2-Amino-5-chloro­pyridinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810032290

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Pages o2323-o2324

https://doi.org/10.1107/S1600536810032290

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2-Amino-5-chloropyridinium 3-carboxy-4-hydroxybenzenesulfonate

Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 8 August 2010; accepted 11 August 2010; online 18 August 2010)

The asymmetric unit of the title salt, C₅H₆ClN₂⁺·C₇H₅O₆S⁻, contains two independent 2-amino-5-chloropyridinium cations and two independent 3-carboxy-4-hydroxybenzenesulfonate anions. In both anions, the O atoms of the sulfonate group are disordered over two sets of positions, with occupancy ratios of 0.47 (5):0.53 (5) and 0.50 (8):0.50 (8). In each anion, an intramolecular O—H⋯O hydrogen bond generating an S(6) motif is observed. In the crystal structure, the cations and anions are linked via N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (110). The structure is further stabilized by π–π interactions between cations and anions [centroid–centroid distance = 3.5454 (12) Å]. The crystal studied was a non-merohedral twin, with a ratio of the twin components of 0.715 (3):0.285 (3).

Related literature

For applications of intermolecular interactions, see: Lam & Mak (2000 ). For sulfosalicylic acid complexes, see: Smith et al. (2004 ); Muthiah et al. (2003 ); Raj et al. (2003 ); Fan et al. (2005 ). For a related structure, see: Pourayoubi et al. (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₆ClN₂⁺·C₇H₅O₆S⁻
M_r = 346.74
Triclinic, $[P \overline 1]$
a = 7.9455 (3) Å
b = 10.9173 (5) Å
c = 16.3535 (7) Å
α = 85.223 (2)°
β = 83.327 (2)°
γ = 85.842 (2)°
V = 1401.22 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 296 K
0.50 × 0.36 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.804, T_max = 0.935
8143 measured reflections
8143 independent reflections
5951 reflections with I > 2σ(I)
R_int = 0.000

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.158
S = 1.04
8143 reflections
478 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O6Xⁱ	0.86	2.08	2.900 (15)	159
N2A—H2AB⋯O5Xⁱⁱ	0.86	2.26	3.115 (9)	171
N2B—H2BA⋯O6B	0.86	2.34	3.114 (19)	150
N2B—H2BA⋯O6Y	0.86	2.20	2.985 (17)	152
N2B—H2BB⋯O5Bⁱⁱⁱ	0.86	2.30	3.146 (17)	168
N2B—H2BB⋯O5Yⁱⁱⁱ	0.86	2.18	3.013 (15)	164
O3A—H2OA⋯O5Bⁱⁱⁱ	0.83 (3)	1.83 (4)	2.657 (16)	180 (5)
O3A—H2OA⋯O5Yⁱⁱⁱ	0.83 (3)	1.84 (4)	2.663 (16)	173 (3)
O3B—H2OB⋯O5X^iv	0.82 (3)	1.90 (3)	2.698 (10)	166 (3)
O1B—H1OB⋯O2B	0.83 (3)	1.84 (3)	2.604 (2)	152 (3)
O1A—H1OA⋯O2A	0.84 (3)	1.85 (3)	2.584 (2)	145 (3)
O1A—H1OO⋯O6B	0.84 (3)	2.51 (4)	3.086 (16)	127 (3)
O1A—H1OA⋯O6Y	0.84 (3)	2.58 (4)	3.163 (18)	128 (3)
N1B—H1NB⋯O4B	0.88 (3)	2.23 (4)	2.999 (19)	146 (3)
N1B—H1NB⋯O4Y	0.88 (3)	2.09 (3)	2.865 (13)	148 (3)
N1A—H1NA⋯O4Xⁱ	0.86 (3)	2.08 (4)	2.87 (2)	153 (3)
C1A—H1AA⋯O1B^v	0.93	2.60	3.422 (3)	148
Symmetry codes: (i) -x+1, -y+2, -z; (ii) x+1, y, z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) x-1, y+1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032290/ci5152sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032290/ci5152Isup2.hkl

checkCIF report

Comment top

Intermolecular interactions are responsible for crystal packing and gaining an understanding of them allows us to comprehend collective properties and permits the design of new crystals with specific physical and chemical properties (Lam & Mak, 2000). 5-Sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) and its organic complexes or salts can develop well-defined non-covalent supramolecular architectures because of their ability to form multiple hydrogen bonds containing components of complementary arrays of hydrogen-bonding sites (Smith et al., 2004; Muthiah et al., 2003; Raj et al., 2003; Fan et al., 2005). The present study has been undertaken to study the hydrogen bonding patterns involving the 3-carboxy-4-hydroxybenzenesulfonate anions with the 2-amino-5-chloropyridinium cations.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-5-chloropyridinium cations (A and B) and two 3-carboxy-4-hydroxybenzenesulfonate anions (A and B) (Fig. 1). Each 2-amino-5-chloropyridinium cation is planar, with a maximum deviation of 0.003 (2) Å for atom C8A in cation A and 0.013 (2) Å for C12B atom in cation B. In the cations, protonation at atoms N1A and N1B lead to a slight increase in the C8A—N1A—C12A [123.3 (2)°] and C8B—N1B—C12B [123.56 (19)°] angles compared to those observed in an unprotonated structure (Pourayoubi et al., 2007). Bond lengths (Allen et al., 1987) and angles are normal. Each 3-carboxy-4-hydroxybenzenesulfonate anions contains an intramolecular O—H···O hydrogen bond, which generates an S(6) ring.

