2-Amino-6-methyl­pyridinium 4-methyl­benzene­sulfonate

Babu, K.S.S.; Dhavamurthy, M.; NizamMohideen, M.; Peramaiyan, G.; Mohan, R.

doi:10.1107/S1600536814008587

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Pages o600-o601

doi:10.1107/S1600536814008587

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2-Amino-6-methylpyridinium 4-methylbenzenesulfonate

K. Syed Suresh Babu,^a,^b M. Dhavamurthy,^a M. NizamMohideen,^b ^* G. Peramaiyan ^a and R. Mohan ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, Tamil Nadu, India, and ^bDepartment of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India
^*Correspondence e-mail: mnizam_new@yahoo.in, professormohan@yahoo.co.in

(Received 10 April 2014; accepted 15 April 2014; online 26 April 2014)

In the asymmetric unit of the title salt, C₆H₉N₂⁺·C₇H₇O₃S⁻, there are two independent 2-amino-6-methylpyridinium cations and two independent 4-methylbenzenesulfonate anions. Both cations are protonated at their pyridine N atoms and their geometries reveal amine–imine tautomerism. In the 4-methylbenzenesulfonate anions, the carboxylate groups are twisted out of the benzene ring planes by 88.4 (1) and 86.2 (2)°. In the crystal, the sulfonate O atoms of an anion interact with the protonated N atoms and the 2-amino groups of a cation via a pair of N—H⋯O hydrogen bonds, forming an R₂²(8) ring motif. These motifs are connected via N—H⋯O hydrogen bonds, forming chains running along the a-axis direction. Within the chains there are weak C—H⋯O hydrogen bonds present. In addition, aromatic π–π stacking interactions [centroid–centroid distances = 3.771 (2), 3.599 (2), 3.599 (2) and 3.497 (2) Å] involving neighbouring chains are also observed.

CCDC reference: 997539

Related literature

For crystal structures of related pyridine derivatives and their applications, see: Babu et al. (2014 ); Rajkumar et al. (2014 ); Jin et al. (2005 ). For unprotonated aminopyridine derivatives, see: Anderson et al. (2005 ). For the structure of amino-methylpyridinium, see: Nahringbauer & Kvick (1977 ). For details of sulfonates, see: Onoda et al. (2001 ); Baskar Raj et al. (2003 ). For applications of benzenesulfonic acid, see: Wang & Wei (2007 ). For simple organic–inorganic salts containing strong intermolecular hydrogen bonds, see: Sethuram et al. (2013a ,b ); Shihabuddeen Syed et al. (2013 ); Showrilu et al. (2013 ); Huq et al. (2013 ). For bond-length data, see: Allen et al. (1987 ). For studies on the tautomeric forms of 2-aminopyridine systems, see: Ishikawa et al. (2002 ). For graph-set analysis, see: Etter (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₉N₂⁺·C₇H₇O₃S⁻
M_r = 280.35
Triclinic, $[P \overline 1]$
a = 7.5343 (2) Å
b = 13.6212 (5) Å
c = 13.9887 (5) Å
α = 106.307 (2)°
β = 97.946 (1)°
γ = 92.103 (2)°
V = 1360.31 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.920, T_max = 0.953
32534 measured reflections
6237 independent reflections
4709 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.119
S = 1.06
6237 reflections
372 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.90 (1)	1.88 (1)	2.772 (2)	171 (2)
N2—H2A⋯O3ⁱ	0.87 (1)	2.01 (1)	2.880 (2)	174 (2)
N2—H2B⋯O1	0.88 (1)	2.07 (1)	2.919 (2)	162 (2)
N3—H3A⋯O5	0.89 (1)	1.90 (1)	2.789 (2)	174 (2)
N4—H4A⋯O4ⁱⁱ	0.88 (1)	2.02 (1)	2.882 (2)	167 (2)
N4—H4B⋯O6	0.88 (1)	2.04 (1)	2.883 (2)	162 (2)
C22—H22⋯O5ⁱⁱ	0.93	2.58	3.455 (2)	157
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 997539

