Bis[4-(5-anilino-1,3,4-thia­diazol-2-yl)pyridinium] sulfate

Bharti, A.; Nath, P.; Bharati, P.; Gupta, S.K.; Bharty, M.K.

doi:10.1107/S2414314616004466

organic compounds

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ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160446

doi:10.1107/S2414314616004466

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Bis[4-(5-anilino-1,3,4-thiadiazol-2-yl)pyridinium] sulfate

Akhilesh Bharti,^a ^* Paras Nath,^b Pooja Bharati,^b Sushil K. Gupta ^c and Manoj K. Bharty ^b ‡

^aDepartment of Chemistry, Kirori Mal College, University of Delhi, Delhi 110 007, India, ^bDepartment of Chemistry, Banaras Hindu University, Varanasi 221 005, India, and ^cSchool of Studies in Chemistry, Jiwaji University, Gwalior 47011, India
^*Correspondence e-mail: akhileshbhu86@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 13 March 2016; accepted 15 March 2016; online 31 March 2016)

The asymmetric unit of the title salt, 2C₁₃H₁₁N₄S⁺·SO₄⁻, comprises two 4-(5-anilino-1,3,4-thiadiazol-2-yl)pyridinium cations and one sulfate anion. In one cation, the phenyl ring is inclined to the pyridinium ring at a dihedral angle of 34.82 (6)°, while in other cation the rings are almost coplanar with a corresponding dihedral angle 5.33 (10)°. Strong N—H⋯O hydrogen bonds link the cations to the sulfate anion in the asymmetric unit. Additional N—H⋯O, C—H⋯N, C—H⋯O and C—H⋯S hydrogen bonds further stabilize the crystal structure. Weak C—H⋯π and π–π interactions are also observed in the crystal structure.

Keywords: crystal structure; pyridinium ion; thiadiazole; hydrogen bonding; π—π interactions.

CCDC reference: 1453083

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Chemical scheme

Structure description

Derivatives of 1,3,4-thiadiazoles belong to an extensively studied and important class of heterocyclic compounds, which have diverse biological applications. These include antibacterial, antifungal, antimicrobial, antitumor, antioxidant, antitubercular and anticonvulsant activities (Shawali, 2014 ). Aroyl hydrazide reacts with phenyl isothiocynate to form thiosemicarbazide derivatives (Singh et al., 2014 ), which can be subsequently cyclized to form the corresponding thiadiazole derivative in the presence of strong acid (Bharti et al., 2013 ; Dulare et al., 2010 ). Aroyl thiosemicarbazide derivatives generally convert to oxadiazoles in the presence of a weak acid or Mn(OAc)₂ (Paswan et al., 2015 ).

The title compound is a salt containing two 4-(5-anilino-1,3,4-thiadiazol-2-yl)pyridinium cations with a sulfate anion balancing the charge (Fig. 1) (Abdel-Aziz et al., 2015 ). The N1,C1–C5 pyridinium and C8–C13 phenyl rings are inclined an angle of 34.82 (6)° in one cation while the second cation is closer to planar, with a corresponding dihedral angle of 5.33 (10)°. An intramolecular C22—H22A⋯N7 hydrogen bond contributes to the planarity of this cation. The C—N bond lengths, N2—C6 1.310 (2), N3—C7 1.324 (2), N6—C19 1.299 (2) and N7—C20 1.320 (2) Å, are well within the reported range (Singh et al., 2007 ) and similar to standard C=N, 1.28 Å, bond lengths. The endocyclic C—S bonds S1—C6 1.7338 (17), S1—C7 1.7495 (18), S2—C19 1.7350 (17) and S2—C20 1.7399 (17) Å are intermediate in length between single and double bonds, suggesting considerable delocalization of charge in the thiadiazole ring.

Figure 1
Molecular structure of the title compound, C₂₆H₂₂N₈O₄S₃, showing 50% probability displacement ellipsoids.

