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ISSN: 2056-9890

2,5-Di­chloro­anilinium 4-chloro­benzene­sulfonate

aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
*Correspondence e-mail: gowdabt@yahoo.com

(Received 20 March 2011; accepted 21 March 2011; online 26 March 2011)

In the crystal of the title compound, C6H6Cl2N+·C6H4ClO3S, the 2,5-dichloroanilinium cations and 4-chlorobenzenesulfonate anions are located on a crystallographic mirror plane and are connected by N—H⋯O hydrogen bonds. In the crystal, the connectivity of the hydrogen bonds leads to double chains propagating in [010].

Related literature

For the effect of substituents on the oxidative strengths of N-chloro, N-aryl­sulfonamides, see: Gowda et al. (2004a[Gowda, B. T. & Shetty, M. (2004a). J. Phys. Org. Chem. 17, 848-864.]). For their effect on the structures of N-(ar­yl)-amides, see: Gowda et al. (2004b[Gowda, B. T., Svoboda, I. & Fuess, H. (2004b). Z. Naturforsch. Teil A, 55, 845-852.]) and of N-(ar­yl)-methane­sulfonamides, see: Gowda et al. (2007[Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2570.]).

[Scheme 1]

Experimental

Crystal data
  • C6H6Cl2N+·C6H4ClO3S

  • Mr = 354.62

  • Monoclinic, P 21 /m

  • a = 9.792 (1) Å

  • b = 6.802 (1) Å

  • c = 10.879 (1) Å

  • β = 94.26 (1)°

  • V = 722.60 (15) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.78 mm−1

  • T = 293 K

  • 0.40 × 0.34 × 0.24 mm

Data collection
  • Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.745, Tmax = 0.834

  • 2700 measured reflections

  • 1603 independent reflections

  • 1439 reflections with I > 2σ(I)

  • Rint = 0.012

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.107

  • S = 1.02

  • 1603 reflections

  • 124 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.39 e Å−3

  • Δρmin = −0.39 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H11N⋯O1i 0.88 (2) 1.85 (2) 2.730 (2) 176 (2)
N1—H12N⋯O2ii 0.89 (2) 1.88 (2) 2.753 (3) 170 (3)
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+1]; (ii) x, y, z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The amine and sulfonate moieties are important constituents of many important compounds. As a part of studying the substituent effects on the structures of this class of compounds (Gowda et al., 2004a, 2004b, 2007), in the present work, the crystal structure of 2,5-dichloroanilinium, 4-chlorobenzenesulfonate (I) has been determined (Fig. 1). The title compound showed interesting H-bonding in its crystal structure (Fig. 2). It forms the structure through N—H···O(S) hydrogen bonding. Three H-atoms of the positively charged NH3 group have three O atoms of the negatively charged sulfonate anion as acceptors, with each oxygen forming H-bonding with three H-atoms, one each from three positively charged NH3 groups.

The crystal packing of (I) through N1—H11N···O1, N1—H11aN···O1a and N1—H12N···O2 hydrogen bonding (Table 1) is shown in Fig.2.

Related literature top

For the effect of substituents on the oxidative strengths of N-chloro, N-arylsulfonamides, see: Gowda et al. (2004a). For their effect on the structures of N-(aryl)-amides, see: Gowda et al. (2004b) and of N-(aryl)-methanesulfonamides, see: Gowda et al. (2007).

Experimental top

The solution of chlorobenzene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 0 ° C. After the initial evolution of hydrogen chloride subsided, the reaction mixture was brought to room temperature and poured into crushed ice in a beaker. The chloroform layer was separated, washed with cold water and allowed to evaporate slowly. The residual 4-chlorobenzenesulfonylchloride was treated with 2,5-dichloroaniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant title compound (I) was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol.