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814008587/su2726sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814008587/su2726Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814008587/su2726Isup3.cml

checkCIF report

Introduction top

2-Aminopyridine and its derivatives play an important role in heterocyclic chemistry. Pyridine heterocycles and their derivatives are present in many large molecules having photo-chemical, electro-chemical and catalytic applications (Babu et al., 2014). Simple organic-inorganic salts containing strong intermolecular hydrogen bonds have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Sethuram, et al., 2013a,b; Huq et al., 2013; Shihabuddeen Syed et al., 2013; Showrilu et al., 2013). Hydrogen-bonding patterns involving sulfonate groups in biological systems and metal complexes are of current interest (Onoda et al., 2001). Such interactions can be utilized for designing supramolecular architectures (Baskar Raj et al., 2003). Benzenesulfonic acid, is a particularly strong organic acid which is capable of protonating N-containing heterocycles and other Lewis bases (Wang & Wei, 2007). We have recently reported the crystal structures of 2-amino-6-methylpyridinium 2,2,2-trichloroacetate (Babu et al., 2014) and 2-Amino-5-nitropyridinium hydrogen oxalate (Rajkumar et al., 2014). In continuation of our studies of pyridinium derivatives, the crystal structure determination of the title compound has been undertaken.

Comment / Result and Discussion top

The asymmetric unit of title salt, Fig. 1, consists of two crystallographically independent protonated 2-amino-6-methylpyridinium cation and two crystallographically independent 4-methyl benzenesulfonate anions. The normal probability plot analyses (International Tables for X-ray Crystallography, 1974, Vol. IV, pp. 293–309) for both bond lengths and angles show that the differences between the two symmetry independent molecules are of a statistical nature. All bond lengths (Allen et al., 1987) and angles are within normal ranges and comparable with those in closely related structures (Babu et al., 2014; Rajkumar et al., 2014). A proton transfer from the carboxyl group of p-toluenesulfonic acid to atom N1 and N3 of 2-amino-6-methyl pyridine resulted in the formation of a salt. This protonation lead to the widening of the C8—N1—C12 and C21—N3—C25 angles of the pyridine rings to 124.0 (2) ° and 123.8 (2) °, compared to 115.3 (2) ° in the unprotonated aminopyridine (Anderson et al., 2005). This type of protonation is observed in various aminopyridine acid complexes (Babu et al., 2014; Rajkumar et al., 2014).

In the cation, the N2—C8 [1.325 (2) Å] N4—C21 bonds [1.325 (2) Å] is shorter than the N1—C8 [1.347 (2) Å], N1—C12 [1.360 (2) Å], N3—C21[1.352 (2) Å] and N3—C25[1.362 (2) Å] bonds, and the C8—C9 [1.406 (3) Å], C10—C11 [1.398 (3) Å], C21—C22 [1.405 (3) Å] and C23—C24 [1.401 (3) Å] bonds are significantly longer than C9—C10 [1.357 (3) Å], C11—C12 [1.356 (3) Å]. C22—C23 [1.357 (3) Å] and C24—C25 [1.353 (3) Å] bonds, are similar to those in the amino-methylprydinium cation (Babu et al., 2014; Rajkumar et al., 2014). In contrast, in the solid state structure of amino-methylpyridinium, the N—C bond out of ring is clearly longer than that in the ring (Nahringbauer et al., 1977). The geometrical features of the amino-methylpyridinium cation (N1/N2/C1/C6 and N3/N4/C9—C13) resemble those observed in other 2-aminopyridinium structures (Babu et al., 2014; Rajkumar et al., 2014) that are believed to be involved in amine-imine tautomerism (Ishikawa et al., 2002). Similar features are also provided by cation amino-methylpyridinium (N3/N4/C7/C12). However, previous study show that a pyridinium cation always possesses an expanded angle of C—N—C in comparison with the parent pyridine (Jin et al., 2005).

The examination of pyridinium rings shows that these units are planar with mean deviation of -0.006 (2) and 0.005 (2) Å for atoms C8 and C21, from the mean planes defined by the six constituent atoms. The dihedral angle between the 2-amino-6-methylpyridinium cation and 4-methylbenzenesulfonate anion group is 88.4 (2) and 86.2 (2)° for the both molecules, respectively. In both the molecules, the protonated 2-amino-6-methylpyridinium cation is essentially planar, with maximum deviations of -0.012 (2) for atom C13 and -0.006 (2) Å for atom C25.

Hydrogen bonding interaction / Intermolecular N—H···O and C—H···O interaction top

In the crystal (Fig. 2), the protonated atoms (N1 and N3) and a nitrogen atom of the 2-amino groups (N2 and N4) of the 2-amino-6-methylpyridinium cations are hydrogen bonded to the carboxylate oxygen atoms (O1, O2, O3 and O4) of the sulfonate groups of the p-toluenesulfonate anions via a pair of intermolecular N—H···O hydrogen bonds (Table 1), forming a ring motif with a graph-set notation of R²₂(8) [Etter, 1990; Bernstein et al., 1995]. The sulfonate group mimics the carboxylate anion's mode of association, which is more commonly seen when binding with 2-aminopyrimidines. It is well known that sulfonates imitate carboxylates in forming such bidentate motifs (Baskar Raj et al., 2003).