In the crystal structure, (Fig. 2), the sulfonate group of each 3-carboxy-4-hydroxybenzenesulfonate anion interacts with the corresponding 2-amino-5-chloropyridinium cations via a pair of N—H···O hydrogen bonds forming an R₂²(8) ring motif (Bernstein et al., 1995). Here, sulfonate groups mimic the role of the carboxylate groups. The ionic units are further linked by N—H···O, O—H···O and C—H···O (Table 1) hydrogen bonds, forming a two dimensional network parallel to the (110) plane.

Related literature top

For applications of intermolecular interactions, see: Lam & Mak (2000). For sulfosalicylic acid complexes, see: Smith et al. (2004); Muthiah et al. (2003); Raj et al. (2003); Fan et al. (2005). For a related structure, see: Pourayoubi et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

A hot methanol solution (20 ml) of 2-amino-5-chloropyridine (32 mg, Aldrich) and sulfosalicylic acid (54 mg, Merck) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Structure description top

For applications of intermolecular interactions, see: Lam & Mak (2000). For sulfosalicylic acid complexes, see: Smith et al. (2004); Muthiah et al. (2003); Raj et al. (2003); Fan et al. (2005). For a related structure, see: Pourayoubi et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Open bonds indicate minor disordered components.
	Fig. 2. The crystal packing of the title compound, showing a hydrogen-bonded (dashed lines) network. H atoms not involved in the interactions have been omitted for clarity. Only the major component of the disordered O atoms of the sulfonate group are shown.

2-Amino-5-chloropyridinium 3-carboxy-4-hydroxybenzenesulfonate top

Crystal data top

C₅H₆ClN₂⁺·C₇H₅O₆S⁻	Z = 4
M_r = 346.74	F(000) = 712
Triclinic, P1	D_x = 1.644 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9455 (3) Å	Cell parameters from 9907 reflections
b = 10.9173 (5) Å	θ = 2.5–29.9°
c = 16.3535 (7) Å	µ = 0.45 mm⁻¹
α = 85.223 (2)°	T = 296 K
β = 83.327 (2)°	Plate, yellow
γ = 85.842 (2)°	0.50 × 0.36 × 0.15 mm
V = 1401.22 (10) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8143 independent reflections
Radiation source: fine-focus sealed tube	5951 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
φ and ω scans	θ_max = 30.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.804, T_max = 0.935	k = −15→15
8143 measured reflections	l = 0→22