In the crystal structure, N1—H1B⋯O2, N1—H1B⋯O4, and N5—H5B⋯O1 hydrogen bonds link the sulfate anion to the two cations in the asymmetric unit, Fig. 2. An extensive series of N4—H4B⋯O2, N8—H8A⋯O4, C1—H1A⋯N2, C4—H4A⋯O2, C4—H4A⋯S2, C5—H5A⋯O3, C15—H15A⋯O3 and C17—H17A⋯N2 hydrogen bonds also stabilize the crystal structure. The crystal packing is further reinforced by a weak C—H⋯π interaction (Table 1). An extensive series of π–π stacking interactions between the thiadiazole, phenyl and pyridinium rings is also observed with centroid-to-centroid distances Cg1⋯Cg1ⁱ = 3.612 (7) Å; Cg3..Cg3ⁱⁱ = 3.633 (3) Å; Cg4..Cg4ⁱⁱⁱ = 3.946 (5) Å; Cg4..Cg4^iv = 3.592 (5) Å; Cg5..Cg6ⁱⁱⁱ = 3.745 (6) Å; Cg5..Cg6^iv = 3.730 (7) Å. Ring centroids: Cg1 = S1/C6/N2/N3/C7; Cg3 = C8–C13; Cg4 = S2/C19/N6/N7/C20; Cg5 = N5/C14–C18; Cg6 = C21–C26; symmetry codes: (i) −x, −y, −z; (ii) 1 − x, 1 − y, −z; (iii) 1 − x, −y, 1 − z; (iv) 2 − x, −y, 1 − z. These contacts lead to a three-dimensional structure.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the pyridine ring, N1/C1–C5.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.88	2.50	3.054 (2)	122
N1—H1B⋯O4	0.88	1.86	2.730 (2)	168
N4—H4B⋯O2ⁱ	0.88	1.98	2.7506 (19)	146
C1—H1A⋯N2ⁱⁱ	0.95	2.66	3.490 (2)	146
C4—H4A⋯S2ⁱⁱⁱ	0.95	3.00	3.6835 (18)	130
C4—H4A⋯O2^iv	0.95	2.44	3.158 (2)	132
C5—H5A⋯O3^iv	0.95	2.45	3.242 (2)	140
N5—H5B⋯O1	0.88	1.67	2.5459 (19)	172
N8—H8A⋯O4^v	0.88	1.92	2.7875 (19)	167
C15—H15A⋯O3^vi	0.95	2.38	3.297 (2)	162
C17—H17A⋯N2^vii	0.95	2.50	3.240 (2)	135
C22—H22A⋯N7	0.95	2.30	2.933 (2)	123
C22—H22A⋯Cg2^iv	0.95	2.94	3.790 (5)	149
Symmetry codes: (i) -x+1, -y+2, -z; (ii) x-1, y, z; (iii) x+1, y+1, z; (iv) x+1, y, z; (v) x, y-1, z; (vi) -x, -y+1, -z+1; (vii) x-1, y-1, z.

Figure 2
Molecular packing of C₂₆H₂₂N₈O₄S₃ viewed along the c axis. Dashed lines indicate pyridinium N—H⋯O_sulfate and phenyl C—H⋯N_thiadiazole interactions.

Synthesis and crystallization

A mixture of isonicotinic acid hydrazide (2.740 g, 20.00 mmol) and phenyl isothiocyanate (2.4 ml, 20.00 mmol) in absolute ethanol (30 ml) was refluxed for 8 h (Fig. 3). The white precipitate of 1-isonicotinoyl-4-phenylthiosemicarbazide obtained upon cooling was filtered off and washed with water and ether (50:50 v/v). 1-Isonicotinoyl-4-phenyl thiosemicarbazide (2.72 g, 10.00 mmol) was added slowly to 10 ml conc. H₂SO₄ and stirred for 2 h with cooling. The mixture was poured over crushed ice and a yellow precipitate of bis-4-(5-phenylamino-[1,3,4]thiadiazol-2-yl)pyridinium sulfate was obtained. It was filtered off, washed with cold water, dried. and recrystallized from a methanol–water mixture. Yellow crystals suitable for X-ray analysis were obtained by slow evaporation of the methanol–water solution over a period of 10–15 days. Yield: 85%; m.p. 497–499 K. Anal. Calc. for C₂₆H₂₂N₈O₄S₃ (%): C, 51.47; H, 3.65; N, 18.47; S, 15.86. Found: C, 51.75; H, 3.80; N, 18.86; S, 15.42. ¹H NMR (DMSO-d₆), δ (p.p.m.) = 10.76 (s, 2H, NH); 7.04 (t, 2H, phenyl H); 7.38 (t, 4H, phenyl H); 7.64 (d, 4H, phenyl H); 7.81 (d, 4H, pyridyl H); 8.67 (d, 4H, pyridyl H); 3.36 (s, 2H, pyridinium NH). ¹³C NMR (DMSO-d₆), δ (p.p.m.) = 117.7 (C9, C13, C22, C26); 120.6 (C2, C4, C15, C17); 122.5 (C11, C24); 129.2 (C10, C12, C23, C25); 137.1 (C8, C21); 140.2 (C3, C16); 150.6 (C1, C5, C14, C18); 155.2 (C6, C19); 165.3 (C7, C20). IR (selected, KBr) 3200 [ν(N—H, pyridinium)], 3129 [ν(N—H, amine)], 1540 [ν(C=N)], 1120; [ν(N—N)], 754 [ν(C—S)] cm⁻¹.

Figure 3
Reaction scheme showing the synthesis of the title compound, C₂₆H₂₂N₈O₄S₃.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	2C₁₃H₁₁N₄S⁺·SO₄²⁻
M_r	606.69
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.4551 (8), 11.9212 (13), 15.1931 (16)
α, β, γ (°)	90.605 (6), 99.245 (5), 105.408 (6)
V (Å³)	1282.8 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.34
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.675, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	13929, 4529, 3975
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.07
No. of reflections	4529
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.39
Computer programs: SMART (Bruker, 2012 ), SAINT (Bruker, 2012), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008).