Furthermore, these motifs are connected via N—H···O hydrogen bonds (Fig. 2 and Table 1), involving the 2-amino group of the 2-amino-6-methyl pyridinium cation and atoms O3 and O4 of an anion, to form a supramolecular chains along the a axis direction. Weak C—H···O hydrogen bonds, involving a pyridine group of the cation and an O atom of a sulfonate anion, within the chains are also observed (Fig. 2 and Table 1).

Aromatic interaction top

In addition, the cations of neighbouring chains are linked through aromatic π-π interactions with centroid distances Cg1···Cg1ⁱⁱⁱ = 3.771 (2), Cg1···Cg2^iv = 3.599 (2), Cg2···Cg1^v = 3.599 (2) and Cg2···Cg2^vi = 3.497 (2) Å [symmetry codes are as in Table 1 and (iii) = -x+1,-y+1,-z+2; (iv) = x, y, z+ (v) = x, y, z+1; (vi) = -x+1, -y, -z; Cg1 and Cg2 are the centroids of the N1/C8—C12 and N3/C21—C25 rings, respectively].

Uses top

The identification of such supramolecular patterns will help us design and construct preferred hydrogen bonding patterns of drug like molecules.

Synthesis and crystallization top

Crystals of the title compound were obtained by slow evaporation of a 1:1 equimolar mixture of 2-amino-6-methylpyridine and benzenesulfonic acid in methanol at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. N-bound H atoms were located in a difference Fourier map and refined with distance restraints: N—H = 0.88 (1) and 0.90 (1) Å for NH₂ and NH H atoms, respectively. The C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms. A rotating group model was used for the methyl group.

Related literature top

For crystal structures of related pyridine derivatives and their applications, see: Babu et al. (2014); Rajkumar et al. (2014); Jin et al. (2005). For unprotonated aminopyridine derivatives, see: Anderson et al. (2005). For the structure of amino-methylpyridinium, see: Nahringbauer & Kvick (1977). For details of sulfonates, see: Onoda et al. (2001); Baskar Raj et al. (2003). For applications of benzenesulfonic acid, see: Wang & Wei (2007). For simple organic–inorganic salts containing strong intermolecular hydrogen bonds, see: Sethuram et al. (2013a,b); Shihabuddeen Syed et al. (2013); Showrilu et al. (2013); Huq et al. (2013). For bond-length data, see: Allen et al. (1987). For studies on the tautomeric forms of 2-aminopyridine systems, see: Ishikawa et al. (2002). For graph-set analysis, see: Etter (1990); Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the molecular structure of the two independent benezesulfonate anions and the two independent 2-amino-6-methylpyridinium cations of the title salt. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. The N—H···O and C—H···O hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

2-Amino-6-methylpyridinium 4-methylbenzenesulfonate top

Crystal data top

C₆H₉N₂⁺·C₇H₇O₃S⁻	Z = 4
M_r = 280.35	F(000) = 592
Triclinic, P1	D_x = 1.369 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5343 (2) Å	Cell parameters from 6237 reflections
b = 13.6212 (5) Å	θ = 2.0–28.1°
c = 13.9887 (5) Å	µ = 0.24 mm⁻¹
α = 106.307 (2)°	T = 293 K
β = 97.946 (1)°	Block, colourless
γ = 92.103 (2)°	0.35 × 0.25 × 0.20 mm
V = 1360.31 (8) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	6237 independent reflections
Radiation source: fine-focus sealed tube	4709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.920, T_max = 0.953	k = −17→17
32534 measured reflections	l = −18→18

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0502P)² + 0.655P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6237 reflections	Δρ_max = 0.33 e Å⁻³
372 parameters	Δρ_min = −0.37 e Å⁻³
6 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: 0.0067 (10)

Crystal data top

C₆H₉N₂⁺·C₇H₇O₃S⁻	γ = 92.103 (2)°
M_r = 280.35	V = 1360.31 (8) Å³
Triclinic, P1	Z = 4
a = 7.5343 (2) Å	Mo Kα radiation
b = 13.6212 (5) Å	µ = 0.24 mm⁻¹
c = 13.9887 (5) Å	T = 293 K
α = 106.307 (2)°	0.35 × 0.25 × 0.20 mm
β = 97.946 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6237 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	4709 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.953	R_int = 0.026
32534 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.33 e Å⁻³
6237 reflections	Δρ_min = −0.37 e Å⁻³
372 parameters

