2,4-Di­chloro­phenyl 4-toluene­sulfonate: supramolecular aggregation through C—H...O, C—H...Cl, C—H...π and π...π interactions

In the crystal structure of the title mol­ecule, C₁₃H₁₀Cl₂O₃S, the dihedral angle between the mean planes of the 4-tolyl and 2,4-di­chloro­phenyl rings is 43.92 (4)°. There are weak C—H...O hydrogen bonds, which generate rings of motifs S(5), S(6), R²₁(4), R¹₂(6) and R²₂(8). The supramolecular aggregation is completed by the presence of C—H...Cl, C—H...π and π...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.028
• wR factor = 0.077
• Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.38
         From the CIF: _reflns_number_total               3074
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3319
         Completeness (_total/calc)             92.62%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

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 4-tolyl and 2,4-dichlorophenyl rings is 43.92 (4)°. 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) agrees with that found for weak C—H···O bonds (Desiraju & Steiner, 1999). The C4—H4···O1 interaction generates a ring of graph set S(5) (Etter, 1990; Bernstein et al., 1995). Another S(5) motif is formed by the C6—H6.·O2 interaction. The C13—H13···O2 interaction generates a S(6) motif. The C6—H6···O2 and C13—H13···O2 interactions constitute a pair of bifurcated acceptor bonds. The C7—H7···O3ⁱⁱⁱ and C7—H7···O1ⁱⁱⁱ (Fig. 2) interactions constitute a pair of bifurcated donor bonds, generating a ring of graph set R²₁(4). The H7···O3ⁱⁱⁱ and H7···O1ⁱⁱⁱ distances differ by 0.42 (2) Å. The resulting configuration is termed as an unsymmetrical three-centered H-bonded chelated (Desiraju, 1989) which is different from the symmetrical three centered hygrogen-bonded chelate observed in similar structures (Vembu, Nallu, Garrison & Youngs, 2003b,c; Vembu, Nallu, Garrison, Hindi & Youngs, 2003). The C1—H1B···O1ⁱⁱⁱ and C7—H7···O1ⁱⁱⁱ (Fig. 2) interactions constitute a pair of bifurcated acceptor bonds, generating a ring of graph set R¹₂(6). The C7—H7···O3ⁱⁱⁱ and C1—H1B···O1ⁱⁱⁱ (Fig. 2) interactions generate a R²₂(8) motif which consists of the R²₁(4) chelate and R¹₂(6) ring motifs. There are several other C—H···O interactions (Fig. 2–4, Table 2) and a C—H···Cl interaction (Fig. 3) which contribute to the supramolecular aggregation. The supramolecular aggregation is completed by the presence of an intramolecular C—H···π interaction (Table 2). The geometry of the C—H···π interaction was obtained from PLATON (Spek, 1998); Cg2 is the centroid of the 2,4-dichlorophenyl ring. In the crystal lattice, the molecules are stacked in layers (Fig. 5) held together by π···π interactions, with a distance of 4.059 Å and 3.672 Å between the centroids of adjacent 4-tolyl rings (Symmetry code: −x, −y, 1 − z) and 2,4-dichlorophenyl rings (Symmetry code: 1 − x, 1 − y, −z), respectively.

S2. Experimental

4-Toluenesulfonyl chloride (4.7 mmol), dissolved in acetone (4 ml), was added dropwise to 2,4-dichlorophenol (5.5 mol) in aqueous NaOH (2.5 ml, 10%) with constant shaking. The precipitated title compound (3.3 mmol, yield 70%) 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 0.91 (3)–0.97 (2) Å, the H—C—H angles for the methyl group are in the range 103 (2)–110 (2)° and the C—C—H angles for the aromatic rings are in the range 117.4 (1)–122.2 (1)°.

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 (I), with displacement ellipsoids drawn at the 50% probablity level.
	Fig. 2. Diagram showing hydrogen bonds 3, 4, 6 and 8 (the numbering relates to sequence of entries in Table 2).
	Fig. 3. Diagram showing hydrogen bonds 2 and 5 (the numbering relates to sequence of entries in Table 2).
	Fig. 4. Diagram showing hydrogen bonds 1 and 7 (the numbering relates to sequence of entries in Table 2).
	Fig. 5. Packing of the molecule in the unit cell.