Structural data

CCDC reference: 1453083

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616004466/sj4013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004466/sj4013Isup2.hkl

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Experimental top

Structure description top

Derivatives of 1,3,4-thiadiazoles belong to an extensively studied and important class of heterocyclic compounds, which have diverse biological applications. These include antibacterial, antifungal, antimicrobial, antitumor, antioxidant, antitubercular and anticonvulsant activities (Shawali, 2014). Aroyl hydrazide reacts with phenyl isothiocynate to form thiosemicarbazide derivatives (Singh et al., 2014), which can be subsequently cyclized to form the corresponding thiadiazole derivative in the presence of strong acid (Bharti et al., 2013; Dulare et al., 2010). Aroyl thiosemicarbazide derivatives generally convert to oxadiazoles in the presence of a weak acid or Mn(OAc)₂ (Paswan et al., 2015).

The title compound is a salt containing two 4-(5-anilino-1,3,4-thiadiazol-2-yl)pyridinium cations with a sulfate anion balancing the charge (Fig. 1) (Abdel-Aziz et al., 2015). The N1,C1–C5 pyridinium and C8–C13 phenyl rings are inclined an angle of 34.82 (6)° in one cation while the second cation is closer to planar, with a corresponding dihedral angle of 5.33 (10)°. An intramolecular C22—H22A···N7 hydrogen bond contributes to the planarity of this cation. The C—N bond lengths, N2—C6 1.310 (2), N3—C7 1.324 (2), N6—C19 1.299 (2) and N7—C20 1.320 (2) Å, are well within the reported range (Singh et al., 2007) and similar to standard C═N, 1.28 Å, bond lengths. The endocyclic C—S bonds S1—C6 1.7338 (17), S1—C7 1.7495 (18), S2—C19 1.7350 (17) and S2—C20 1.7399 (17) Å are intermediate in length between single and double bonds, suggesting considerable delocalization of charge in the thiadiazole ring.

In the crystal structure, N1—H1B···O2, N1—H1B···O4, and N5—H5B···O1 hydrogen bonds link the sulfate anion to the two cations in the asymmetric unit, Fig. 2. An extensive series of N4—H4B···O2, N8—H8A···O4, C1—H1A···N2, C4—H4A···O2, C4—H4A···S2, C5—H5A···O3, C15—H15A···O3 and C17—H17A···N2 hydrogen bonds also stabilize the crystal structure. The crystal packing is further reinforced by a weak intermolecular C—H···π interaction (Table 1). An extensive series of π–π stacking interactions between the thiadiazole, phenyl and pyridinium rings is also observed with centroid-to-centroid distances Cg1···Cg1ⁱ = 3.612 (7) Å; Cg3..Cg3ⁱⁱ = 3.633 (3) Å; Cg4..Cg4ⁱⁱⁱ = 3.946 (5) Å; Cg4..Cg4^iv = 3.592 (5) Å; Cg5..Cg6ⁱⁱⁱ = 3.745 (6) Å; Cg5..Cg6^iv = 3.730 (7) Å. Ring centroids: Cg1 = S1/C6/N2/N3/C7; Cg3 = C8–C13; Cg4 = S2/C19/N6/N7/C20; Cg5 = N5/C14–C18; Cg6 = C21–C26; symmetry codes: (i) −x, −y, −z; (ii) 1 − x, 1 − y, −z; (iii) 1 − x, −y, 1 − z; (iv) 2 − x, −y, 1 − z. These contacts lead to a three-dimensional structure.

Computing details top

Data collection: SMART (Bruker, 2012); cell refinement: SMART (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, C₂₆H₂₂N₈O₄S₃, showing 50% probability displacement ellipsoids.
	Fig. 2. Molecular packing of C₂₆H₂₂N₈O₄S₃ viewed along the c axis. Dashed lines indicate pyridinium N—H···O_sulfate and phenyl C—H···N_thiadiazole interactions.
	Fig. 3. Reaction scheme showing the synthesis of the title compound, C₂₆H₂₂N₈O₄S₃.

Bis[4-(5-anilino-1,3,4-thiadiazol-2-yl)pyridinium] sulfate top

Crystal data top

2C₁₃H₁₁N₄S⁺·SO₄²⁻	F(000) = 628
M_r = 606.69	D_x = 1.571 Mg m⁻³
Triclinic, P1	Melting point = 497–499 K
a = 7.4551 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9212 (13) Å	Cell parameters from 6650 reflections
c = 15.1931 (16) Å	θ = 2.9–34.1°
α = 90.605 (6)°	µ = 0.34 mm⁻¹
β = 99.245 (5)°	T = 100 K
γ = 105.408 (6)°	Block, yellow
V = 1282.8 (2) Å³	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4529 independent reflections
Radiation source: sealed tube	3975 reflections with I > 2σ(I)
Detector resolution: 8 pixels mm^-1	R_int = 0.030
ω and φ scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.675, T_max = 0.747	k = −14→14
13929 measured reflections	l = −18→18