Special details top

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
C1	0.7573 (2)	0.33148 (14)	0.65370 (12)	0.0340 (4)
C2	0.6441 (3)	0.28156 (17)	0.56563 (15)	0.0510 (5)
H2	0.5822	0.2192	0.5594	0.061*
C3	0.6232 (3)	0.32433 (19)	0.48708 (16)	0.0568 (6)
H3	0.5472	0.2897	0.4279	0.068*
C4	0.7111 (3)	0.41650 (17)	0.49332 (15)	0.0450 (5)
C5	0.8219 (3)	0.46630 (18)	0.58213 (16)	0.0525 (5)
H5	0.8818	0.5293	0.5886	0.063*
C6	0.8455 (3)	0.42432 (17)	0.66170 (15)	0.0498 (5)
H6	0.9213	0.4590	0.7209	0.060*
C7	0.6848 (3)	0.4621 (2)	0.40658 (18)	0.0658 (7)
H7A	0.7653	0.4341	0.3602	0.099*
H7B	0.7093	0.5352	0.4315	0.099*
H7C	0.5630	0.4461	0.3727	0.099*
O1	0.63184 (18)	0.20570 (11)	0.73960 (10)	0.0473 (3)
O2	0.80180 (19)	0.36019 (11)	0.84663 (10)	0.0482 (3)
O3	0.95409 (17)	0.22525 (12)	0.74752 (10)	0.0487 (4)
S1	0.78890 (6)	0.27601 (4)	0.75373 (3)	0.03657 (13)
C14	0.1612 (2)	0.16545 (14)	0.35185 (12)	0.0335 (4)
C15	0.2427 (3)	0.07546 (17)	0.34413 (15)	0.0497 (5)
H15	0.2824	0.0416	0.2843	0.060*
C16	0.2656 (3)	0.03531 (17)	0.42480 (16)	0.0532 (5)
H16	0.3205	−0.0258	0.4186	0.064*
C17	0.2085 (3)	0.08433 (16)	0.51461 (14)	0.0427 (4)
C18	0.1255 (3)	0.17361 (18)	0.52060 (15)	0.0522 (5)
H18	0.0851	0.2074	0.5802	0.063*
C19	0.1007 (3)	0.21434 (16)	0.44031 (15)	0.0471 (5)
H19	0.0434	0.2746	0.4459	0.057*
C20	0.2366 (3)	0.0415 (2)	0.60338 (17)	0.0610 (6)
H20A	0.3489	0.0705	0.6450	0.092*
H20B	0.2384	−0.0317	0.5797	0.092*
H20C	0.1403	0.0584	0.6420	0.092*
O4	−0.01417 (17)	0.27792 (12)	0.25616 (11)	0.0496 (4)
O5	0.13593 (18)	0.13852 (11)	0.15948 (9)	0.0471 (3)
O6	0.30945 (17)	0.28838 (11)	0.27035 (10)	0.0453 (3)
S2	0.14592 (6)	0.22210 (4)	0.25238 (3)	0.03629 (13)
C21	0.5816 (2)	0.16145 (13)	0.08860 (13)	0.0327 (4)
C22	0.7160 (2)	0.14424 (14)	0.02675 (14)	0.0368 (4)
H22	0.8366	0.1588	0.0550	0.044*
C23	0.6682 (2)	0.10619 (15)	−0.07461 (14)	0.0407 (4)
H23	0.7569	0.0954	−0.1157	0.049*
C24	0.4871 (2)	0.08288 (14)	−0.11818 (14)	0.0392 (4)
H24	0.4556	0.0568	−0.1877	0.047*
C25	0.3584 (2)	0.09863 (13)	−0.05818 (13)	0.0340 (4)
C26	0.1613 (2)	0.07772 (16)	−0.09541 (15)	0.0452 (5)
H26A	0.1106	0.1403	−0.0996	0.068*
H26B	0.1047	0.0509	−0.0496	0.068*
H26C	0.1419	0.0285	−0.1609	0.068*
N3	0.40875 (19)	0.13737 (11)	0.04333 (11)	0.0325 (3)
N4	0.6161 (2)	0.19844 (15)	0.18808 (12)	0.0445 (4)
C8	0.3602 (2)	0.33977 (13)	0.91967 (13)	0.0334 (4)
C9	0.2264 (2)	0.35815 (15)	0.98204 (14)	0.0393 (4)
H9	0.1055	0.3440	0.9543	0.047*
C10	0.2761 (3)	0.39686 (16)	1.08322 (15)	0.0449 (5)
H10	0.1883	0.4085	1.1248	0.054*
C11	0.4573 (3)	0.41950 (16)	1.12590 (14)	0.0432 (4)
H11	0.4896	0.4463	1.1953	0.052*
C12	0.5854 (2)	0.40210 (13)	1.06520 (13)	0.0348 (4)
C13	0.7826 (3)	0.42082 (16)	1.10162 (15)	0.0460 (5)
H13A	0.8040	0.4713	1.1664	0.069*
H13B	0.8402	0.4453	1.0547	0.069*
H13C	0.8305	0.3580	1.1072	0.069*
N1	0.53289 (19)	0.36343 (11)	0.96397 (11)	0.0326 (3)
N2	0.3236 (2)	0.30260 (14)	0.82019 (13)	0.0449 (4)
H2A	0.2112 (15)	0.2825 (16)	0.7953 (15)	0.050 (6)*
H4B	0.531 (2)	0.2199 (16)	0.2235 (14)	0.050 (6)*
