O2	0.0196 (8)	0.0326 (9)	0.0236 (9)	−0.0036 (6)	0.0032 (6)	0.0062 (7)
O3	0.0245 (8)	0.0225 (8)	0.0155 (7)	−0.0005 (6)	−0.0036 (6)	0.0003 (6)
C1	0.0281 (14)	0.0265 (12)	0.0200 (12)	0.0034 (10)	0.0081 (9)	0.0027 (9)
C2	0.0200 (10)	0.0162 (9)	0.0176 (11)	0.0056 (7)	0.0057 (8)	0.0028 (8)
C3	0.0150 (11)	0.0186 (10)	0.0240 (11)	−0.0008 (8)	0.0009 (9)	0.0016 (8)
C4	0.0161 (10)	0.0201 (9)	0.0164 (10)	0.0004 (8)	−0.0017 (8)	0.0000 (9)
C5	0.0165 (10)	0.0182 (9)	0.0122 (9)	0.0023 (7)	0.0016 (7)	0.0018 (7)
C6	0.0165 (10)	0.0231 (10)	0.0169 (11)	−0.0025 (8)	0.0000 (8)	−0.0022 (8)
C7	0.0225 (10)	0.0235 (10)	0.0156 (11)	−0.0009 (8)	−0.0020 (9)	−0.0032 (8)
C8	0.0184 (10)	0.0203 (9)	0.0158 (10)	0.0008 (8)	−0.0030 (7)	0.0030 (8)
C9	0.0182 (10)	0.0272 (11)	0.0299 (14)	−0.0055 (9)	0.0028 (8)	0.0036 (9)
C10	0.0212 (12)	0.0281 (11)	0.0295 (13)	0.0040 (8)	0.0061 (10)	0.0015 (10)
C11	0.0249 (11)	0.0222 (10)	0.0203 (12)	0.0035 (8)	−0.0033 (8)	0.0013 (8)
C12	0.0234 (12)	0.0235 (11)	0.0320 (13)	−0.0019 (9)	0.0028 (9)	0.0073 (9)
C13	0.0218 (11)	0.0277 (12)	0.0254 (12)	0.0010 (9)	0.0072 (9)	0.0069 (9)

Geometric parameters (Å, º)