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0311P)² + 0.7088P] where P = (F_o² + 2F_c²)/3
4529 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

2C₁₃H₁₁N₄S⁺·SO₄²⁻	γ = 105.408 (6)°
M_r = 606.69	V = 1282.8 (2) Å³
Triclinic, P1	Z = 2
a = 7.4551 (8) Å	Mo Kα radiation
b = 11.9212 (13) Å	µ = 0.34 mm⁻¹
c = 15.1931 (16) Å	T = 100 K
α = 90.605 (6)°	0.2 × 0.2 × 0.2 mm
β = 99.245 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4529 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3975 reflections with I > 2σ(I)
T_min = 0.675, T_max = 0.747	R_int = 0.030
13929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
4529 reflections	Δρ_min = −0.39 e Å⁻³
370 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.86656 (6)	1.16414 (4)	0.01533 (3)	0.01666 (12)
N1	0.5081 (2)	0.87361 (13)	0.24034 (9)	0.0152 (3)
H1B	0.4244	0.8302	0.2694	0.018*
N2	1.0918 (2)	1.07959 (13)	0.12273 (10)	0.0160 (3)
N3	1.2061 (2)	1.15163 (13)	0.07287 (10)	0.0169 (3)
N4	1.1793 (2)	1.27474 (13)	−0.04811 (10)	0.0167 (3)
H4B	1.0973	1.2920	−0.0905	0.020*
C1	0.4531 (3)	0.94483 (16)	0.18063 (11)	0.0166 (4)
H1A	0.3258	0.9487	0.1708	0.020*
C2	0.5815 (3)	1.01274 (16)	0.13334 (11)	0.0161 (4)
H2A	0.5432	1.0634	0.0909	0.019*
C3	0.7690 (2)	1.00609 (15)	0.14859 (11)	0.0140 (4)
C4	0.8198 (3)	0.93160 (15)	0.21186 (11)	0.0152 (4)
H4A	0.9461	0.9260	0.2236	0.018*
C5	0.6868 (3)	0.86629 (15)	0.25720 (11)	0.0153 (4)
H5A	0.7214	0.8157	0.3007	0.018*
C6	0.9129 (2)	1.07610 (15)	0.10135 (11)	0.0142 (4)
C7	1.1087 (2)	1.20118 (15)	0.01211 (11)	0.0149 (4)
C8	1.3723 (2)	1.32689 (15)	−0.04979 (12)	0.0152 (4)
C9	1.5098 (3)	1.35018 (16)	0.02694 (12)	0.0171 (4)
H9A	1.4763	1.3282	0.0833	0.021*
C10	1.6951 (3)	1.40552 (16)	0.02058 (13)	0.0201 (4)
H10A	1.7880	1.4233	0.0731	0.024*
C11	1.7473 (3)	1.43550 (16)	−0.06159 (13)	0.0211 (4)
H11A	1.8758	1.4703	−0.0658	0.025*
C12	1.6093 (3)	1.41396 (16)	−0.13740 (12)	0.0188 (4)
H12A	1.6435	1.4352	−0.1937	0.023*
C13	1.4219 (3)	1.36171 (15)	−0.13185 (12)	0.0164 (4)
H13A	1.3278	1.3497	−0.1838	0.020*
S2	0.23101 (6)	−0.01835 (4)	0.39241 (3)	0.01541 (11)
N5	0.1036 (2)	0.39691 (13)	0.32752 (10)	0.0170 (3)
H5B	0.0829	0.4592	0.3019	0.020*
N6	0.2292 (2)	0.09266 (13)	0.53715 (10)	0.0164 (3)
N7	0.2674 (2)	−0.00908 (13)	0.56431 (10)	0.0171 (3)
N8	0.3111 (2)	−0.18121 (13)	0.49976 (9)	0.0146 (3)
H8A	0.3196	−0.2130	0.4486	0.018*
C14	0.1019 (2)	0.38726 (16)	0.41526 (12)	0.0172 (4)
H14A	0.0773	0.4478	0.4486	0.021*
C15	0.1348 (2)	0.29209 (16)	0.45807 (12)	0.0165 (4)
H15A	0.1335	0.2865	0.5203	0.020*
C16	0.1704 (2)	0.20354 (15)	0.40815 (12)	0.0146 (4)
C17	0.1705 (3)	0.21536 (16)	0.31685 (12)	0.0168 (4)
H17A	0.1940	0.1562	0.2815	0.020*
C18	0.1365 (3)	0.31296 (16)	0.27849 (12)	0.0183 (4)
H18A	0.1362	0.3210	0.2163	0.022*
C19	0.2077 (2)	0.10113 (15)	0.45117 (11)	0.0143 (4)
C20	0.2736 (2)	−0.07629 (15)	0.49586 (11)	0.0141 (4)
C21	0.3381 (2)	−0.24591 (15)	0.57507 (11)	0.0144 (4)
C22	0.3396 (3)	−0.20759 (16)	0.66238 (12)	0.0168 (4)
H22A	0.3269	−0.1320	0.6746	0.020*
C23	0.3599 (3)	−0.28141 (17)	0.73117 (12)	0.0208 (4)
H23A	0.3616	−0.2554	0.7907	0.025*
C24	0.3777 (3)	−0.39180 (17)	0.71503 (13)	0.0216 (4)
H24A	0.3886	−0.4418	0.7627	0.026*
C25	0.3796 (3)	−0.42896 (16)	0.62851 (13)	0.0211 (4)
H25A	0.3930	−0.5045	0.6169	0.025*
C26	0.3619 (3)	−0.35642 (16)	0.55884 (12)	0.0180 (4)