Prism like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Refinement top

The N bounded H atoms were located in a difference map and later restrained to the distance N—H = 0.86 (2) Å. The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 Å. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the Ueq of the parent atom.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing in the title compound. Hydrogen bonds are shown as dashed lines.
2,5-Dichloroanilinium 4-chlorobenzenesulfonate top
Crystal data top
C6H6Cl2N+·C6H4ClO3SF(000) = 360
Mr = 354.62Dx = 1.630 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 1811 reflections
a = 9.792 (1) Åθ = 2.7–27.8°
b = 6.802 (1) ŵ = 0.78 mm1
c = 10.879 (1) ÅT = 293 K
β = 94.26 (1)°Prism, colourless
V = 722.60 (15) Å30.40 × 0.34 × 0.24 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1603 independent reflections
Radiation source: fine-focus sealed tube1439 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.012
Rotation method data acquisition using ω scansθmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
h = 1212
Tmin = 0.745, Tmax = 0.834k = 86
2700 measured reflectionsl = 1310
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.4408P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.023
1603 reflectionsΔρmax = 0.39 e Å3
124 parametersΔρmin = 0.39 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.036 (4)
Crystal data top
C6H6Cl2N+·C6H4ClO3SV = 722.60 (15) Å3
Mr = 354.62Z = 2
Monoclinic, P21/mMo Kα radiation
a = 9.792 (1) ŵ = 0.78 mm1
b = 6.802 (1) ÅT = 293 K
c = 10.879 (1) Å0.40 × 0.34 × 0.24 mm
β = 94.26 (1)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1603 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
1439 reflections with I > 2σ(I)
Tmin = 0.745, Tmax = 0.834Rint = 0.012
2700 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0372 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.39 e Å3
1603 reflectionsΔρmin = 0.39 e Å3
124 parameters
Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Å2) top
xyzUiso*/Ueq
Cl10.87369 (7)0.75000.13209 (9)0.0577 (3)
S10.23468 (6)0.75000.11153 (5)0.0274 (2)
O10.19906 (14)0.5759 (2)0.17720 (16)0.0519 (4)
O20.1854 (2)0.75000.01564 (19)0.0575 (7)
C10.4152 (2)0.75000.1146 (2)0.0277 (5)
C20.4901 (3)0.75000.2257 (3)0.0740 (15)
H20.44540.75000.29820.089*
C30.6311 (3)0.75000.2313 (3)0.0833 (17)
H30.68180.75000.30710.100*
C40.6952 (3)0.75000.1251 (3)0.0398 (7)
C50.6231 (3)0.75000.0130 (3)0.0406 (7)
H50.66840.75000.05920.049*
C60.4811 (3)0.75000.0082 (3)0.0372 (6)
H60.43070.75000.06770.045*
Cl20.23538 (8)0.75000.58953 (8)0.0540 (3)
Cl30.39589 (11)0.75000.57932 (12)0.0947 (5)
N10.0373 (2)0.75000.8143 (2)0.0293 (5)
H11N0.0933 (19)0.852 (3)0.8172 (19)0.035*
H12N0.027 (3)0.75000.876 (2)0.035*
C70.0232 (3)0.75000.6963 (2)0.0298 (5)
C80.0594 (3)0.75000.5875 (3)0.0365 (6)
C90.0000 (4)0.75000.4767 (3)0.0487 (8)
H90.05520.75000.40330.058*
C100.1392 (4)0.75000.4734 (3)0.0530 (9)
H100.17900.75000.39840.064*
C110.2195 (4)0.75000.5822 (3)0.0504 (8)
C120.1633 (3)0.75000.6941 (3)0.0425 (7)
H120.21900.75000.76720.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0194 (3)0.0852 (7)0.0683 (6)0.0000.0028 (3)0.000
S10.0183 (3)0.0362 (4)0.0279 (3)0.0000.0028 (2)0.000
O10.0376 (8)0.0493 (9)0.0692 (10)0.0112 (7)0.0078 (7)0.0157 (8)
O20.0271 (10)0.114 (2)0.0306 (10)0.0000.0029 (8)0.000
C10.0217 (11)0.0327 (13)0.0290 (12)0.0000.0029 (9)0.000
C20.0256 (15)0.167 (5)0.0293 (14)0.0000.0043 (12)0.000
C30.0268 (15)0.187 (5)0.0349 (16)0.0000.0058 (13)0.000
C40.0198 (12)0.0510 (17)0.0487 (16)0.0000.0037 (11)0.000
C50.0269 (13)0.0555 (18)0.0406 (15)0.0000.0113 (11)0.000
C60.0257 (13)0.0556 (17)0.0304 (12)0.0000.0033 (10)0.000
Cl20.0422 (4)0.0676 (6)0.0495 (5)0.0000.0150 (3)0.000
Cl30.0499 (6)0.1572 (13)0.0820 (7)0.0000.0370 (5)0.000
