S-Benzyl­thiouronium 4-anilinobenzene­sulfonate

Fun, H.-K.; Chantrapromma, S.; D'Silva, E.D.; Patil, P.S.; Dharmaprakash, S.M.

doi:10.1107/S160053680802727X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages o1858-o1859

doi:10.1107/S160053680802727X

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S-Benzylthiouronium 4-anilinobenzenesulfonate

Hoong-Kun Fun,^a ^* Suchada Chantrapromma,^b ‡ E. Deepak D'Silva,^c P. S. Patil ^d § and S. M. Dharmaprakash ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, ^cDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and ^dDepartment of Physics, KLE Society's KLE Institute of Technology, Gokul Road, Hubli 590 030, India
^*Correspondence e-mail: hkfun@usm.my

(Received 23 August 2008; accepted 24 August 2008; online 30 August 2008)

In the title compound, C₈H₁₁N₂S⁺·C₁₂H₁₀NO₃S⁻, the NH group of the S-benzylthiuronium is protonated and the interplanar angle between the phenyl ring and the CH₂—S=C(NH₂)₂ unit is 47.44 (10)°. In the 4-anilinobenzenesulfonate anion, the interplanar angle between the two rings is 44.07 (8)°. In the crystal structure, anions are linked into chains along the c-axis direction by N—H⋯O hydrogen bonds, while additional N—H⋯O interactions link the cations to the anions in chains along the b-axis direction. These chains are further interconnected into a two-dimensional network parallel to the bc plane by C—H⋯O interactions. C—H⋯π contacts are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ). For background to the applications of S-benzylthiuronium chloride and sodium diphenylamine-4-sulfonate, see, for example: Liao et al. (2004 ); Liu et al. (2006a ,b ); Mostafa (2006 ).

Experimental

Crystal data

C₁₂H₁₀NO₃S⁺·C₈H₁₁N₂S⁻
M_r = 415.54
Monoclinic, P 2₁ /c
a = 14.4918 (4) Å
b = 9.2024 (2) Å
c = 16.3944 (4) Å
β = 113.529 (1)°
V = 2004.57 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100.0 (1) K
0.24 × 0.07 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.879, T_max = 0.992
45812 measured reflections
5838 independent reflections
4320 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.107
S = 1.07
5838 reflections
337 parameters
All H-atom parameters refined
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.85 (2)	1.99 (2)	2.836 (2)	173.0 (18)
N2—H1N2⋯O3ⁱⁱ	0.92 (3)	2.04 (3)	2.9561 (19)	172 (3)
N3—H1N3⋯O1	0.809 (19)	2.015 (19)	2.8204 (19)	174 (2)
N2—H2N2⋯O3ⁱⁱⁱ	0.839 (19)	2.015 (19)	2.8069 (19)	157.2 (19)
N3—H2N3⋯O2ⁱⁱ	0.91 (2)	1.96 (2)	2.8633 (17)	173 (2)
C9—H9⋯O1	0.97 (2)	2.463 (18)	2.8563 (18)	103.8 (13)
C19—H19B⋯O2^iv	0.97 (2)	2.57 (2)	3.332 (2)	134.8 (14)
C4—H4⋯Cg2^v	0.947 (19)	3.22 (2)	3.943 (2)	134.7 (14)
C17—H17⋯Cg1ⁱⁱⁱ	0.99 (2)	2.92 (2)	3.471 (2)	116.0 (15)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) x, y+1, z; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z+1. Cg1 and Cg2 are the centroids of C7–C12 and C13–C18 benzene rings, respectively.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802727X/sj2532sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802727X/sj2532Isup2.hkl

checkCIF report

Comment top

S-benzylthiouronium chloride is a useful compound in pharmaceutical and biomedical science (Mostafa, 2006) and also in electrochemistry (Liao et al., 2004) whereas sodium diphenylamine-4-sulfonate is extensively used in nanomaterial studies (Liu et al., (2006a, b). Both compounds have the potential to form hydrogen bonds. As part of our investigations into solid state hydrogen bonding, the title compound (I) was synthesized and herein we report its crystal structure.

The molecular structure of the title compound consists of a C₈H₁₁N₂S⁺ cation and a C₁₂H₁₀NO₃S^- anion (Fig. 1). An NH group of the S-benzylthiouronium unit was protonated to become a NH₂ moiety. Neither the cation and the anion are planar as can be seen from the interplanar angle between the C13–C18 benzene ring and the least-squares plane through the S2/C20/N2/N3 unit being 47.44 (10)°. In the diphenylamine-4-sulfonate anion, the interplanar angle between the the two benzene rings (C1–C6 and C7–C12) is 44.07 (8)°. The C13–C18 benzene ring makes dihedral angles of 71.72 (9)° and 29.45 (9)° with the C1–C6 and C7–C12 benzene rings, respectively. The cation is linked to the anion by an N—H···O hydrogen bond (Fig. 1). The conformation of the dimethylamino group with respect to the S-benzyl substituent is reflected in the torsion angles C20–S2–C19–C18 = -177.78 (11)° and C19–S2–C20–N2 = 14.60 (17)°. Bond lengths and angles in (I) are in normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2 and Table 1), the anions are linked into chains along the c direction by N1—H1N1···O1 hydrogen bonds whereas the cations are linked with the anions into chains along the b direction by N2—H1N2···O3, N2—H2N2···O3 and N3—H2N3···O2 hydrogen bonds. These chains are further inter-connected into a two dimensional network parallel to the bc plane by C19—H19B···O2 interactions. C—H···π interactions were also observed in the crystal (Table 1); Cg₁ and Cg₂ are the centroids of C7–C12 and C13–C18 benzene rings, respectively.