H4A	0.7276 (16)	0.2181 (17)	0.2166 (16)	0.058 (7)*
H2B	0.409 (2)	0.2798 (17)	0.7850 (15)	0.055 (7)*
H1A	0.619 (2)	0.3551 (17)	0.9244 (14)	0.051 (6)*
H3A	0.322 (2)	0.1430 (16)	0.0815 (13)	0.045 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0265 (8)	0.0429 (10)	0.0285 (8)	0.0011 (7)	0.0034 (6)	0.0043 (7)
C2	0.0497 (12)	0.0530 (12)	0.0423 (11)	−0.0155 (9)	−0.0094 (9)	0.0114 (10)
C3	0.0541 (13)	0.0694 (15)	0.0389 (11)	−0.0148 (11)	−0.0147 (9)	0.0157 (10)
C4	0.0383 (10)	0.0593 (12)	0.0387 (10)	0.0060 (9)	0.0052 (8)	0.0166 (9)
C5	0.0553 (13)	0.0522 (12)	0.0472 (12)	−0.0124 (10)	0.0042 (10)	0.0140 (10)
C6	0.0486 (11)	0.0569 (13)	0.0341 (10)	−0.0154 (10)	−0.0048 (8)	0.0050 (9)
C7	0.0627 (15)	0.0858 (18)	0.0588 (15)	0.0065 (13)	0.0054 (11)	0.0386 (14)
O1	0.0392 (7)	0.0579 (9)	0.0471 (8)	−0.0029 (6)	0.0109 (6)	0.0176 (7)
O2	0.0492 (8)	0.0618 (9)	0.0292 (7)	0.0042 (7)	0.0089 (6)	0.0047 (6)
O3	0.0341 (7)	0.0696 (10)	0.0431 (8)	0.0140 (6)	0.0050 (6)	0.0164 (7)
S1	0.0285 (2)	0.0514 (3)	0.0289 (2)	0.00414 (18)	0.00579 (16)	0.00929 (19)
C14	0.0279 (8)	0.0418 (10)	0.0281 (8)	0.0000 (7)	0.0043 (6)	0.0060 (7)
C15	0.0591 (13)	0.0552 (13)	0.0343 (10)	0.0181 (10)	0.0157 (9)	0.0065 (9)
C16	0.0624 (13)	0.0512 (12)	0.0461 (12)	0.0192 (10)	0.0076 (10)	0.0129 (10)
C17	0.0374 (10)	0.0538 (12)	0.0359 (10)	−0.0053 (8)	0.0003 (8)	0.0151 (9)
C18	0.0590 (13)	0.0651 (14)	0.0342 (10)	0.0124 (11)	0.0193 (9)	0.0106 (10)
C19	0.0527 (12)	0.0499 (12)	0.0413 (11)	0.0156 (9)	0.0171 (9)	0.0111 (9)
C20	0.0603 (14)	0.0771 (17)	0.0494 (13)	−0.0044 (12)	−0.0013 (10)	0.0302 (12)
O4	0.0337 (7)	0.0652 (9)	0.0513 (8)	0.0065 (6)	−0.0015 (6)	0.0226 (7)
O5	0.0446 (7)	0.0630 (9)	0.0281 (7)	−0.0099 (6)	0.0044 (5)	0.0064 (6)
O6	0.0335 (7)	0.0574 (9)	0.0437 (7)	−0.0099 (6)	0.0020 (6)	0.0163 (6)
S2	0.0269 (2)	0.0506 (3)	0.0298 (2)	−0.00331 (18)	0.00094 (16)	0.01147 (19)
C21	0.0292 (8)	0.0340 (9)	0.0360 (9)	0.0009 (7)	0.0005 (7)	0.0140 (7)
C22	0.0264 (8)	0.0400 (10)	0.0446 (10)	0.0042 (7)	0.0037 (7)	0.0140 (8)
C23	0.0367 (9)	0.0460 (11)	0.0420 (10)	0.0081 (8)	0.0109 (8)	0.0144 (9)
C24	0.0405 (10)	0.0438 (10)	0.0328 (9)	0.0034 (8)	0.0024 (7)	0.0117 (8)
C25	0.0330 (9)	0.0334 (9)	0.0367 (9)	−0.0004 (7)	−0.0012 (7)	0.0154 (7)
C26	0.0346 (10)	0.0527 (12)	0.0464 (11)	−0.0040 (8)	−0.0051 (8)	0.0177 (9)
N3	0.0269 (7)	0.0378 (8)	0.0345 (8)	0.0008 (6)	0.0036 (6)	0.0140 (6)
N4	0.0319 (8)	0.0622 (11)	0.0351 (9)	−0.0002 (8)	0.0003 (7)	0.0098 (8)
C8	0.0309 (8)	0.0348 (9)	0.0366 (9)	0.0069 (7)	0.0038 (7)	0.0139 (7)
C9	0.0303 (9)	0.0456 (11)	0.0445 (10)	0.0088 (7)	0.0074 (7)	0.0154 (8)
C10	0.0436 (10)	0.0532 (12)	0.0445 (11)	0.0133 (9)	0.0175 (9)	0.0185 (9)
C11	0.0497 (11)	0.0494 (11)	0.0316 (9)	0.0083 (9)	0.0052 (8)	0.0133 (8)
C12	0.0379 (9)	0.0333 (9)	0.0353 (9)	0.0038 (7)	0.0016 (7)	0.0149 (7)
C13	0.0397 (10)	0.0508 (12)	0.0457 (11)	−0.0001 (9)	−0.0040 (8)	0.0167 (9)
N1	0.0301 (7)	0.0365 (8)	0.0325 (8)	0.0055 (6)	0.0055 (6)	0.0116 (6)
N2	0.0328 (8)	0.0611 (11)	0.0365 (9)	0.0045 (8)	0.0028 (7)	0.0081 (8)