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0866P)² + 0.2919P] where P = (F_o² + 2F_c²)/3
8143 reflections	(Δ/σ)_max = 0.001
478 parameters	Δρ_max = 0.54 e Å⁻³
6 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₅H₆ClN₂⁺·C₇H₅O₆S⁻	γ = 85.842 (2)°
M_r = 346.74	V = 1401.22 (10) Å³
Triclinic, P1	Z = 4
a = 7.9455 (3) Å	Mo Kα radiation
b = 10.9173 (5) Å	µ = 0.45 mm⁻¹
c = 16.3535 (7) Å	T = 296 K
α = 85.223 (2)°	0.50 × 0.36 × 0.15 mm
β = 83.327 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8143 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5951 reflections with I > 2σ(I)
T_min = 0.804, T_max = 0.935	R_int = 0.000
8143 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	6 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.54 e Å⁻³
8143 reflections	Δρ_min = −0.42 e Å⁻³
478 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
S1A	0.35527 (7)	0.80743 (5)	0.00751 (3)	0.04328 (15)
O1A	0.7640 (2)	0.53220 (16)	0.24854 (11)	0.0476 (4)
O2A	0.5653 (2)	0.63703 (16)	0.36240 (9)	0.0513 (4)
O3A	0.3497 (2)	0.76513 (15)	0.32837 (10)	0.0455 (4)
O4A	0.460 (2)	0.837 (2)	−0.0643 (13)	0.072 (5)	0.47 (5)
O5A	0.233 (3)	0.711 (3)	−0.0064 (12)	0.086 (4)	0.47 (5)
O6A	0.266 (3)	0.906 (2)	0.0472 (9)	0.075 (4)	0.47 (5)
O4X	0.465 (2)	0.822 (2)	−0.0720 (11)	0.061 (3)	0.53 (5)
O5X	0.2139 (10)	0.7391 (10)	0.0023 (6)	0.045 (2)	0.53 (5)
O6X	0.304 (2)	0.9285 (11)	0.0377 (11)	0.074 (3)	0.53 (5)
C1A	0.4393 (2)	0.74515 (17)	0.16239 (11)	0.0312 (4)
H1AA	0.3498	0.8004	0.1792	0.037*
C2A	0.4802 (3)	0.72879 (19)	0.07962 (12)	0.0352 (4)
C3A	0.6153 (3)	0.6469 (2)	0.05434 (14)	0.0496 (6)
H3AA	0.6427	0.6358	−0.0015	0.060*
C4A	0.7087 (3)	0.5821 (2)	0.11146 (14)	0.0506 (6)
H4AA	0.7989	0.5279	0.0940	0.061*
C5A	0.6684 (2)	0.59768 (18)	0.19527 (12)	0.0352 (4)
C6A	0.5314 (2)	0.67910 (16)	0.22106 (11)	0.0291 (4)
C7A	0.4856 (2)	0.69252 (17)	0.30980 (12)	0.0327 (4)
Cl1A	0.65336 (10)	0.96478 (9)	0.40572 (4)	0.0741 (2)
N1A	0.6964 (2)	0.97630 (18)	0.16358 (12)	0.0434 (4)
N2A	0.8778 (3)	0.8864 (2)	0.06209 (13)	0.0584 (6)
H2AA	0.8203	0.9251	0.0255	0.070*
H2AB	0.9646	0.8383	0.0472	0.070*
C8A	0.8330 (3)	0.9006 (2)	0.14072 (14)	0.0415 (5)
C9A	0.9200 (3)	0.8392 (2)	0.20505 (16)	0.0469 (5)
H9AA	1.0138	0.7854	0.1922	0.056*
C10A	0.8675 (3)	0.8583 (2)	0.28486 (15)	0.0460 (5)
H10A	0.9259	0.8186	0.3266	0.055*
C11A	0.7244 (3)	0.9383 (2)	0.30458 (14)	0.0438 (5)
C12A	0.6419 (3)	0.9960 (2)	0.24326 (15)	0.0448 (5)
H12A	0.5475	1.0494	0.2557	0.054*
S1B	0.85425 (6)	0.30940 (5)	0.47122 (3)	0.03661 (13)
O1B	1.2477 (2)	0.02225 (16)	0.21626 (10)	0.0469 (4)
O2B	1.0653 (2)	0.14325 (18)	0.11015 (10)	0.0600 (5)
O3B	0.8506 (2)	0.27142 (16)	0.15525 (11)	0.0530 (4)
O4B	0.9689 (18)	0.322 (2)	0.5284 (9)	0.078 (5)	0.50 (8)
O5B	0.7188 (19)	0.226 (2)	0.5092 (10)	0.053 (3)	0.50 (8)
O6B	0.784 (2)	0.4156 (19)	0.4259 (9)	0.061 (3)	0.50 (8)
O4Y	0.9709 (15)	0.3365 (13)	0.5308 (7)	0.042 (3)	0.50 (8)
O5Y	0.7124 (15)	0.2449 (19)	0.5077 (10)	0.041 (2)	0.50 (8)
O6Y	0.802 (2)	0.4296 (15)	0.4326 (11)	0.059 (3)	0.50 (8)
C1B	0.9347 (2)	0.24440 (17)	0.31394 (12)	0.0309 (4)
H1BA	0.8522	0.3052	0.3003	0.037*
C2B	0.9681 (2)	0.22231 (17)	0.39468 (11)	0.0310 (4)
C3B	1.0904 (3)	0.13016 (19)	0.41552 (12)	0.0370 (4)
H3BA	1.1114	0.1140	0.4703	0.044*
C4B	1.1802 (3)	0.06305 (19)	0.35518 (13)	0.0390 (4)
H4BA	1.2607	0.0013	0.3695	0.047*
C5B	1.1508 (2)	0.08727 (17)	0.27276 (12)	0.0323 (4)
C6B	1.0231 (2)	0.17659 (16)	0.25225 (11)	0.0292 (4)
C7B	0.9840 (3)	0.19622 (19)	0.16594 (13)	0.0371 (4)
Cl1B	0.81241 (10)	0.51032 (8)	0.86096 (4)	0.0679 (2)
N1B	0.7949 (2)	0.52963 (17)	0.62141 (11)	0.0374 (4)
N2B	0.6228 (3)	0.6290 (2)	0.53013 (13)	0.0544 (5)
H2BA	0.6839	0.5943	0.4905	0.065*
H2BB	0.5371	0.6782	0.5199	0.065*
C8B	0.6606 (3)	0.60676 (19)	0.60619 (13)	0.0375 (4)
C9B	0.5673 (3)	0.6602 (2)	0.67497 (15)	0.0450 (5)
H9BA	0.4743	0.7149	0.6671	0.054*
C10B	0.6122 (3)	0.6323 (2)	0.75211 (14)	0.0456 (5)
H10B	0.5497	0.6669	0.7971	0.055*
C11B	0.7538 (3)	0.5506 (2)	0.76350 (13)	0.0402 (4)
C12B	0.8428 (3)	0.5010 (2)	0.69775 (14)	0.0397 (4)