H26A	0.3659	−0.3818	0.4999	0.022*
S3	0.08058 (6)	0.68673 (4)	0.27783 (3)	0.01258 (11)
O1	0.02984 (18)	0.56462 (10)	0.23978 (8)	0.0167 (3)
O2	0.08188 (17)	0.76412 (11)	0.20296 (8)	0.0169 (3)
O3	−0.05074 (18)	0.70046 (11)	0.33570 (8)	0.0202 (3)
O4	0.27727 (17)	0.71575 (11)	0.33018 (8)	0.0162 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0133 (2)	0.0196 (2)	0.0172 (2)	0.00468 (18)	0.00223 (17)	0.00663 (18)
N1	0.0154 (8)	0.0165 (8)	0.0134 (7)	0.0020 (6)	0.0049 (6)	0.0006 (6)
N2	0.0159 (8)	0.0166 (8)	0.0156 (7)	0.0041 (6)	0.0037 (6)	0.0035 (6)
N3	0.0147 (8)	0.0198 (8)	0.0170 (8)	0.0047 (6)	0.0043 (6)	0.0048 (6)
N4	0.0139 (8)	0.0214 (8)	0.0142 (7)	0.0040 (6)	0.0012 (6)	0.0065 (6)
C1	0.0152 (9)	0.0184 (10)	0.0165 (9)	0.0060 (7)	0.0011 (7)	−0.0003 (7)
C2	0.0163 (9)	0.0169 (9)	0.0150 (9)	0.0054 (7)	0.0005 (7)	0.0012 (7)
C3	0.0167 (9)	0.0127 (9)	0.0122 (8)	0.0033 (7)	0.0026 (7)	−0.0027 (7)
C4	0.0147 (9)	0.0160 (9)	0.0145 (8)	0.0051 (7)	0.0004 (7)	−0.0015 (7)
C5	0.0196 (10)	0.0147 (9)	0.0120 (8)	0.0060 (7)	0.0012 (7)	−0.0004 (7)
C6	0.0158 (9)	0.0138 (9)	0.0137 (8)	0.0055 (7)	0.0023 (7)	0.0005 (7)
C7	0.0148 (9)	0.0155 (9)	0.0141 (8)	0.0036 (7)	0.0026 (7)	−0.0009 (7)
C8	0.0148 (9)	0.0124 (9)	0.0196 (9)	0.0046 (7)	0.0047 (7)	0.0004 (7)
C9	0.0175 (10)	0.0180 (9)	0.0165 (9)	0.0050 (7)	0.0040 (7)	0.0034 (7)
C10	0.0169 (10)	0.0193 (10)	0.0229 (10)	0.0049 (8)	−0.0006 (8)	0.0004 (8)
C11	0.0146 (9)	0.0200 (10)	0.0293 (10)	0.0042 (8)	0.0060 (8)	0.0014 (8)
C12	0.0229 (10)	0.0165 (9)	0.0197 (9)	0.0064 (8)	0.0094 (8)	0.0030 (7)
C13	0.0177 (10)	0.0158 (9)	0.0166 (9)	0.0061 (7)	0.0027 (7)	−0.0002 (7)
S2	0.0192 (2)	0.0154 (2)	0.0125 (2)	0.00660 (18)	0.00193 (17)	0.00194 (17)
N5	0.0148 (8)	0.0134 (8)	0.0227 (8)	0.0041 (6)	0.0020 (6)	0.0032 (6)
N6	0.0173 (8)	0.0165 (8)	0.0165 (8)	0.0067 (6)	0.0022 (6)	0.0025 (6)
N7	0.0201 (8)	0.0169 (8)	0.0155 (7)	0.0077 (6)	0.0019 (6)	0.0022 (6)
N8	0.0164 (8)	0.0164 (8)	0.0117 (7)	0.0055 (6)	0.0026 (6)	0.0012 (6)
C14	0.0130 (9)	0.0161 (9)	0.0220 (9)	0.0032 (7)	0.0032 (7)	−0.0013 (7)
C15	0.0135 (9)	0.0179 (9)	0.0167 (9)	0.0020 (7)	0.0028 (7)	−0.0006 (7)
C16	0.0077 (8)	0.0165 (9)	0.0182 (9)	0.0013 (7)	0.0012 (7)	0.0019 (7)
C17	0.0163 (9)	0.0173 (9)	0.0171 (9)	0.0051 (7)	0.0023 (7)	−0.0002 (7)
C18	0.0185 (10)	0.0187 (10)	0.0171 (9)	0.0045 (8)	0.0022 (7)	0.0025 (8)
C19	0.0101 (9)	0.0169 (9)	0.0151 (9)	0.0025 (7)	0.0014 (7)	0.0003 (7)
C20	0.0100 (9)	0.0175 (9)	0.0139 (8)	0.0028 (7)	0.0013 (7)	0.0024 (7)
C21	0.0088 (9)	0.0155 (9)	0.0170 (9)	0.0011 (7)	0.0005 (7)	0.0038 (7)
C22	0.0152 (9)	0.0170 (9)	0.0171 (9)	0.0033 (7)	0.0011 (7)	0.0024 (7)
C23	0.0201 (10)	0.0246 (10)	0.0168 (9)	0.0051 (8)	0.0022 (7)	0.0034 (8)
C24	0.0190 (10)	0.0215 (10)	0.0222 (10)	0.0033 (8)	0.0007 (8)	0.0098 (8)
C25	0.0186 (10)	0.0153 (10)	0.0285 (10)	0.0047 (8)	0.0008 (8)	0.0038 (8)
C26	0.0142 (9)	0.0193 (10)	0.0194 (9)	0.0039 (7)	0.0006 (7)	0.0001 (8)
S3	0.0126 (2)	0.0137 (2)	0.0123 (2)	0.00470 (17)	0.00261 (16)	0.00257 (16)
O1	0.0199 (7)	0.0134 (6)	0.0168 (6)	0.0042 (5)	0.0035 (5)	0.0021 (5)
O2	0.0174 (7)	0.0162 (7)	0.0162 (6)	0.0037 (5)	0.0014 (5)	0.0057 (5)
O3	0.0180 (7)	0.0253 (7)	0.0200 (7)	0.0078 (6)	0.0074 (5)	0.0007 (6)
O4	0.0133 (6)	0.0215 (7)	0.0142 (6)	0.0057 (5)	0.0013 (5)	0.0034 (5)

