2,5-Dichloro­anilinium 4-chloro­benzene­sulfonate

Shakuntala, K.; Foro, S.; Gowda, B.T.

doi:10.1107/S1600536811010518

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o967

doi:10.1107/S1600536811010518

Open

access

2,5-Dichloroanilinium 4-chlorobenzenesulfonate

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

^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 ). 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

Crystal data

C₆H₆Cl₂N⁺·C₆H₄ClO₃S⁻
M_r = 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 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.745, T_max = 0.834
2700 measured reflections
1603 independent reflections
1439 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010518/bt5496sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010518/bt5496Isup2.hkl

checkCIF report

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.

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

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	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⁺·C₆H₄ClO₃S⁻	F(000) = 360
M_r = 354.62	D_x = 1.630 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1811 reflections
a = 9.792 (1) Å	θ = 2.7–27.8°
b = 6.802 (1) Å	µ = 0.78 mm⁻¹
c = 10.879 (1) Å	T = 293 K
β = 94.26 (1)°	Prism, colourless
V = 722.60 (15) Å³	0.40 × 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 tube	1439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
Rotation method data acquisition using ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −12→12
T_min = 0.745, T_max = 0.834	k = −8→6
2700 measured reflections	l = −13→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0626P)² + 0.4408P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.023
1603 reflections	Δρ_max = 0.39 e Å⁻³
124 parameters	Δρ_min = −0.39 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (4)

Crystal data top

C₆H₆Cl₂N⁺·C₆H₄ClO₃S⁻	V = 722.60 (15) Å³
M_r = 354.62	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 9.792 (1) Å	µ = 0.78 mm⁻¹
b = 6.802 (1) Å	T = 293 K
c = 10.879 (1) Å	0.40 × 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)
T_min = 0.745, T_max = 0.834	R_int = 0.012
2700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.39 e Å⁻³
1603 reflections	Δρ_min = −0.39 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl1	0.87369 (7)	0.7500	0.13209 (9)	0.0577 (3)
S1	0.23468 (6)	0.7500	0.11153 (5)	0.0274 (2)
O1	0.19906 (14)	0.5759 (2)	0.17720 (16)	0.0519 (4)
O2	0.1854 (2)	0.7500	−0.01564 (19)	0.0575 (7)
C1	0.4152 (2)	0.7500	0.1146 (2)	0.0277 (5)
C2	0.4901 (3)	0.7500	0.2257 (3)	0.0740 (15)
H2	0.4454	0.7500	0.2982	0.089*
C3	0.6311 (3)	0.7500	0.2313 (3)	0.0833 (17)
H3	0.6818	0.7500	0.3071	0.100*
C4	0.6952 (3)	0.7500	0.1251 (3)	0.0398 (7)
C5	0.6231 (3)	0.7500	0.0130 (3)	0.0406 (7)
H5	0.6684	0.7500	−0.0592	0.049*
C6	0.4811 (3)	0.7500	0.0082 (3)	0.0372 (6)
H6	0.4307	0.7500	−0.0677	0.045*
Cl2	−0.23538 (8)	0.7500	0.58953 (8)	0.0540 (3)
Cl3	0.39589 (11)	0.7500	0.57932 (12)	0.0947 (5)
N1	−0.0373 (2)	0.7500	0.8143 (2)	0.0293 (5)
H11N	−0.0933 (19)	0.852 (3)	0.8172 (19)	0.035*
H12N	0.027 (3)	0.7500	0.876 (2)	0.035*
C7	0.0232 (3)	0.7500	0.6963 (2)	0.0298 (5)
C8	−0.0594 (3)	0.7500	0.5875 (3)	0.0365 (6)
C9	0.0000 (4)	0.7500	0.4767 (3)	0.0487 (8)
H9	−0.0552	0.7500	0.4033	0.058*
C10	0.1392 (4)	0.7500	0.4734 (3)	0.0530 (9)
H10	0.1790	0.7500	0.3984	0.064*
C11	0.2195 (4)	0.7500	0.5822 (3)	0.0504 (8)
C12	0.1633 (3)	0.7500	0.6941 (3)	0.0425 (7)
H12	0.2190	0.7500	0.7672	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0194 (3)	0.0852 (7)	0.0683 (6)	0.000	0.0028 (3)	0.000
S1	0.0183 (3)	0.0362 (4)	0.0279 (3)	0.000	0.0028 (2)	0.000
O1	0.0376 (8)	0.0493 (9)	0.0692 (10)	−0.0112 (7)	0.0078 (7)	0.0157 (8)
O2	0.0271 (10)	0.114 (2)	0.0306 (10)	0.000	−0.0029 (8)	0.000
C1	0.0217 (11)	0.0327 (13)	0.0290 (12)	0.000	0.0029 (9)	0.000
C2	0.0256 (15)	0.167 (5)	0.0293 (14)	0.000	0.0043 (12)	0.000
C3	0.0268 (15)	0.187 (5)	0.0349 (16)	0.000	−0.0058 (13)	0.000
C4	0.0198 (12)	0.0510 (17)	0.0487 (16)	0.000	0.0037 (11)	0.000
C5	0.0269 (13)	0.0555 (18)	0.0406 (15)	0.000	0.0113 (11)	0.000
C6	0.0257 (13)	0.0556 (17)	0.0304 (12)	0.000	0.0033 (10)	0.000
Cl2	0.0422 (4)	0.0676 (6)	0.0495 (5)	0.000	−0.0150 (3)	0.000
Cl3	0.0499 (6)	0.1572 (13)	0.0820 (7)	0.000	0.0370 (5)	0.000
N1	0.0267 (10)	0.0344 (12)	0.0268 (10)	0.000	0.0009 (8)	0.000
C7	0.0338 (13)	0.0290 (13)	0.0267 (12)	0.000	0.0040 (10)	0.000
C8	0.0450 (16)	0.0314 (14)	0.0323 (13)	0.000	−0.0029 (11)	0.000
C9	0.072 (2)	0.0452 (17)	0.0279 (14)	0.000	−0.0037 (14)	0.000
C10	0.078 (2)	0.0502 (19)	0.0336 (15)	0.000	0.0208 (15)	0.000
C11	0.0479 (18)	0.057 (2)	0.0484 (17)	0.000	0.0202 (14)	0.000
C12	0.0368 (15)	0.0563 (19)	0.0348 (14)	0.000	0.0054 (11)	0.000