H12B	0.9370	0.4471	0.7048	0.048*
H2OA	0.328 (4)	0.768 (3)	0.379 (2)	0.075 (10)*
H2OB	0.840 (4)	0.279 (3)	0.106 (2)	0.062 (9)*
H1OB	1.210 (4)	0.046 (3)	0.172 (2)	0.058 (8)*
H1OA	0.724 (4)	0.545 (3)	0.297 (2)	0.069 (9)*
H1NB	0.855 (3)	0.496 (3)	0.5796 (19)	0.055 (8)*
H1NA	0.644 (4)	1.017 (3)	0.126 (2)	0.065 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0503 (3)	0.0502 (3)	0.0293 (3)	0.0092 (2)	−0.0148 (2)	0.0015 (2)
O1A	0.0462 (9)	0.0562 (10)	0.0372 (8)	0.0221 (7)	−0.0100 (7)	0.0004 (7)
O2A	0.0643 (10)	0.0587 (10)	0.0276 (7)	0.0213 (8)	−0.0099 (7)	0.0010 (7)
O3A	0.0515 (9)	0.0503 (9)	0.0298 (7)	0.0173 (7)	0.0029 (6)	−0.0019 (6)
O4A	0.070 (7)	0.085 (6)	0.049 (8)	0.030 (5)	0.002 (5)	0.027 (5)
O5A	0.125 (9)	0.081 (8)	0.066 (6)	−0.031 (6)	−0.071 (6)	0.024 (5)
O6A	0.088 (7)	0.093 (9)	0.037 (3)	0.063 (6)	−0.017 (4)	−0.007 (5)
O4X	0.061 (6)	0.093 (7)	0.027 (3)	−0.001 (5)	−0.007 (3)	0.011 (4)
O5X	0.044 (4)	0.055 (3)	0.036 (2)	0.002 (2)	−0.015 (3)	0.002 (2)
O6X	0.107 (7)	0.039 (3)	0.078 (7)	0.019 (4)	−0.040 (5)	−0.007 (3)
C1A	0.0317 (9)	0.0326 (9)	0.0295 (9)	0.0047 (7)	−0.0072 (7)	−0.0037 (7)
C2A	0.0392 (10)	0.0390 (10)	0.0280 (9)	0.0057 (8)	−0.0099 (7)	−0.0036 (7)
C3A	0.0586 (14)	0.0608 (14)	0.0274 (10)	0.0219 (11)	−0.0074 (9)	−0.0101 (9)
C4A	0.0527 (13)	0.0596 (14)	0.0357 (11)	0.0279 (11)	−0.0050 (9)	−0.0090 (10)
C5A	0.0363 (9)	0.0375 (10)	0.0311 (9)	0.0089 (8)	−0.0075 (7)	−0.0023 (8)
C6A	0.0302 (8)	0.0300 (9)	0.0270 (8)	0.0029 (7)	−0.0046 (6)	−0.0032 (7)
C7A	0.0385 (9)	0.0305 (9)	0.0282 (9)	0.0017 (7)	−0.0036 (7)	−0.0010 (7)
Cl1A	0.0750 (5)	0.1075 (6)	0.0413 (3)	0.0024 (4)	−0.0094 (3)	−0.0165 (4)
N1A	0.0434 (10)	0.0474 (10)	0.0375 (9)	0.0002 (8)	−0.0086 (8)	0.0109 (8)
N2A	0.0645 (13)	0.0678 (14)	0.0390 (11)	0.0034 (11)	0.0013 (9)	0.0032 (10)
C8A	0.0443 (11)	0.0414 (11)	0.0380 (11)	−0.0072 (9)	−0.0035 (9)	0.0042 (9)
C9A	0.0401 (11)	0.0455 (12)	0.0539 (13)	0.0031 (9)	−0.0080 (10)	0.0021 (10)
C10A	0.0472 (12)	0.0487 (12)	0.0435 (12)	−0.0025 (10)	−0.0173 (9)	0.0056 (10)
C11A	0.0428 (11)	0.0520 (13)	0.0375 (11)	−0.0071 (10)	−0.0071 (9)	−0.0022 (9)
C12A	0.0405 (11)	0.0436 (12)	0.0485 (12)	0.0016 (9)	−0.0036 (9)	0.0007 (10)
S1B	0.0375 (3)	0.0410 (3)	0.0302 (2)	0.00613 (19)	0.00170 (18)	−0.01102 (19)
O1B	0.0503 (9)	0.0549 (10)	0.0337 (8)	0.0255 (7)	−0.0069 (7)	−0.0143 (7)
O2B	0.0735 (12)	0.0750 (12)	0.0305 (8)	0.0284 (10)	−0.0126 (8)	−0.0174 (8)
O3B	0.0641 (11)	0.0569 (10)	0.0401 (9)	0.0240 (8)	−0.0265 (8)	−0.0124 (8)
O4B	0.051 (5)	0.115 (10)	0.076 (7)	0.002 (5)	−0.006 (4)	−0.067 (7)
O5B	0.067 (7)	0.052 (5)	0.039 (4)	−0.015 (4)	0.022 (4)	−0.018 (3)
O6B	0.079 (5)	0.057 (6)	0.043 (3)	0.041 (5)	−0.012 (5)	−0.014 (3)
O4Y	0.044 (4)	0.049 (5)	0.035 (4)	0.006 (2)	−0.009 (3)	−0.024 (3)
O5Y	0.035 (4)	0.053 (5)	0.035 (4)	0.004 (3)	−0.001 (3)	−0.007 (3)
O6Y	0.078 (5)	0.033 (3)	0.058 (6)	0.007 (4)	0.028 (5)	−0.009 (3)
C1B	0.0306 (8)	0.0294 (9)	0.0324 (9)	0.0055 (7)	−0.0051 (7)	−0.0053 (7)
C2B	0.0299 (8)	0.0334 (9)	0.0292 (9)	0.0036 (7)	−0.0006 (7)	−0.0077 (7)
C3B	0.0416 (10)	0.0429 (11)	0.0259 (9)	0.0084 (8)	−0.0077 (7)	−0.0027 (8)
C4B	0.0421 (10)	0.0386 (10)	0.0349 (10)	0.0146 (8)	−0.0082 (8)	−0.0044 (8)
C5B	0.0329 (9)	0.0323 (9)	0.0316 (9)	0.0073 (7)	−0.0044 (7)	−0.0092 (7)
C6B	0.0308 (8)	0.0293 (8)	0.0284 (8)	0.0027 (7)	−0.0069 (7)	−0.0059 (7)
C7B	0.0446 (11)	0.0368 (10)	0.0314 (9)	0.0057 (8)	−0.0117 (8)	−0.0077 (8)
Cl1B	0.0757 (5)	0.0929 (5)	0.0356 (3)	−0.0065 (4)	−0.0114 (3)	0.0010 (3)
N1B	0.0349 (8)	0.0443 (10)	0.0331 (8)	0.0013 (7)	0.0007 (7)	−0.0125 (7)
N2B	0.0505 (11)	0.0758 (15)	0.0366 (10)	0.0078 (10)	−0.0084 (8)	−0.0080 (10)
C8B	0.0354 (10)	0.0415 (11)	0.0357 (10)	−0.0041 (8)	−0.0011 (8)	−0.0070 (8)
C9B	0.0405 (11)	0.0451 (12)	0.0480 (12)	0.0086 (9)	−0.0007 (9)	−0.0113 (10)
C10B	0.0476 (12)	0.0508 (13)	0.0379 (11)	−0.0012 (10)	0.0055 (9)	−0.0166 (9)
C11B	0.0465 (11)	0.0437 (11)	0.0315 (10)	−0.0092 (9)	−0.0047 (8)	−0.0040 (8)
C12B	0.0377 (10)	0.0396 (11)	0.0421 (11)	−0.0010 (8)	−0.0048 (8)	−0.0052 (9)