2,4-dichlorophenyl 4-toluenesulfonate

Crystal data

C13H10Cl2O3S	F(000) = 324
Mr = 317.17	Dx = 1.598 Mg m^−3
Triclinic, P1	Melting point = 373–375 K
a = 7.7314 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3724 (11) Å	Cell parameters from 7298 reflections
c = 10.7055 (15) Å	θ = 2.5–28.4°
α = 99.079 (2)°	µ = 0.65 mm^−1
β = 96.119 (2)°	T = 100 K
γ = 103.134 (2)°	Block, colorless
V = 659.04 (16) Å^3	0.55 × 0.50 × 0.40 mm
Z = 2

Data collection

CCD area detector diffractometer	3074 independent reflections
Radiation source: fine-focus sealed tube	2954 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.716, Tmax = 0.781	k = −11→10
8295 measured reflections	l = −14→14

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0378P)^2 + 0.4025P] where P = (Fo^2 + 2Fc^2)/3
3074 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

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 0.901603 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	0.35514 (5)	0.00280 (4)	0.23813 (3)	0.01748 (10)
Cl1	0.45681 (5)	0.49434 (4)	0.31856 (3)	0.02440 (10)
Cl2	0.14177 (5)	0.52405 (5)	−0.14652 (4)	0.02600 (10)
O1	0.47889 (15)	−0.04614 (14)	0.32349 (11)	0.0250 (2)
O2	0.25961 (15)	−0.11069 (13)	0.12540 (11)	0.0236 (2)
O3	0.48113 (13)	0.16079 (12)	0.19492 (10)	0.0174 (2)
C1	−0.1690 (2)	0.3051 (2)	0.51223 (18)	0.0267 (3)
C2	−0.03703 (19)	0.23010 (17)	0.44474 (15)	0.0193 (3)
C3	0.1225 (2)	0.21731 (19)	0.51221 (14)	0.0205 (3)
C4	0.2440 (2)	0.14659 (18)	0.45074 (14)	0.0194 (3)
C5	0.20369 (18)	0.08855 (17)	0.31954 (13)	0.0162 (3)
C6	0.04635 (19)	0.10076 (18)	0.24933 (14)	0.0184 (3)
C7	−0.07293 (19)	0.17108 (18)	0.31323 (15)	0.0198 (3)
C8	0.39860 (18)	0.24500 (17)	0.11238 (13)	0.0157 (3)
C9	0.37926 (18)	0.40343 (17)	0.16049 (13)	0.0165 (3)
C10	0.30044 (18)	0.49065 (17)	0.08087 (14)	0.0183 (3)
C11	0.24333 (19)	0.41690 (18)	−0.04656 (14)	0.0187 (3)
C12	0.2659 (2)	0.26087 (18)	−0.09650 (14)	0.0206 (3)