S—O1	1.4216 (18)	C4—H4	0.96 (3)
S—O2	1.4227 (17)	C5—C6	1.390 (3)
S—O3	1.6071 (16)	C6—C7	1.383 (3)
S—C5	1.743 (2)	C6—H6	0.98 (5)
Cl—C11	1.745 (2)	C7—H7	0.98 (3)
O3—C8	1.410 (3)	C8—C9	1.375 (3)
C1—C2	1.508 (3)	C8—C13	1.384 (3)
C1—H1A	0.89 (5)	C9—C10	1.387 (4)
C1—H1B	0.96 (3)	C9—H9	0.82 (4)
C1—H1C	0.92 (4)	C10—C11	1.366 (3)
C2—C3	1.390 (3)	C10—H10	0.83 (4)
C2—C7	1.397 (3)	C11—C12	1.377 (3)
C3—C4	1.387 (3)	C12—C13	1.387 (4)
C3—H3	0.91 (3)	C12—H12	0.97 (4)
C4—C5	1.393 (3)	C13—H13	1.00 (3)
O1—S—O2	120.66 (11)	C7—C6—C5	119.3 (2)
O1—S—O3	102.58 (10)	C7—C6—H6	130 (3)
O2—S—O3	108.58 (9)	C5—C6—H6	111 (3)
O1—S—C5	110.11 (10)	C6—C7—C2	120.7 (2)
O2—S—C5	109.40 (10)	C6—C7—H7	124.3 (16)
O3—S—C5	104.06 (9)	C2—C7—H7	115.0 (16)
C8—O3—S	119.71 (13)	C9—C8—C13	122.0 (2)
C2—C1—H1A	112 (3)	C9—C8—O3	118.50 (19)
C2—C1—H1B	114.2 (18)	C13—C8—O3	119.3 (2)
H1A—C1—H1B	101 (3)	C8—C9—C10	118.7 (2)
C2—C1—H1C	114 (2)	C8—C9—H9	120 (3)
H1A—C1—H1C	106 (4)	C10—C9—H9	121 (3)
H1B—C1—H1C	108 (3)	C11—C10—C9	119.6 (2)
C3—C2—C7	118.8 (2)	C11—C10—H10	123 (2)
C3—C2—C1	121.0 (2)	C9—C10—H10	117 (2)
C7—C2—C1	120.2 (2)	C10—C11—C12	122.0 (2)
C4—C3—C2	121.6 (2)	C10—C11—Cl	119.08 (18)
C4—C3—H3	118 (2)	C12—C11—Cl	118.95 (18)
C2—C3—H3	120.4 (19)	C11—C12—C13	119.0 (2)
C3—C4—C5	118.2 (2)	C11—C12—H12	122 (2)
C3—C4—H4	123.6 (17)	C13—C12—H12	119 (2)
C5—C4—H4	117.6 (17)	C8—C13—C12	118.7 (2)
C6—C5—C4	121.4 (2)	C8—C13—H13	117.9 (17)
C6—C5—S	119.60 (16)	C12—C13—H13	123.4 (17)
C4—C5—S	119.04 (17)
O1—S—O3—C8	−171.93 (16)	C5—C6—C7—C2	−0.6 (3)
O2—S—O3—C8	−43.16 (18)	C3—C2—C7—C6	0.5 (3)
C5—S—O3—C8	73.30 (17)	C1—C2—C7—C6	−179.0 (2)
C7—C2—C3—C4	0.1 (3)	S—O3—C8—C9	−102.2 (2)
C1—C2—C3—C4	179.6 (2)	S—O3—C8—C13	82.7 (2)
C2—C3—C4—C5	−0.5 (3)	C13—C8—C9—C10	1.5 (4)
C3—C4—C5—C6	0.4 (3)	O3—C8—C9—C10	−173.4 (2)
C3—C4—C5—S	179.71 (16)	C8—C9—C10—C11	−0.1 (4)
O1—S—C5—C6	136.71 (18)	C9—C10—C11—C12	−1.6 (4)
O2—S—C5—C6	1.9 (2)	C9—C10—C11—Cl	177.81 (19)
O3—S—C5—C6	−113.97 (18)	C10—C11—C12—C13	1.8 (4)
O1—S—C5—C4	−42.6 (2)	Cl—C11—C12—C13	−177.6 (2)
O2—S—C5—C4	−177.40 (16)	C9—C8—C13—C12	−1.4 (4)
O3—S—C5—C4	66.73 (18)	O3—C8—C13—C12	173.6 (2)
C4—C5—C6—C7	0.1 (3)	C11—C12—C13—C8	−0.3 (4)
S—C5—C6—C7	−179.17 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1^i	0.89 (5)	2.56 (5)	3.380 (3)	154 (4)
C1—H1B···O1^ii	0.96 (3)	2.83 (3)	3.471 (3)	125 (2)
C1—H1C···O3^iii	0.92 (4)	2.87 (4)	3.697 (3)	151 (3)
C4—H4···O1^iv	0.96 (3)	3.05 (3)	3.713 (3)	127.7 (19)
C4—H4···O2^v	0.96 (3)	2.91 (3)	3.269 (3)	103.2 (18)
C7—H7···O1^iii	0.98 (3)	2.75 (3)	3.537 (3)	138 (2)
C7—H7···O3^iii	0.98 (3)	2.57 (3)	3.500 (3)	160 (2)
C9—H9···O2^v	0.82 (4)	2.46 (4)	3.228 (3)	156 (4)
C13—H13···Cl^vi	1.00 (3)	2.77 (3)	3.709 (3)	158 (2)
C4—H4···O1	0.96 (3)	2.80 (3)	3.054 (3)	96.2 (18)
C4—H4···O3	0.96 (3)	2.98 (3)	3.210 (3)	94.8 (17)
C6—H6···O2	0.97 (5)	2.37 (5)	2.905 (3)	114 (4)
C13—H13···O2	1.00 (3)	2.79 (3)	3.108 (3)	99.0 (19)
C3—H3···Cg1^iv	0.91 (3)	2.87	3.574	134.7
C10—H10···Cg2^vii	0.83 (4)	3.17	3.845	140.7

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