Geometric parameters (Å, º) top

S1A—O4A	1.386 (18)	S1B—O4B	1.400 (15)
S1A—O5X	1.407 (10)	S1B—O5Y	1.418 (14)
S1A—O6A	1.411 (13)	S1B—O6B	1.436 (11)
S1A—O6X	1.463 (12)	S1B—O6Y	1.462 (12)
S1A—O4X	1.481 (16)	S1B—O4Y	1.481 (13)
S1A—O5A	1.527 (17)	S1B—O5B	1.502 (17)
S1A—C2A	1.7586 (19)	S1B—C2B	1.7605 (18)
O1A—C5A	1.348 (2)	O1B—C5B	1.347 (2)
O1A—H1OA	0.84 (3)	O1B—H1OB	0.84 (3)
O2A—C7A	1.222 (2)	O2B—C7B	1.217 (3)
O3A—C7A	1.314 (2)	O3B—C7B	1.312 (2)
O3A—H2OA	0.83 (4)	O3B—H2OB	0.82 (3)
C1A—C2A	1.378 (3)	C1B—C2B	1.375 (3)
C1A—C6A	1.396 (2)	C1B—C6B	1.394 (2)
C1A—H1AA	0.93	C1B—H1BA	0.93
C2A—C3A	1.394 (3)	C2B—C3B	1.397 (3)
C3A—C4A	1.378 (3)	C3B—C4B	1.378 (3)
C3A—H3AA	0.93	C3B—H3BA	0.93
C4A—C5A	1.392 (3)	C4B—C5B	1.395 (3)
C4A—H4AA	0.93	C4B—H4BA	0.93
C5A—C6A	1.403 (2)	C5B—C6B	1.405 (2)
C6A—C7A	1.472 (3)	C6B—C7B	1.475 (3)
Cl1A—C11A	1.725 (2)	Cl1B—C11B	1.725 (2)
N1A—C8A	1.352 (3)	N1B—C8B	1.344 (3)
N1A—C12A	1.354 (3)	N1B—C12B	1.353 (3)
N1A—H1NA	0.85 (3)	N1B—H1NB	0.88 (3)
N2A—C8A	1.313 (3)	N2B—C8B	1.312 (3)
N2A—H2AA	0.86	N2B—H2BA	0.86
N2A—H2AB	0.86	N2B—H2BB	0.86
C8A—C9A	1.421 (3)	C8B—C9B	1.417 (3)
C9A—C10A	1.352 (4)	C9B—C10B	1.355 (3)
C9A—H9AA	0.93	C9B—H9BA	0.93
C10A—C11A	1.406 (3)	C10B—C11B	1.404 (3)
C10A—H10A	0.93	C10B—H10B	0.93
C11A—C12A	1.350 (3)	C11B—C12B	1.347 (3)
C12A—H12A	0.93	C12B—H12B	0.93