C13	0.34456 (19)	0.17467 (18)	−0.01564 (14)	0.0185 (3)
H1A	−0.202 (4)	0.387 (4)	0.472 (3)	0.069 (9)*
H1B	−0.273 (3)	0.224 (3)	0.519 (2)	0.048 (7)*
H1C	−0.126 (4)	0.354 (4)	0.595 (3)	0.066 (8)*
H3	0.152 (3)	0.256 (3)	0.602 (2)	0.032 (5)*
H4	0.350 (3)	0.138 (3)	0.499 (2)	0.032 (5)*
H6	0.022 (2)	0.063 (2)	0.1578 (18)	0.017 (4)*
H7	−0.180 (3)	0.177 (3)	0.268 (2)	0.035 (5)*
H10	0.286 (3)	0.599 (2)	0.1125 (18)	0.026 (5)*
H12	0.231 (3)	0.214 (3)	−0.185 (2)	0.029 (5)*
H13	0.356 (2)	0.064 (2)	−0.0455 (18)	0.021 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.01871 (17)	0.01458 (16)	0.02211 (18)	0.00756 (13)	0.00526 (13)	0.00569 (13)
Cl1	0.0303 (2)	0.02017 (18)	0.02093 (18)	0.00586 (14)	0.00299 (14)	−0.00047 (13)
Cl2	0.02321 (19)	0.0284 (2)	0.0309 (2)	0.01036 (15)	0.00224 (14)	0.01456 (15)
O1	0.0249 (5)	0.0269 (6)	0.0314 (6)	0.0153 (5)	0.0077 (5)	0.0142 (5)
O2	0.0281 (6)	0.0143 (5)	0.0279 (6)	0.0052 (4)	0.0072 (4)	0.0007 (4)
O3	0.0155 (4)	0.0170 (5)	0.0219 (5)	0.0060 (4)	0.0036 (4)	0.0068 (4)
C1	0.0238 (8)	0.0249 (8)	0.0340 (9)	0.0093 (6)	0.0108 (7)	0.0042 (7)
C2	0.0177 (7)	0.0152 (6)	0.0265 (7)	0.0040 (5)	0.0072 (5)	0.0060 (5)
C3	0.0220 (7)	0.0214 (7)	0.0180 (7)	0.0048 (6)	0.0037 (5)	0.0037 (5)
C4	0.0176 (7)	0.0212 (7)	0.0208 (7)	0.0059 (5)	0.0011 (5)	0.0074 (5)
C5	0.0158 (6)	0.0141 (6)	0.0201 (7)	0.0046 (5)	0.0043 (5)	0.0045 (5)
C6	0.0174 (6)	0.0182 (6)	0.0189 (7)	0.0029 (5)	0.0015 (5)	0.0046 (5)
C7	0.0146 (6)	0.0208 (7)	0.0252 (7)	0.0050 (5)	0.0016 (5)	0.0076 (6)
C8	0.0134 (6)	0.0148 (6)	0.0206 (7)	0.0048 (5)	0.0041 (5)	0.0056 (5)
C9	0.0153 (6)	0.0158 (6)	0.0181 (6)	0.0029 (5)	0.0049 (5)	0.0016 (5)
C10	0.0161 (6)	0.0141 (6)	0.0265 (7)	0.0047 (5)	0.0071 (5)	0.0049 (5)
C11	0.0144 (6)	0.0190 (6)	0.0250 (7)	0.0048 (5)	0.0035 (5)	0.0093 (6)
C12	0.0217 (7)	0.0203 (7)	0.0186 (7)	0.0032 (6)	0.0023 (5)	0.0038 (6)
C13	0.0199 (7)	0.0151 (6)	0.0214 (7)	0.0051 (5)	0.0056 (5)	0.0029 (5)