Related literature top

For bond-length data, see: Allen et al. (1987). For background to the applications of S-benzylthiouronium chloride and sodium diphenylamine-4-sulfonate, see, for example: Liao et al. (2004); Liu et al. (2006a,b); Mostafa (2006). Cg1 and Cg2 are the centroids of C7–C12 and C13–C18 benzene rings, respectively.

Experimental top

The title compound was synthesized by mixing solutions of the sodium salt of diphenylamine sulfonate (0.54 g) in distilled water (5 ml) with 5 drops of 1 M HCl and S-benzylthiouronium chloride (1.0 g) in distilled water (5 ml). The mixed solution immediately yields a precipitate in ice cold water. This was filtered and dried. Colorless block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering. The N—H···O hydrogen bond is drawn as a dashed line.
	Fig. 2. The crystal packing of (I), viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

S-Benzylthiouronium 4-anilinobenzenesulfonate top

Crystal data top

C₁₂H₁₀NO₃S⁺·C₈H₁₁N₂S⁻	F(000) = 872
M_r = 415.54	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5838 reflections
a = 14.4918 (4) Å	θ = 2.5–30.0°
b = 9.2024 (2) Å	µ = 0.29 mm⁻¹
c = 16.3944 (4) Å	T = 100 K
β = 113.529 (1)°	Block, colorless
V = 2004.57 (9) Å³	0.24 × 0.07 × 0.03 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5838 independent reflections
Radiation source: fine-focus sealed tube	4320 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 8.33 pixels mm^-1	θ_max = 30.0°, θ_min = 2.5°
ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
T_min = 0.879, T_max = 0.992	l = −23→23
45812 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0444P)² + 0.7114P] where P = (F_o² + 2F_c²)/3
5838 reflections	(Δ/σ)_max < 0.001
337 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₂H₁₀NO₃S⁺·C₈H₁₁N₂S⁻	V = 2004.57 (9) Å³
M_r = 415.54	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.4918 (4) Å	µ = 0.29 mm⁻¹
b = 9.2024 (2) Å	T = 100 K
c = 16.3944 (4) Å	0.24 × 0.07 × 0.03 mm
β = 113.529 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5838 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4320 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.992	R_int = 0.057
45812 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.107	All H-atom parameters refined
S = 1.07	Δρ_max = 0.50 e Å⁻³
5838 reflections	Δρ_min = −0.43 e Å⁻³
337 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
S1	0.08636 (3)	0.27987 (4)	0.16160 (2)	0.01695 (10)
S2	0.19068 (4)	0.70226 (5)	0.20872 (3)	0.02907 (12)
O1	0.15746 (9)	0.34329 (13)	0.12876 (7)	0.0216 (3)
O2	−0.00092 (8)	0.37242 (12)	0.14360 (7)	0.0200 (2)
O3	0.05615 (10)	0.13272 (12)	0.12701 (7)	0.0274 (3)
N1	0.28844 (11)	0.27210 (17)	0.55470 (9)	0.0234 (3)
N2	0.08033 (12)	0.85826 (16)	0.06346 (10)	0.0231 (3)
N3	0.10880 (11)	0.61743 (16)	0.04555 (9)	0.0221 (3)
C1	0.37263 (13)	0.4172 (2)	0.68520 (11)	0.0237 (4)
C2	0.45695 (15)	0.4866 (2)	0.74499 (12)	0.0303 (4)
C3	0.54646 (15)	0.4825 (2)	0.73360 (12)	0.0319 (4)
C4	0.55080 (13)	0.4064 (2)	0.66248 (11)	0.0267 (4)