N10.0267 (10)0.0344 (12)0.0268 (10)0.0000.0009 (8)0.000
C70.0338 (13)0.0290 (13)0.0267 (12)0.0000.0040 (10)0.000
C80.0450 (16)0.0314 (14)0.0323 (13)0.0000.0029 (11)0.000
C90.072 (2)0.0452 (17)0.0279 (14)0.0000.0037 (14)0.000
C100.078 (2)0.0502 (19)0.0336 (15)0.0000.0208 (15)0.000
C110.0479 (18)0.057 (2)0.0484 (17)0.0000.0202 (14)0.000
C120.0368 (15)0.0563 (19)0.0348 (14)0.0000.0054 (11)0.000
Geometric parameters (Å, º) top
Cl1—C41.744 (3)Cl2—C81.725 (3)
S1—O21.431 (2)Cl3—C111.730 (4)
S1—O1i1.4390 (16)N1—C71.453 (3)
S1—O11.4390 (16)N1—H11N0.884 (15)
S1—C11.766 (2)N1—H12N0.886 (18)
C1—C61.367 (4)C7—C121.373 (4)
C1—C21.366 (4)C7—C81.383 (4)
C2—C31.378 (4)C8—C91.377 (4)
C2—H20.9300C9—C101.367 (5)
C3—C41.355 (5)C9—H90.9300
C3—H30.9300C10—C111.371 (5)
C4—C51.363 (4)C10—H100.9300
C5—C61.387 (4)C11—C121.374 (4)
C5—H50.9300C12—H120.9300
C6—H60.9300
O2—S1—O1i113.77 (8)C5—C6—H6119.9
O2—S1—O1113.77 (8)C7—N1—H11N109.0 (14)
O1i—S1—O1110.72 (14)C7—N1—H12N111 (2)
O2—S1—C1106.49 (12)H11N—N1—H12N112.4 (18)
O1i—S1—C1105.65 (8)C12—C7—C8120.5 (3)
O1—S1—C1105.65 (8)C12—C7—N1119.2 (2)
C6—C1—C2119.6 (2)C8—C7—N1120.3 (2)
C6—C1—S1121.2 (2)C9—C8—C7119.4 (3)
C2—C1—S1119.2 (2)C9—C8—Cl2119.9 (2)
C1—C2—C3120.6 (3)C7—C8—Cl2120.7 (2)
C1—C2—H2119.7C10—C9—C8120.6 (3)
C3—C2—H2119.7C10—C9—H9119.7
C4—C3—C2119.2 (3)C8—C9—H9119.7
C4—C3—H3120.4C11—C10—C9119.1 (3)
C2—C3—H3120.4C11—C10—H10120.4
C3—C4—C5121.4 (3)C9—C10—H10120.4
C3—C4—Cl1119.3 (2)C10—C11—C12121.6 (3)
C5—C4—Cl1119.3 (2)C10—C11—Cl3119.6 (3)
C4—C5—C6119.0 (3)C12—C11—Cl3118.9 (3)
C4—C5—H5120.5C11—C12—C7118.8 (3)
C6—C5—H5120.5C11—C12—H12120.6
C1—C6—C5120.2 (3)C7—C12—H12120.6
C1—C6—H6119.9
O2—S1—C1—C60.0C4—C5—C6—C10.0
O1i—S1—C1—C6121.30 (8)C12—C7—C8—C90.000 (1)
O1—S1—C1—C6121.30 (8)N1—C7—C8—C9180.0
O2—S1—C1—C2180.0C12—C7—C8—Cl2180.0
O1i—S1—C1—C258.70 (8)N1—C7—C8—Cl20.0
O1—S1—C1—C258.70 (8)C7—C8—C9—C100.000 (1)
C6—C1—C2—C30.0Cl2—C8—C9—C10180.0
S1—C1—C2—C3180.0C8—C9—C10—C110.0
C1—C2—C3—C40.0C9—C10—C11—C120.000 (1)
C2—C3—C4—C50.0C9—C10—C11—Cl3180.0
C2—C3—C4—Cl1180.0C10—C11—C12—C70.000 (1)
C3—C4—C5—C60.0Cl3—C11—C12—C7180.0
Cl1—C4—C5—C6180.0C8—C7—C12—C110.0
C2—C1—C6—C50.0N1—C7—C12—C11180.0
S1—C1—C6—C5180.0
Symmetry code: (i) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11N···O1ii0.88 (2)1.85 (2)2.730 (2)176 (2)
N1—H12N···O2iii0.89 (2)1.88 (2)2.753 (3)170 (3)
Symmetry codes: (ii) x, y+1/2, z+1; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC6H6Cl2N+·C6H4ClO3S
Mr354.62
Crystal system, space groupMonoclinic, P21/m
Temperature (K)293
a, b, c (Å)9.792 (1), 6.802 (1), 10.879 (1)
β (°) 94.26 (1)
V3)722.60 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.78
Crystal size (mm)0.40 × 0.34 × 0.24
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.745, 0.834
No. of measured, independent and
observed [I > 2σ(I)] reflections
2700, 1603, 1439
Rint0.012
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.107, 1.02
No. of reflections1603
No. of parameters124
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.39, 0.39

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11N···O1i0.884 (15)1.848 (15)2.730 (2)176 (2)
N1—H12N···O2ii0.886 (18)1.876 (19)2.753 (3)170 (3)
Symmetry codes: (i) x, y+1/2, z+1; (ii) x, y, z+1.
 

Acknowledgements

KS thanks the University Grants Commission, Government of India, New Delhi for the award of a research fellowship under its faculty improvement program.

References

First citationGowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2570.  Web of Science CSD CrossRef IUCr Journals
First citationGowda, B. T. & Shetty, M. (2004a). J. Phys. Org. Chem. 17, 848–864.  CrossRef CAS
First citationGowda, B. T., Svoboda, I. & Fuess, H. (2004b). Z. Naturforsch. Teil A, 55, 845–852.
First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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