2,4-Dichloro­anilinium 4-chloro­benzene­sulfonate monohydrate

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811012463

. 2011 Apr 7;67(Pt 5):o1077. doi: 10.1107/S1600536811012463

2,4-Dichloroanilinium 4-chlorobenzenesulfonate monohydrate

K Shakuntala ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3089207 PMID: 21754400

Abstract

The asymmetric unit of the title compound, C₆H₆Cl₂N⁺·C₆H₄ClO₃S⁻·H₂O, contains two 2,4-dichloroanilinium cations, two 4-chlorophenylsulfonate anions and two water molecules. The three H atoms of the positively charged NH₃ group have two O atoms of the negatively charged sulfonate anion and one O atom of the water molecule as acceptors. Similarly, the two H atoms of the water molecule have two O atoms of two different negatively charged sulfonate anions as acceptors. Further, one of the O atoms of the sulfonate anion is involved in simultaneous hydrogen bonds with two H atoms, one from the positively charged NH₃ group and the other from the water molecule. In the crystal, molecules are packed into a layer structure through N—H⋯O(S), N—H⋯O(H₂O) and N—H⋯O(S)⋯H—O(H₂O) (three-centre) hydrogen bonding, the chains running along the c axis.

Related literature

For the effect of substituents on the oxidative strengths of N-chloro, N-arylsulfonamides, see: Gowda & Kumar (2003 ▶). For the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2004 ▶), on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and on anilinium arylsulfonates, see: Shakuntala et al. (2011 ▶). For restrained geometry, see: Nardelli (1999 ▶).

Experimental

Crystal data

C₆H₆Cl₂N⁺·C₆H₄ClO₃S⁻·H₂O
M _r = 372.64
Triclinic,
a = 7.7589 (8) Å
b = 14.143 (2) Å
c = 14.358 (2) Å
α = 90.99 (1)°
β = 99.56 (1)°
γ = 90.68 (1)°
V = 1553.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 293 K
0.40 × 0.16 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.757, T _max = 0.957
11006 measured reflections
6341 independent reflections
2585 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.081
S = 0.84
6341 reflections
409 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012463/bq2293sup1.cif

e-67-o1077-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012463/bq2293Isup2.hkl

e-67-o1077-Isup2.hkl^{(310.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O1ⁱ	0.91 (2)	1.89 (2)	2.765 (4)	160 (3)
N1—H12N⋯O3ⁱⁱ	0.93 (2)	1.83 (2)	2.752 (4)	171 (3)
N1—H13N⋯O7	0.90 (2)	1.90 (2)	2.785 (4)	169 (3)
N2—H21N⋯O6ⁱⁱⁱ	0.91 (2)	1.92 (2)	2.777 (4)	156 (3)
N2—H22N⋯O4^iv	0.93 (2)	1.82 (2)	2.741 (4)	176 (3)
N2—H23N⋯O8ⁱⁱⁱ	0.91 (2)	1.92 (2)	2.807 (4)	164 (3)
O7—H71O⋯O2	0.84 (2)	1.96 (2)	2.778 (4)	163 (4)
O7—H72O⋯O6ⁱⁱ	0.84 (2)	2.13 (3)	2.879 (4)	148 (5)
O8—H81O⋯O1ⁱⁱ	0.83 (2)	2.18 (3)	2.900 (4)	146 (4)
O8—H82O⋯O5ⁱ	0.85 (2)	2.03 (2)	2.830 (4)	158 (4)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

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

supplementary crystallographic information

Comment

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 & Kumar, 2003; Gowda et al., 2004, 2007; Shakuntala et al., 2011), in the present work, the crystal structure of 2,4-dichloroanilinium, 4-chlorobenzenesulfonate monohydrate (I) has been determined. The compound (I) showed interesting H-bonding in its crystal structure (Fig. 1). It shows 3-centre H-bonding.

The asymmetric unit of (I) contains two 2,4-dichloroanilinium cations, two 4-chlorophenylsulfonate anions and two water molecules. Three H-atoms of the positively charged NH₃ group have two O atoms of the negatively charged sulfonate anion and one O atom of the water molecule as acceptors. Similarly two H atoms of the water molecule have two O atoms of two different negatively charged sulfonate anions as acceptors. Further, one of the O atoms of the sulfonate anion is involved in simultaneous H-bonding with two H atoms one from the positively charged NH₃ group of 2,4-dichloroanilinium cation and the other from the water molecule.

The above behavior is in contrast to the N—H···O(S) hydrogen bonding of the three H-atoms of the positively charged NH₃ group of 2,5-Dichloroanilinium, 4-chlorobenzenesulfonate, having 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 (Shakuntala et al., 2011).

The crystal packing of (I) through N1—H11N···O1, N1—H12N···O3, N1—H13N···O7, N2—H21N···O6, N2—H22N···O4 and N2—H23N···O8 hydrogen bonding (Table 1) is shown in Fig. 2.

Experimental

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 2,4-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.

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