Geometric parameters (Å, º) top

S1—C6	1.7338 (17)	N5—C18	1.338 (2)
S1—C7	1.7495 (18)	N5—C14	1.341 (2)
N1—C1	1.339 (2)	N5—H5B	0.8800
N1—C5	1.342 (2)	N6—C19	1.299 (2)
N1—H1B	0.8800	N6—N7	1.371 (2)
N2—C6	1.310 (2)	N7—C20	1.320 (2)
N2—N3	1.367 (2)	N8—C20	1.352 (2)
N3—C7	1.324 (2)	N8—C21	1.404 (2)
N4—C7	1.345 (2)	N8—H8A	0.8800
N4—C8	1.412 (2)	C14—C15	1.372 (3)
N4—H4B	0.8800	C14—H14A	0.9500
C1—C2	1.382 (3)	C15—C16	1.399 (2)
C1—H1A	0.9500	C15—H15A	0.9500
C2—C3	1.403 (2)	C16—C17	1.396 (3)
C2—H2A	0.9500	C16—C19	1.461 (2)
C3—C4	1.391 (2)	C17—C18	1.372 (3)
C3—C6	1.465 (3)	C17—H17A	0.9500
C4—C5	1.373 (3)	C18—H18A	0.9500
C4—H4A	0.9500	C21—C22	1.396 (3)
C5—H5A	0.9500	C21—C26	1.400 (3)
C8—C13	1.393 (3)	C22—C23	1.389 (3)
C8—C9	1.394 (2)	C22—H22A	0.9500
C9—C10	1.384 (3)	C23—C24	1.381 (3)
C9—H9A	0.9500	C23—H23A	0.9500
C10—C11	1.389 (3)	C24—C25	1.386 (3)
C10—H10A	0.9500	C24—H24A	0.9500
C11—C12	1.387 (3)	C25—C26	1.386 (3)
C11—H11A	0.9500	C25—H25A	0.9500
C12—C13	1.387 (3)	C26—H26A	0.9500
C12—H12A	0.9500	S3—O3	1.4550 (13)
C13—H13A	0.9500	S3—O2	1.4717 (13)
S2—C19	1.7350 (17)	S3—O1	1.4885 (13)
S2—C20	1.7399 (17)	S3—O4	1.5008 (12)