O4A—S1A—O5X	118.5 (11)	O4B—S1B—O5Y	111.5 (9)
O4A—S1A—O6A	116.7 (12)	O4B—S1B—O6B	120.8 (18)
O5X—S1A—O6A	96.8 (11)	O5Y—S1B—O6B	105.3 (9)
O4A—S1A—O6X	102.2 (12)	O4B—S1B—O6Y	110.8 (18)
O5X—S1A—O6X	111.5 (7)	O5Y—S1B—O6Y	111.5 (7)
O5X—S1A—O4X	112.8 (8)	O5Y—S1B—O4Y	113.8 (7)
O6A—S1A—O4X	123.8 (12)	O6B—S1B—O4Y	115.0 (14)
O6X—S1A—O4X	109.6 (9)	O6Y—S1B—O4Y	105.0 (13)
O4A—S1A—O5A	111.0 (11)	O4B—S1B—O5B	109.7 (10)
O6A—S1A—O5A	110.2 (8)	O6B—S1B—O5B	111.7 (7)
O6X—S1A—O5A	124.9 (10)	O6Y—S1B—O5B	118.3 (9)
O4X—S1A—O5A	104.3 (10)	O4Y—S1B—O5B	112.6 (8)
O4A—S1A—C2A	108.6 (9)	O4B—S1B—C2B	105.3 (8)
O5X—S1A—C2A	108.6 (5)	O5Y—S1B—C2B	109.0 (8)
O6A—S1A—C2A	106.6 (6)	O6B—S1B—C2B	104.2 (7)
O6X—S1A—C2A	106.7 (6)	O6Y—S1B—C2B	108.4 (7)
O4X—S1A—C2A	107.3 (8)	O4Y—S1B—C2B	109.0 (5)
O5A—S1A—C2A	102.7 (7)	O5B—S1B—C2B	103.3 (9)
C5A—O1A—H1OA	110 (2)	C5B—O1B—H1OB	104.2 (19)
C7A—O3A—H2OA	111 (2)	C7B—O3B—H2OB	108 (2)
C2A—C1A—C6A	120.28 (17)	C2B—C1B—C6B	120.67 (16)
C2A—C1A—H1AA	119.9	C2B—C1B—H1BA	119.7
C6A—C1A—H1AA	119.9	C6B—C1B—H1BA	119.7
C1A—C2A—C3A	119.85 (18)	C1B—C2B—C3B	119.86 (17)
C1A—C2A—S1A	119.28 (15)	C1B—C2B—S1B	119.63 (14)
C3A—C2A—S1A	120.82 (15)	C3B—C2B—S1B	120.51 (15)
C4A—C3A—C2A	120.5 (2)	C4B—C3B—C2B	120.22 (18)
C4A—C3A—H3AA	119.7	C4B—C3B—H3BA	119.9
C2A—C3A—H3AA	119.7	C2B—C3B—H3BA	119.9
C3A—C4A—C5A	120.18 (19)	C3B—C4B—C5B	120.35 (17)
C3A—C4A—H4AA	119.9	C3B—C4B—H4BA	119.8
C5A—C4A—H4AA	119.9	C5B—C4B—H4BA	119.8
O1A—C5A—C4A	117.78 (18)	O1B—C5B—C4B	117.54 (17)
O1A—C5A—C6A	122.72 (18)	O1B—C5B—C6B	123.07 (17)
C4A—C5A—C6A	119.49 (18)	C4B—C5B—C6B	119.39 (17)
C1A—C6A—C5A	119.67 (17)	C1B—C6B—C5B	119.41 (17)
C1A—C6A—C7A	120.87 (16)	C1B—C6B—C7B	121.17 (16)
C5A—C6A—C7A	119.46 (16)	C5B—C6B—C7B	119.41 (17)
O2A—C7A—O3A	122.55 (18)	O2B—C7B—O3B	123.09 (19)
O2A—C7A—C6A	122.24 (18)	O2B—C7B—C6B	122.51 (18)
O3A—C7A—C6A	115.18 (17)	O3B—C7B—C6B	114.34 (18)
C8A—N1A—C12A	123.3 (2)	C8B—N1B—C12B	123.56 (19)
C8A—N1A—H1NA	119 (2)	C8B—N1B—H1NB	118.3 (19)
C12A—N1A—H1NA	117 (2)	C12B—N1B—H1NB	118.1 (19)
C8A—N2A—H2AA	120.0	C8B—N2B—H2BA	120.0
C8A—N2A—H2AB	120.0	C8B—N2B—H2BB	120.0
H2AA—N2A—H2AB	120.0	H2BA—N2B—H2BB	120.0
N2A—C8A—N1A	119.6 (2)	N2B—C8B—N1B	119.5 (2)
N2A—C8A—C9A	123.5 (2)	N2B—C8B—C9B	123.7 (2)
N1A—C8A—C9A	116.9 (2)	N1B—C8B—C9B	116.86 (19)
C10A—C9A—C8A	120.5 (2)	C10B—C9B—C8B	120.7 (2)
C10A—C9A—H9AA	119.8	C10B—C9B—H9BA	119.7
C8A—C9A—H9AA	119.8	C8B—C9B—H9BA	119.7
C9A—C10A—C11A	119.9 (2)	C9B—C10B—C11B	119.4 (2)
C9A—C10A—H10A	120.1	C9B—C10B—H10B	120.3
C11A—C10A—H10A	120.1	C11B—C10B—H10B	120.3
C12A—C11A—C10A	119.4 (2)	C12B—C11B—C10B	119.6 (2)
C12A—C11A—Cl1A	119.39 (19)	C12B—C11B—Cl1B	119.53 (18)
C10A—C11A—Cl1A	121.21 (18)	C10B—C11B—Cl1B	120.81 (17)
C11A—C12A—N1A	120.1 (2)	C11B—C12B—N1B	119.9 (2)
C11A—C12A—H12A	120.0	C11B—C12B—H12B	120.1
N1A—C12A—H12A	120.0	N1B—C12B—H12B	120.1