Geometric parameters (Å, º) top

C1—C6	1.375 (3)	O6—S2	1.4497 (13)
C1—C2	1.380 (2)	C21—N4	1.325 (2)
C1—S1	1.7609 (18)	C21—N3	1.352 (2)
C2—C3	1.375 (3)	C21—C22	1.405 (3)
C2—H2	0.9300	C22—C23	1.357 (3)
C3—C4	1.372 (3)	C22—H22	0.9300
C3—H3	0.9300	C23—C24	1.401 (3)
C4—C5	1.378 (3)	C23—H23	0.9300
C4—C7	1.504 (3)	C24—C25	1.353 (3)
C5—C6	1.381 (3)	C24—H24	0.9300
C5—H5	0.9300	C25—N3	1.362 (2)
C6—H6	0.9300	C25—C26	1.493 (2)
C7—H7A	0.9600	C26—H26A	0.9600
C7—H7B	0.9600	C26—H26B	0.9600
C7—H7C	0.9600	C26—H26C	0.9600
O1—S1	1.4499 (14)	N3—H3A	0.894 (9)
O2—S1	1.4605 (14)	N4—H4B	0.876 (9)
O3—S1	1.4469 (13)	N4—H4A	0.876 (10)
C14—C15	1.375 (3)	C8—N2	1.325 (2)
C14—C19	1.378 (3)	C8—N1	1.347 (2)
C14—S2	1.7636 (18)	C8—C9	1.406 (3)
C15—C16	1.379 (3)	C9—C10	1.357 (3)
C15—H15	0.9300	C9—H9	0.9300
C16—C17	1.382 (3)	C10—C11	1.398 (3)
C16—H16	0.9300	C10—H10	0.9300
C17—C18	1.375 (3)	C11—C12	1.356 (3)
C17—C20	1.507 (3)	C11—H11	0.9300
C18—C19	1.380 (3)	C12—N1	1.360 (2)
C18—H18	0.9300	C12—C13	1.491 (3)
C19—H19	0.9300	C13—H13A	0.9600
C20—H20A	0.9600	C13—H13B	0.9600
C20—H20B	0.9600	C13—H13C	0.9600
C20—H20C	0.9600	N1—H1A	0.900 (9)
O4—S2	1.4485 (14)	N2—H2A	0.873 (10)
O5—S2	1.4582 (14)	N2—H2B	0.877 (10)

