Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005841/om6135sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005841/om6135Isup2.hkl |
CCDC reference: 209965
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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.
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)°.
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.
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. |
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) Å3 | 0.40 × 0.10 × 0.10 mm |
Z = 2 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0594P)2] where P = (Fo2 + 2Fc2)/3 |
2227 reflections | (Δ/σ)max < 0.001 |
207 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C13H11ClO3S | γ = 96.404 (6)° |
Mr = 282.73 | V = 653.0 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.487 (3) Å | Mo Kα radiation |
b = 8.675 (4) Å | µ = 0.45 mm−1 |
c = 10.277 (4) Å | T = 100 K |
α = 95.378 (6)° | 0.40 × 0.10 × 0.10 mm |
β = 97.886 (6)° |
Bruker SMART CCD area-detector diffractometer | 2227 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | 1762 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 0.957 | Rint = 0.027 |
4385 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.096 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.49 e Å−3 |
2227 reflections | Δρmin = −0.34 e Å−3 |
207 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cli | 1.02 (3) | 3.11 (3) | 3.748 (3) | 122 (2) |
C3—H3···Cli | 0.97 (2) | 3.20 (2) | 4.017 (3) | 143.0 (16) |
C3—H3···O3i | 0.97 (2) | 2.70 (2) | 3.613 (3) | 156.2 (17) |
C4—H4···O1ii | 0.89 (2) | 2.70 (2) | 3.571 (3) | 164.1 (19) |
C6—H6···O2iii | 0.95 (2) | 2.76 (2) | 3.477 (3) | 132.9 (16) |
C7—H7···Cliv | 0.98 (2) | 3.30 (2) | 3.774 (2) | 111.8 (15) |
C9—H9···O2v | 1.00 (2) | 2.97 (2) | 3.591 (3) | 121.2 (15) |
C12—H12···O1vi | 0.96 (3) | 2.77 (2) | 3.466 (3) | 130.2 (17) |
C12—H12···O2vi | 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. |
Experimental details
Crystal data | |
Chemical formula | C13H11ClO3S |
Mr | 282.73 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.487 (3), 8.675 (4), 10.277 (4) |
α, β, γ (°) | 95.378 (6), 97.886 (6), 96.404 (6) |
V (Å3) | 653.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1995) |
Tmin, Tmax | 0.841, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4385, 2227, 1762 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.096, 1.02 |
No. of reflections | 2227 |
No. of parameters | 207 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.49, −0.34 |
Computer programs: SMART-NT (Bruker, 1998), SMART, SAINT-NT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998), SHELXTL.
S—O2 | 1.4439 (16) | Cl—C13 | 1.758 (2) |
S—O1 | 1.4460 (16) | O3—C8 | 1.433 (3) |
S—O3 | 1.6276 (16) | C1—C2 | 1.524 (3) |
S—C5 | 1.777 (2) | ||
O2—S—O1 | 119.82 (9) | O1—S—C5 | 109.25 (10) |
O2—S—O3 | 102.91 (9) | O3—S—C5 | 104.10 (9) |
O1—S—O3 | 108.77 (9) | C8—O3—S | 118.70 (13) |
O2—S—C5 | 110.68 (10) | ||
C5—S—O3—C8 | −55.94 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1i | 0.89 (2) | 2.70 (2) | 3.571 (3) | 164.1 (19) |
C6—H6···O2ii | 0.95 (2) | 2.76 (2) | 3.477 (3) | 132.9 (16) |
C12—H12···O1iii | 0.96 (3) | 2.77 (2) | 3.466 (3) | 130.2 (17) |
C12—H12···O2iii | 0.96 (3) | 2.65 (3) | 3.592 (3) | 167.2 (19) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z. |
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.