C6A—C1A—C2A—C3A	−0.7 (3)	C6B—C1B—C2B—C3B	−0.7 (3)
C6A—C1A—C2A—S1A	176.84 (15)	C6B—C1B—C2B—S1B	−179.98 (14)
O4A—S1A—C2A—C1A	145.7 (11)	O4B—S1B—C2B—C1B	−146.3 (9)
O5X—S1A—C2A—C1A	−84.1 (4)	O5Y—S1B—C2B—C1B	93.8 (6)
O6A—S1A—C2A—C1A	19.2 (13)	O6B—S1B—C2B—C1B	−18.2 (11)
O6X—S1A—C2A—C1A	36.2 (8)	O6Y—S1B—C2B—C1B	−27.7 (10)
O4X—S1A—C2A—C1A	153.7 (9)	O4Y—S1B—C2B—C1B	−141.4 (5)
O5A—S1A—C2A—C1A	−96.7 (12)	O5B—S1B—C2B—C1B	98.6 (7)
O4A—S1A—C2A—C3A	−36.8 (11)	O4B—S1B—C2B—C3B	34.4 (9)
O5X—S1A—C2A—C3A	93.4 (4)	O5Y—S1B—C2B—C3B	−85.4 (6)
O6A—S1A—C2A—C3A	−163.3 (13)	O6B—S1B—C2B—C3B	162.5 (11)
O6X—S1A—C2A—C3A	−146.3 (8)	O6Y—S1B—C2B—C3B	153.1 (10)
O4X—S1A—C2A—C3A	−28.8 (9)	O4Y—S1B—C2B—C3B	39.3 (5)
O5A—S1A—C2A—C3A	80.8 (12)	O5B—S1B—C2B—C3B	−80.6 (8)
C1A—C2A—C3A—C4A	−0.1 (4)	C1B—C2B—C3B—C4B	1.3 (3)
S1A—C2A—C3A—C4A	−177.6 (2)	S1B—C2B—C3B—C4B	−179.42 (17)
C2A—C3A—C4A—C5A	0.2 (4)	C2B—C3B—C4B—C5B	0.6 (3)
C3A—C4A—C5A—O1A	−179.9 (2)	C3B—C4B—C5B—O1B	177.2 (2)
C3A—C4A—C5A—C6A	0.4 (4)	C3B—C4B—C5B—C6B	−3.1 (3)
C2A—C1A—C6A—C5A	1.3 (3)	C2B—C1B—C6B—C5B	−1.8 (3)
C2A—C1A—C6A—C7A	−177.93 (18)	C2B—C1B—C6B—C7B	177.69 (18)
O1A—C5A—C6A—C1A	179.19 (19)	O1B—C5B—C6B—C1B	−176.61 (18)
C4A—C5A—C6A—C1A	−1.2 (3)	C4B—C5B—C6B—C1B	3.7 (3)
O1A—C5A—C6A—C7A	−1.6 (3)	O1B—C5B—C6B—C7B	3.9 (3)
C4A—C5A—C6A—C7A	178.1 (2)	C4B—C5B—C6B—C7B	−175.82 (19)
C1A—C6A—C7A—O2A	−179.1 (2)	C1B—C6B—C7B—O2B	175.9 (2)
C5A—C6A—C7A—O2A	1.7 (3)	C5B—C6B—C7B—O2B	−4.7 (3)
C1A—C6A—C7A—O3A	3.1 (3)	C1B—C6B—C7B—O3B	−6.8 (3)
C5A—C6A—C7A—O3A	−176.13 (18)	C5B—C6B—C7B—O3B	172.69 (18)
C12A—N1A—C8A—N2A	−180.0 (2)	C12B—N1B—C8B—N2B	−179.7 (2)
C12A—N1A—C8A—C9A	0.6 (3)	C12B—N1B—C8B—C9B	0.5 (3)
N2A—C8A—C9A—C10A	179.8 (2)	N2B—C8B—C9B—C10B	179.4 (2)
N1A—C8A—C9A—C10A	−0.8 (3)	N1B—C8B—C9B—C10B	−0.8 (3)
C8A—C9A—C10A—C11A	0.8 (4)	C8B—C9B—C10B—C11B	0.7 (4)
C9A—C10A—C11A—C12A	−0.6 (3)	C9B—C10B—C11B—C12B	−0.1 (3)
C9A—C10A—C11A—Cl1A	179.90 (19)	C9B—C10B—C11B—Cl1B	−178.64 (18)
C10A—C11A—C12A—N1A	0.3 (3)	C10B—C11B—C12B—N1B	−0.3 (3)
Cl1A—C11A—C12A—N1A	179.87 (17)	Cl1B—C11B—C12B—N1B	178.26 (16)
C8A—N1A—C12A—C11A	−0.4 (4)	C8B—N1B—C12B—C11B	0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O6Xⁱ	0.86	2.08	2.900 (15)	159
N2A—H2AB···O5Xⁱⁱ	0.86	2.26	3.115 (9)	171
N2B—H2BA···O6B	0.86	2.34	3.114 (19)	150
N2B—H2BA···O6Y	0.86	2.20	2.985 (17)	152
N2B—H2BB···O5Bⁱⁱⁱ	0.86	2.30	3.146 (17)	168
N2B—H2BB···O5Yⁱⁱⁱ	0.86	2.18	3.013 (15)	164
O3A—H2OA···O5Bⁱⁱⁱ	0.83 (3)	1.83 (4)	2.657 (16)	180 (5)
O3A—H2OA···O5Yⁱⁱⁱ	0.83 (3)	1.84 (4)	2.663 (16)	173 (3)
O3B—H2OB···O5X^iv	0.82 (3)	1.90 (3)	2.698 (10)	166 (3)
O1B—H1OB···O2B	0.83 (3)	1.84 (3)	2.604 (2)	152 (3)
O1A—H1OA···O2A	0.84 (3)	1.85 (3)	2.584 (2)	145 (3)
O1A—H1OA···O6B	0.84 (3)	2.51 (4)	3.086 (16)	127 (3)
O1A—H1OA···O6Y	0.84 (3)	2.58 (4)	3.163 (18)	128 (3)
N1B—H1NB···O4B	0.88 (3)	2.23 (4)	2.999 (19)	146 (3)
N1B—H1NB···O4Y	0.88 (3)	2.09 (3)	2.865 (13)	148 (3)
N1A—H1NA···O4Xⁱ	0.86 (3)	2.08 (4)	2.87 (2)	153 (3)
C1A—H1AA···O1B^v	0.93	2.60	3.422 (3)	148