C6—S1—C7	86.67 (8)	C14—N5—H5B	119.6
C1—N1—C5	122.10 (16)	C19—N6—N7	113.61 (14)
C1—N1—H1B	118.9	C20—N7—N6	111.60 (14)
C5—N1—H1B	118.9	C20—N8—C21	128.25 (15)
C6—N2—N3	113.95 (14)	C20—N8—H8A	115.9
C7—N3—N2	111.76 (15)	C21—N8—H8A	115.9
C7—N4—C8	126.25 (15)	N5—C14—C15	121.58 (16)
C7—N4—H4B	116.9	N5—C14—H14A	119.2
C8—N4—H4B	116.9	C15—C14—H14A	119.2
N1—C1—C2	120.00 (16)	C14—C15—C16	118.60 (17)
N1—C1—H1A	120.0	C14—C15—H15A	120.7
C2—C1—H1A	120.0	C16—C15—H15A	120.7
C1—C2—C3	119.33 (16)	C17—C16—C15	118.74 (16)
C1—C2—H2A	120.3	C17—C16—C19	120.84 (16)
C3—C2—H2A	120.3	C15—C16—C19	120.42 (16)
C4—C3—C2	118.58 (16)	C18—C17—C16	119.50 (17)
C4—C3—C6	119.12 (16)	C18—C17—H17A	120.3
C2—C3—C6	122.29 (16)	C16—C17—H17A	120.3
C5—C4—C3	119.74 (16)	N5—C18—C17	120.82 (17)
C5—C4—H4A	120.1	N5—C18—H18A	119.6
C3—C4—H4A	120.1	C17—C18—H18A	119.6
N1—C5—C4	120.24 (16)	N6—C19—C16	122.64 (16)
N1—C5—H5A	119.9	N6—C19—S2	114.22 (13)
C4—C5—H5A	119.9	C16—C19—S2	123.13 (13)
N2—C6—C3	122.10 (15)	N7—C20—N8	126.48 (16)
N2—C6—S1	113.74 (13)	N7—C20—S2	114.25 (13)
C3—C6—S1	124.14 (13)	N8—C20—S2	119.27 (13)
N3—C7—N4	126.24 (17)	C22—C21—C26	119.51 (16)
N3—C7—S1	113.85 (13)	C22—C21—N8	124.35 (16)
N4—C7—S1	119.91 (13)	C26—C21—N8	116.14 (15)
C13—C8—C9	119.77 (17)	C23—C22—C21	119.11 (17)
C13—C8—N4	117.24 (16)	C23—C22—H22A	120.4
C9—C8—N4	122.89 (16)	C21—C22—H22A	120.4
C10—C9—C8	119.66 (17)	C24—C23—C22	121.51 (17)
C10—C9—H9A	120.2	C24—C23—H23A	119.2
C8—C9—H9A	120.2	C22—C23—H23A	119.2
C9—C10—C11	120.90 (17)	C23—C24—C25	119.31 (17)
C9—C10—H10A	119.6	C23—C24—H24A	120.3
C11—C10—H10A	119.6	C25—C24—H24A	120.3
C12—C11—C10	119.10 (18)	C26—C25—C24	120.30 (17)
C12—C11—H11A	120.5	C26—C25—H25A	119.8
C10—C11—H11A	120.5	C24—C25—H25A	119.8
C11—C12—C13	120.72 (18)	C25—C26—C21	120.21 (17)
C11—C12—H12A	119.6	C25—C26—H26A	119.9
C13—C12—H12A	119.6	C21—C26—H26A	119.9
C12—C13—C8	119.75 (17)	O3—S3—O2	112.11 (7)
C12—C13—H13A	120.1	O3—S3—O1	110.58 (8)
C8—C13—H13A	120.1	O2—S3—O1	107.89 (7)
C19—S2—C20	86.32 (8)	O3—S3—O4	109.81 (7)
C18—N5—C14	120.77 (16)	O2—S3—O4	107.61 (7)
C18—N5—H5B	119.6	O1—S3—O4	108.73 (7)