C6—C1—C2	119.11 (18)	O4—S2—C14	106.93 (8)
C6—C1—S1	120.76 (13)	O6—S2—C14	106.19 (8)
C2—C1—S1	120.13 (15)	O5—S2—C14	106.66 (8)
C3—C2—C1	119.76 (19)	N4—C21—N3	118.92 (16)
C3—C2—H2	120.1	N4—C21—C22	123.44 (16)
C1—C2—H2	120.1	N3—C21—C22	117.63 (16)
C4—C3—C2	122.01 (18)	C23—C22—C21	119.40 (16)
C4—C3—H3	119.0	C23—C22—H22	120.3
C2—C3—H3	119.0	C21—C22—H22	120.3
C3—C4—C5	117.70 (19)	C22—C23—C24	120.92 (17)
C3—C4—C7	120.99 (19)	C22—C23—H23	119.5
C5—C4—C7	121.3 (2)	C24—C23—H23	119.5
C4—C5—C6	121.2 (2)	C25—C24—C23	119.41 (17)
C4—C5—H5	119.4	C25—C24—H24	120.3
C6—C5—H5	119.4	C23—C24—H24	120.3
C1—C6—C5	120.25 (18)	C24—C25—N3	118.87 (16)
C1—C6—H6	119.9	C24—C25—C26	124.50 (17)
C5—C6—H6	119.9	N3—C25—C26	116.63 (16)
C4—C7—H7A	109.5	C25—C26—H26A	109.5
C4—C7—H7B	109.5	C25—C26—H26B	109.5
H7A—C7—H7B	109.5	H26A—C26—H26B	109.5
C4—C7—H7C	109.5	C25—C26—H26C	109.5
H7A—C7—H7C	109.5	H26A—C26—H26C	109.5
H7B—C7—H7C	109.5	H26B—C26—H26C	109.5
O3—S1—O1	113.06 (9)	C21—N3—C25	123.75 (15)
O3—S1—O2	111.56 (8)	C21—N3—H3A	119.2 (13)
O1—S1—O2	111.86 (8)	C25—N3—H3A	117.0 (13)
O3—S1—C1	107.19 (8)	C21—N4—H4B	121.1 (15)
O1—S1—C1	106.16 (8)	C21—N4—H4A	118.4 (16)
O2—S1—C1	106.52 (9)	H4B—N4—H4A	118 (2)
C15—C14—C19	119.43 (18)	N2—C8—N1	119.09 (16)
C15—C14—S2	120.43 (14)	N2—C8—C9	123.12 (16)
C19—C14—S2	120.03 (15)	N1—C8—C9	117.77 (16)
C14—C15—C16	120.19 (18)	C10—C9—C8	119.13 (17)
C14—C15—H15	119.9	C10—C9—H9	120.4
C16—C15—H15	119.9	C8—C9—H9	120.4
C15—C16—C17	121.08 (19)	C9—C10—C11	121.08 (18)
C15—C16—H16	119.5	C9—C10—H10	119.5
C17—C16—H16	119.5	C11—C10—H10	119.5
C18—C17—C16	117.94 (18)	C12—C11—C10	119.44 (18)
C18—C17—C20	120.96 (19)	C12—C11—H11	120.3
C16—C17—C20	121.1 (2)	C10—C11—H11	120.3
C17—C18—C19	121.60 (18)	C11—C12—N1	118.61 (17)
C17—C18—H18	119.2	C11—C12—C13	124.54 (17)
C19—C18—H18	119.2	N1—C12—C13	116.85 (16)
C14—C19—C18	119.74 (19)	C12—C13—H13A	109.5
C14—C19—H19	120.1	C12—C13—H13B	109.5
C18—C19—H19	120.1	H13A—C13—H13B	109.5
C17—C20—H20A	109.5	C12—C13—H13C	109.5
C17—C20—H20B	109.5	H13A—C13—H13C	109.5
H20A—C20—H20B	109.5	H13B—C13—H13C	109.5
C17—C20—H20C	109.5	C8—N1—C12	123.96 (15)
H20A—C20—H20C	109.5	C8—N1—H1A	118.4 (14)
H20B—C20—H20C	109.5	C12—N1—H1A	117.6 (14)
O4—S2—O6	112.84 (9)	C8—N2—H2A	115.9 (15)
O4—S2—O5	112.66 (8)	C8—N2—H2B	120.4 (15)
O6—S2—O5	111.06 (8)	H2A—N2—H2B	120 (2)