Symmetry codes: (i) −x+1, −y+2, −z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₅H₆ClN₂⁺·C₇H₅O₆S⁻
M_r	346.74
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.9455 (3), 10.9173 (5), 16.3535 (7)
α, β, γ (°)	85.223 (2), 83.327 (2), 85.842 (2)
V (Å³)	1401.22 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.50 × 0.36 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.804, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	8143, 8143, 5951
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.158, 1.04
No. of reflections	8143
No. of parameters	478
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.42

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O6Xⁱ	0.86	2.08	2.900 (15)	159
N2A—H2AB···O5Xⁱⁱ	0.86	2.26	3.115 (9)	171
N2B—H2BA···O6B	0.86	2.34	3.114 (19)	150
N2B—H2BA···O6Y	0.86	2.20	2.985 (17)	152
N2B—H2BB···O5Bⁱⁱⁱ	0.86	2.30	3.146 (17)	168
N2B—H2BB···O5Yⁱⁱⁱ	0.86	2.18	3.013 (15)	164
O3A—H2OA···O5Bⁱⁱⁱ	0.83 (3)	1.83 (4)	2.657 (16)	180 (5)
O3A—H2OA···O5Yⁱⁱⁱ	0.83 (3)	1.84 (4)	2.663 (16)	173 (3)
O3B—H2OB···O5X^iv	0.82 (3)	1.90 (3)	2.698 (10)	166 (3)
O1B—H1OB···O2B	0.83 (3)	1.84 (3)	2.604 (2)	152 (3)
O1A—H1OA···O2A	0.84 (3)	1.85 (3)	2.584 (2)	145 (3)
O1A—H1OA···O6B	0.84 (3)	2.51 (4)	3.086 (16)	127 (3)
O1A—H1OA···O6Y	0.84 (3)	2.58 (4)	3.163 (18)	128 (3)
N1B—H1NB···O4B	0.88 (3)	2.23 (4)	2.999 (19)	146 (3)
N1B—H1NB···O4Y	0.88 (3)	2.09 (3)	2.865 (13)	148 (3)
N1A—H1NA···O4Xⁱ	0.86 (3)	2.08 (4)	2.87 (2)	153 (3)
C1A—H1AA···O1B^v	0.93	2.60	3.422 (3)	148

Symmetry codes: (i) −x+1, −y+2, −z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x−1, y+1, z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia for Research University Golden Goose grant No. 1001/PFIZIK/811012. MH also thanks Universiti Sains Malaysia for a postdoctoral research fellowship.

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