Geometric parameters (Å, º) top

Cl1—C4	1.744 (3)	Cl2—C8	1.725 (3)
S1—O2	1.431 (2)	Cl3—C11	1.730 (4)
S1—O1ⁱ	1.4390 (16)	N1—C7	1.453 (3)
S1—O1	1.4390 (16)	N1—H11N	0.884 (15)
S1—C1	1.766 (2)	N1—H12N	0.886 (18)
C1—C6	1.367 (4)	C7—C12	1.373 (4)
C1—C2	1.366 (4)	C7—C8	1.383 (4)
C2—C3	1.378 (4)	C8—C9	1.377 (4)
C2—H2	0.9300	C9—C10	1.367 (5)
C3—C4	1.355 (5)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.371 (5)
C4—C5	1.363 (4)	C10—H10	0.9300
C5—C6	1.387 (4)	C11—C12	1.374 (4)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300

O2—S1—O1ⁱ	113.77 (8)	C5—C6—H6	119.9
O2—S1—O1	113.77 (8)	C7—N1—H11N	109.0 (14)
O1ⁱ—S1—O1	110.72 (14)	C7—N1—H12N	111 (2)
O2—S1—C1	106.49 (12)	H11N—N1—H12N	112.4 (18)
O1ⁱ—S1—C1	105.65 (8)	C12—C7—C8	120.5 (3)
O1—S1—C1	105.65 (8)	C12—C7—N1	119.2 (2)
C6—C1—C2	119.6 (2)	C8—C7—N1	120.3 (2)
C6—C1—S1	121.2 (2)	C9—C8—C7	119.4 (3)
C2—C1—S1	119.2 (2)	C9—C8—Cl2	119.9 (2)
C1—C2—C3	120.6 (3)	C7—C8—Cl2	120.7 (2)
C1—C2—H2	119.7	C10—C9—C8	120.6 (3)
C3—C2—H2	119.7	C10—C9—H9	119.7
C4—C3—C2	119.2 (3)	C8—C9—H9	119.7
C4—C3—H3	120.4	C11—C10—C9	119.1 (3)
C2—C3—H3	120.4	C11—C10—H10	120.4
C3—C4—C5	121.4 (3)	C9—C10—H10	120.4
C3—C4—Cl1	119.3 (2)	C10—C11—C12	121.6 (3)
C5—C4—Cl1	119.3 (2)	C10—C11—Cl3	119.6 (3)
C4—C5—C6	119.0 (3)	C12—C11—Cl3	118.9 (3)
C4—C5—H5	120.5	C11—C12—C7	118.8 (3)
C6—C5—H5	120.5	C11—C12—H12	120.6
C1—C6—C5	120.2 (3)	C7—C12—H12	120.6
C1—C6—H6	119.9

O2—S1—C1—C6	0.0	C4—C5—C6—C1	0.0
O1ⁱ—S1—C1—C6	−121.30 (8)	C12—C7—C8—C9	0.000 (1)
O1—S1—C1—C6	121.30 (8)	N1—C7—C8—C9	180.0
O2—S1—C1—C2	180.0	C12—C7—C8—Cl2	180.0
O1ⁱ—S1—C1—C2	58.70 (8)	N1—C7—C8—Cl2	0.0
O1—S1—C1—C2	−58.70 (8)	C7—C8—C9—C10	0.000 (1)
C6—C1—C2—C3	0.0	Cl2—C8—C9—C10	180.0
S1—C1—C2—C3	180.0	C8—C9—C10—C11	0.0
C1—C2—C3—C4	0.0	C9—C10—C11—C12	0.000 (1)
C2—C3—C4—C5	0.0	C9—C10—C11—Cl3	180.0
C2—C3—C4—Cl1	180.0	C10—C11—C12—C7	0.000 (1)
C3—C4—C5—C6	0.0	Cl3—C11—C12—C7	180.0
Cl1—C4—C5—C6	180.0	C8—C7—C12—C11	0.0
C2—C1—C6—C5	0.0	N1—C7—C12—C11	180.0
S1—C1—C6—C5	180.0

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1ⁱⁱ	0.88 (2)	1.85 (2)	2.730 (2)	176 (2)
N1—H12N···O2ⁱⁱⁱ	0.89 (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 formula	C₆H₆Cl₂N⁺·C₆H₄ClO₃S⁻
M_r	354.62
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	9.792 (1), 6.802 (1), 10.879 (1)
β (°)	94.26 (1)
V (Å³)	722.60 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.40 × 0.34 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.745, 0.834
No. of measured, independent and observed [I > 2σ(I)] reflections	2700, 1603, 1439
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.107, 1.02
No. of reflections	1603
No. of parameters	124
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1ⁱ	0.884 (15)	1.848 (15)	2.730 (2)	176 (2)
N1—H12N···O2ⁱⁱ	0.886 (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

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