C6—C1—C2—C3	0.9 (3)	C15—C14—S2—O4	151.01 (16)
S1—C1—C2—C3	−178.58 (18)	C19—C14—S2—O4	−32.74 (18)
C1—C2—C3—C4	−0.5 (4)	C15—C14—S2—O6	−88.27 (17)
C2—C3—C4—C5	−0.4 (4)	C19—C14—S2—O6	87.97 (17)
C2—C3—C4—C7	−179.5 (2)	C15—C14—S2—O5	30.25 (18)
C3—C4—C5—C6	0.8 (3)	C19—C14—S2—O5	−153.50 (15)
C7—C4—C5—C6	179.9 (2)	N4—C21—C22—C23	−179.93 (18)
C2—C1—C6—C5	−0.5 (3)	N3—C21—C22—C23	1.0 (3)
S1—C1—C6—C5	178.96 (17)	C21—C22—C23—C24	−0.7 (3)
C4—C5—C6—C1	−0.3 (3)	C22—C23—C24—C25	0.0 (3)
C6—C1—S1—O3	−81.39 (18)	C23—C24—C25—N3	0.3 (3)
C2—C1—S1—O3	98.11 (17)	C23—C24—C25—C26	179.47 (17)
C6—C1—S1—O1	157.51 (16)	N4—C21—N3—C25	−179.79 (17)
C2—C1—S1—O1	−22.99 (19)	C22—C21—N3—C25	−0.7 (3)
C6—C1—S1—O2	38.15 (18)	C24—C25—N3—C21	0.0 (3)
C2—C1—S1—O2	−142.35 (17)	C26—C25—N3—C21	−179.21 (16)
C19—C14—C15—C16	−0.9 (3)	N2—C8—C9—C10	−179.67 (19)
S2—C14—C15—C16	175.40 (17)	N1—C8—C9—C10	−1.1 (3)
C14—C15—C16—C17	−0.3 (3)	C8—C9—C10—C11	0.6 (3)
C15—C16—C17—C18	1.0 (3)	C9—C10—C11—C12	−0.3 (3)
C15—C16—C17—C20	−178.9 (2)	C10—C11—C12—N1	0.4 (3)
C16—C17—C18—C19	−0.6 (3)	C10—C11—C12—C13	−178.58 (18)
C20—C17—C18—C19	179.3 (2)	N2—C8—N1—C12	179.90 (17)
C15—C14—C19—C18	1.2 (3)	C9—C8—N1—C12	1.3 (3)
S2—C14—C19—C18	−175.05 (16)	C11—C12—N1—C8	−0.9 (3)
C17—C18—C19—C14	−0.5 (3)	C13—C12—N1—C8	178.12 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.90 (1)	1.88 (1)	2.772 (2)	171 (2)
N2—H2A···O3ⁱ	0.87 (1)	2.01 (1)	2.880 (2)	174 (2)
N2—H2B···O1	0.88 (1)	2.07 (1)	2.919 (2)	162 (2)
N3—H3A···O5	0.89 (1)	1.90 (1)	2.789 (2)	174 (2)
N4—H4A···O4ⁱⁱ	0.88 (1)	2.02 (1)	2.882 (2)	167 (2)
N4—H4B···O6	0.88 (1)	2.04 (1)	2.883 (2)	162 (2)
C22—H22···O5ⁱⁱ	0.93	2.58	3.455 (2)	157

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₇H₇O₃S⁻
M_r	280.35
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5343 (2), 13.6212 (5), 13.9887 (5)
α, β, γ (°)	106.307 (2), 97.946 (1), 92.103 (2)
V (Å³)	1360.31 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.920, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	32534, 6237, 4709
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.06
No. of reflections	6237
No. of parameters	372
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)	0.33, −0.37

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.900 (9)	1.880 (10)	2.772 (2)	171 (2)
N2—H2A···O3ⁱ	0.873 (10)	2.011 (10)	2.880 (2)	174 (2)
N2—H2B···O1	0.877 (10)	2.074 (12)	2.919 (2)	162 (2)
N3—H3A···O5	0.894 (9)	1.899 (10)	2.789 (2)	174 (2)
N4—H4A···O4ⁱⁱ	0.876 (10)	2.022 (11)	2.882 (2)	167 (2)
N4—H4B···O6	0.876 (9)	2.036 (12)	2.883 (2)	162 (2)
C22—H22···O5ⁱⁱ	0.93	2.58	3.455 (2)	156.9

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

Acknowledgements

The authors are thankful to the SAIF, IIT Madras, for the data collection.

References

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Volume 70| Part 5| May 2014| Pages o600-o601

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