Geometric parameters (Å, º)

S—O1	1.4242 (11)	C4—C5	1.389 (2)
S—O2	1.4262 (11)	C4—H4	0.95 (2)
S—O3	1.6174 (10)	C5—C6	1.3932 (19)
S—C5	1.7458 (14)	C6—C7	1.385 (2)
Cl1—C9	1.7239 (14)	C6—H6	0.965 (18)
Cl2—C11	1.7350 (15)	C7—H7	0.93 (2)
O3—C8	1.4021 (16)	C8—C13	1.382 (2)
C1—C2	1.504 (2)	C8—C9	1.3922 (19)
C1—H1A	0.93 (3)	C9—C10	1.385 (2)
C1—H1B	0.94 (3)	C10—C11	1.385 (2)
C1—H1C	0.91 (3)	C10—H10	0.95 (2)
C2—C7	1.392 (2)	C11—C12	1.388 (2)
C2—C3	1.396 (2)	C12—C13	1.387 (2)
C3—C4	1.388 (2)	C12—H12	0.95 (2)
C3—H3	0.95 (2)	C13—H13	0.959 (19)
O1—S—O2	120.41 (7)	C7—C6—C5	118.66 (13)
O1—S—O3	102.48 (6)	C7—C6—H6	120.8 (11)
O2—S—O3	108.04 (6)	C5—C6—H6	120.5 (11)
O1—S—C5	111.35 (7)	C6—C7—C2	121.18 (13)
O2—S—C5	109.13 (7)	C6—C7—H7	119.6 (14)
O3—S—C5	103.91 (6)	C2—C7—H7	119.2 (14)
C8—O3—S	117.63 (8)	C13—C8—C9	120.71 (13)
C2—C1—H1A	111.5 (18)	C13—C8—O3	120.44 (12)
C2—C1—H1B	112.2 (15)	C9—C8—O3	118.80 (12)
H1A—C1—H1B	110 (2)	C10—C9—C8	120.13 (13)
C2—C1—H1C	113.6 (18)	C10—C9—Cl1	119.45 (11)
H1A—C1—H1C	106 (2)	C8—C9—Cl1	120.41 (11)
H1B—C1—H1C	103 (2)	C9—C10—C11	118.45 (13)
C7—C2—C3	118.77 (13)	C9—C10—H10	120.9 (12)
C7—C2—C1	120.25 (14)	C11—C10—H10	120.6 (12)
C3—C2—C1	120.97 (14)	C10—C11—C12	122.01 (13)
C4—C3—C2	121.27 (14)	C10—C11—Cl2	118.77 (11)
C4—C3—H3	117.4 (13)	C12—C11—Cl2	119.22 (12)
C2—C3—H3	121.3 (13)	C13—C12—C11	118.94 (14)
C3—C4—C5	118.46 (13)	C13—C12—H12	119.9 (12)
C3—C4—H4	119.4 (13)	C11—C12—H12	121.1 (12)
C5—C4—H4	122.2 (13)	C8—C13—C12	119.73 (13)
C4—C5—C6	121.66 (13)	C8—C13—H13	118.9 (11)
C4—C5—S	119.87 (11)	C12—C13—H13	121.3 (11)
C6—C5—S	118.45 (11)
O1—S—O3—C8	−177.68 (10)	C3—C2—C7—C6	0.0 (2)
O2—S—O3—C8	54.19 (11)	C1—C2—C7—C6	−179.66 (14)
C5—S—O3—C8	−61.64 (11)	S—O3—C8—C13	−74.50 (15)
C7—C2—C3—C4	−0.3 (2)	S—O3—C8—C9	108.25 (12)
C1—C2—C3—C4	179.30 (14)	C13—C8—C9—C10	1.9 (2)
C2—C3—C4—C5	0.2 (2)	O3—C8—C9—C10	179.14 (12)
C3—C4—C5—C6	0.4 (2)	C13—C8—C9—Cl1	−176.87 (11)
C3—C4—C5—S	178.64 (11)	O3—C8—C9—Cl1	0.37 (18)
O1—S—C5—C4	18.90 (14)	C8—C9—C10—C11	−0.4 (2)
O2—S—C5—C4	154.21 (11)	Cl1—C9—C10—C11	178.35 (10)
O3—S—C5—C4	−90.73 (12)	C9—C10—C11—C12	−1.2 (2)
O1—S—C5—C6	−162.80 (11)	C9—C10—C11—Cl2	179.16 (10)
O2—S—C5—C6	−27.49 (13)	C10—C11—C12—C13	1.4 (2)
O3—S—C5—C6	87.57 (12)	Cl2—C11—C12—C13	−178.96 (11)
C4—C5—C6—C7	−0.7 (2)	C9—C8—C13—C12	−1.7 (2)
S—C5—C6—C7	−179.01 (11)	O3—C8—C13—C12	−178.89 (12)
C5—C6—C7—C2	0.6 (2)	C11—C12—C13—C8	0.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3^i	0.959 (19)	2.871 (19)	3.7361 (18)	150.5 (14)
C10—H10···O2^ii	0.95 (2)	2.47 (2)	3.3876 (18)	162.0 (16)
C7—H7···O3^iii	0.93 (2)	2.62 (2)	3.5211 (18)	163.8 (18)
C7—H7···O1^iii	0.93 (2)	3.04 (2)	3.5505 (19)	116.3 (16)
C7—H7···Cl2^iv	0.93 (2)	2.97 (2)	3.4404 (15)	112.9 (16)
C4—H4···O1^v	0.95 (2)	2.52 (2)	3.3907 (18)	153.6 (17)
C1—H1B···O1^vi	0.94 (3)	2.81 (3)	3.644 (2)	147.7 (19)
C1—H1B···O1^iii	0.94 (3)	2.97 (3)	3.668 (2)	131.7 (18)
C4—H4···O1	0.95 (2)	2.66 (2)	2.9874 (19)	100.7 (14)
C6—H6···O2	0.965 (18)	2.605 (18)	2.9436 (18)	100.9 (12)
C13—H13···O2	0.959 (19)	2.583 (19)	3.0093 (18)	107.2 (13)
C6—H6···Cg2	0.97 (2)	3.388	3.778	106.6

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