C6—N2—N3—C7	−1.1 (2)	C19—N6—N7—C20	−0.1 (2)
C5—N1—C1—C2	0.8 (2)	C18—N5—C14—C15	0.5 (3)
N1—C1—C2—C3	0.0 (3)	N5—C14—C15—C16	−0.2 (3)
C1—C2—C3—C4	−0.6 (2)	C14—C15—C16—C17	−0.2 (3)
C1—C2—C3—C6	−179.57 (16)	C14—C15—C16—C19	179.49 (16)
C2—C3—C4—C5	0.4 (2)	C15—C16—C17—C18	0.2 (3)
C6—C3—C4—C5	179.41 (15)	C19—C16—C17—C18	−179.48 (17)
C1—N1—C5—C4	−1.0 (2)	C14—N5—C18—C17	−0.5 (3)
C3—C4—C5—N1	0.4 (2)	C16—C17—C18—N5	0.1 (3)
N3—N2—C6—C3	−178.51 (15)	N7—N6—C19—C16	−178.58 (15)
N3—N2—C6—S1	−0.15 (19)	N7—N6—C19—S2	0.4 (2)
C4—C3—C6—N2	−6.8 (2)	C17—C16—C19—N6	172.31 (17)
C2—C3—C6—N2	172.17 (16)	C15—C16—C19—N6	−7.3 (3)
C4—C3—C6—S1	175.01 (13)	C17—C16—C19—S2	−6.6 (2)
C2—C3—C6—S1	−6.0 (2)	C15—C16—C19—S2	173.74 (14)
C7—S1—C6—N2	0.94 (13)	C20—S2—C19—N6	−0.51 (14)
C7—S1—C6—C3	179.26 (15)	C20—S2—C19—C16	178.50 (15)
N2—N3—C7—N4	−178.79 (16)	N6—N7—C20—N8	178.81 (16)
N2—N3—C7—S1	1.79 (18)	N6—N7—C20—S2	−0.35 (19)
C8—N4—C7—N3	−10.2 (3)	C21—N8—C20—N7	5.0 (3)
C8—N4—C7—S1	169.24 (13)	C21—N8—C20—S2	−175.91 (14)
C6—S1—C7—N3	−1.55 (14)	C19—S2—C20—N7	0.48 (14)
C6—S1—C7—N4	178.98 (15)	C19—S2—C20—N8	−178.74 (15)
C7—N4—C8—C13	155.55 (17)	C20—N8—C21—C22	−3.4 (3)
C7—N4—C8—C9	−28.2 (3)	C20—N8—C21—C26	175.62 (17)
C13—C8—C9—C10	−1.4 (3)	C26—C21—C22—C23	−1.6 (3)
N4—C8—C9—C10	−177.54 (16)	N8—C21—C22—C23	177.37 (17)
C8—C9—C10—C11	−1.7 (3)	C21—C22—C23—C24	−0.3 (3)
C9—C10—C11—C12	2.9 (3)	C22—C23—C24—C25	1.5 (3)
C10—C11—C12—C13	−0.9 (3)	C23—C24—C25—C26	−0.6 (3)
C11—C12—C13—C8	−2.1 (3)	C24—C25—C26—C21	−1.3 (3)
C9—C8—C13—C12	3.3 (3)	C22—C21—C26—C25	2.4 (3)
N4—C8—C13—C12	179.68 (15)	N8—C21—C26—C25	−176.64 (16)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of pyridine ring, N1/C1–C5.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.88	2.50	3.054 (2)	122
N1—H1B···O4	0.88	1.86	2.730 (2)	168
N4—H4B···O2ⁱ	0.88	1.98	2.7506 (19)	146
C1—H1A···N2ⁱⁱ	0.95	2.66	3.490 (2)	146
C4—H4A···S2ⁱⁱⁱ	0.95	3.00	3.6835 (18)	130
C4—H4A···O2^iv	0.95	2.44	3.158 (2)	132
C5—H5A···O3^iv	0.95	2.45	3.242 (2)	140
N5—H5B···O1	0.88	1.67	2.5459 (19)	172
N8—H8A···O4^v	0.88	1.92	2.7875 (19)	167
C15—H15A···O3^vi	0.95	2.38	3.297 (2)	162
C17—H17A···N2^vii	0.95	2.50	3.240 (2)	135
C22—H22A···N7	0.95	2.30	2.933 (2)	123
C22—H22A···Cg2^iv	0.95	2.94	3.790 (5)	149

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

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of pyridine ring, N1/C1–C5.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.88	2.50	3.054 (2)	121.6
N1—H1B···O4	0.88	1.86	2.730 (2)	167.8
N4—H4B···O2ⁱ	0.88	1.98	2.7506 (19)	145.6
C1—H1A···N2ⁱⁱ	0.95	2.66	3.490 (2)	146.2
C4—H4A···S2ⁱⁱⁱ	0.95	3.00	3.6835 (18)	130.1
C4—H4A···O2^iv	0.95	2.44	3.158 (2)	131.8
C5—H5A···O3^iv	0.95	2.45	3.242 (2)	140.3
N5—H5B···O1	0.88	1.67	2.5459 (19)	171.6
N8—H8A···O4^v	0.88	1.92	2.7875 (19)	166.7
C15—H15A···O3^vi	0.95	2.38	3.297 (2)	162.0
C17—H17A···N2^vii	0.95	2.50	3.240 (2)	135.2
C22—H22A···N7	0.95	2.30	2.933 (2)	123.1
C22—H22A···Cg2^iv	0.95	2.94	3.790 (5)	149.0

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

Experimental details

Crystal data
Chemical formula	2C₁₃H₁₁N₄S⁺·SO₄²⁻
M_r	606.69
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.4551 (8), 11.9212 (13), 15.1931 (16)
α, β, γ (°)	90.605 (6), 99.245 (5), 105.408 (6)
V (Å³)	1282.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.675, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	13929, 4529, 3975
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.07
No. of reflections	4529
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.39

Computer programs: SMART (Bruker, 2012), SAINT (Bruker, 2012), SHELXS2013 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

Footnotes

‡Additional correspondence author, e-mail: manoj_vns2005@yahoo.co.in

Acknowledgements

This work was supported by the Science and Engineering Research Board (SERB), India (Project No. SERB/F/372/2015–16). We express our sincere thanks to Professor Ray J. Butcher for useful discussions.

References

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