C5	0.46709 (12)	0.33550 (19)	0.60270 (11)	0.0215 (3)
C6	0.37628 (12)	0.34205 (18)	0.61244 (10)	0.0191 (3)
C7	0.24732 (12)	0.27071 (17)	0.46289 (10)	0.0176 (3)
C8	0.29225 (12)	0.33508 (18)	0.41073 (10)	0.0188 (3)
C9	0.24368 (12)	0.33377 (18)	0.31869 (10)	0.0186 (3)
C10	0.15065 (12)	0.26719 (16)	0.27700 (9)	0.0163 (3)
C11	0.10566 (12)	0.19952 (17)	0.32809 (10)	0.0183 (3)
C12	0.15354 (12)	0.20140 (18)	0.41962 (10)	0.0195 (3)
C13	0.22213 (14)	0.71334 (19)	0.40844 (11)	0.0235 (4)
C14	0.28471 (15)	0.6889 (2)	0.49686 (12)	0.0287 (4)
C15	0.36132 (15)	0.7846 (2)	0.54192 (12)	0.0325 (4)
C16	0.37589 (15)	0.9061 (2)	0.49858 (12)	0.0325 (4)
C17	0.31450 (13)	0.9297 (2)	0.40940 (11)	0.0248 (4)
C18	0.23738 (12)	0.83402 (18)	0.36394 (10)	0.0192 (3)
C19	0.17094 (13)	0.85965 (18)	0.26715 (10)	0.0199 (3)
C20	0.11899 (12)	0.73130 (18)	0.09651 (10)	0.0191 (3)
H1	0.3074 (15)	0.419 (2)	0.6925 (13)	0.032 (5)*
H2	0.4509 (15)	0.539 (2)	0.7926 (14)	0.041 (6)*
H3	0.6056 (15)	0.527 (2)	0.7781 (13)	0.035 (5)*
H4	0.6119 (15)	0.402 (2)	0.6544 (12)	0.029 (5)*
H5	0.4718 (13)	0.2865 (19)	0.5562 (12)	0.020 (5)*
H8	0.3557 (14)	0.384 (2)	0.4365 (12)	0.023 (5)*
H9	0.2763 (13)	0.381 (2)	0.2840 (12)	0.022 (5)*
H11	0.0404 (13)	0.1511 (19)	0.2983 (11)	0.015 (4)*
H12	0.1223 (13)	0.156 (2)	0.4549 (12)	0.023 (5)*
H13	0.1681 (15)	0.647 (2)	0.3794 (13)	0.029 (5)*
H14	0.2756 (14)	0.609 (2)	0.5268 (13)	0.029 (5)*
H15	0.4034 (17)	0.771 (2)	0.6006 (15)	0.042 (6)*
H16	0.4294 (15)	0.973 (2)	0.5305 (13)	0.038 (6)*
H17	0.3262 (14)	1.017 (2)	0.3794 (12)	0.034 (5)*
H19A	0.1915 (13)	0.943 (2)	0.2439 (12)	0.024 (5)*
H19B	0.1000 (14)	0.863 (2)	0.2565 (12)	0.023 (5)*
H1N1	0.2478 (15)	0.245 (2)	0.5773 (13)	0.027 (5)*
H1N2	0.0428 (18)	0.863 (3)	0.0029 (17)	0.058 (7)*
H2N2	0.0853 (15)	0.931 (2)	0.0958 (13)	0.032 (6)*
H1N3	0.1265 (15)	0.539 (2)	0.0688 (13)	0.030 (6)*
H2N3	0.0790 (17)	0.624 (2)	−0.0146 (15)	0.045 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0226 (2)	0.01564 (19)	0.01148 (17)	0.00260 (15)	0.00556 (15)	0.00000 (14)
S2	0.0387 (3)	0.0255 (2)	0.01363 (19)	0.0129 (2)	0.00060 (18)	−0.00185 (16)
O1	0.0260 (6)	0.0249 (6)	0.0173 (5)	0.0073 (5)	0.0123 (5)	0.0050 (5)
O2	0.0197 (6)	0.0224 (6)	0.0167 (5)	0.0031 (5)	0.0061 (4)	0.0002 (4)
O3	0.0423 (7)	0.0159 (6)	0.0162 (5)	0.0007 (5)	0.0034 (5)	−0.0021 (5)
N1	0.0212 (7)	0.0359 (8)	0.0135 (6)	−0.0095 (6)	0.0075 (6)	−0.0006 (6)
N2	0.0325 (8)	0.0175 (7)	0.0143 (7)	0.0026 (6)	0.0043 (6)	−0.0017 (6)
N3	0.0312 (8)	0.0168 (7)	0.0138 (6)	0.0035 (6)	0.0045 (6)	0.0005 (6)
C1	0.0231 (9)	0.0303 (9)	0.0184 (7)	−0.0017 (7)	0.0089 (7)	−0.0008 (7)
C2	0.0356 (10)	0.0353 (10)	0.0193 (8)	−0.0066 (9)	0.0102 (8)	−0.0068 (8)
C3	0.0282 (10)	0.0414 (11)	0.0207 (8)	−0.0135 (9)	0.0041 (7)	−0.0027 (8)
C4	0.0186 (8)	0.0371 (10)	0.0223 (8)	−0.0013 (8)	0.0060 (7)	0.0047 (7)
C5	0.0214 (8)	0.0246 (8)	0.0182 (7)	0.0015 (7)	0.0075 (6)	0.0013 (7)
C6	0.0198 (8)	0.0214 (8)	0.0130 (7)	−0.0009 (7)	0.0032 (6)	0.0032 (6)
C7	0.0191 (8)	0.0191 (8)	0.0139 (7)	−0.0006 (6)	0.0058 (6)	−0.0004 (6)
C8	0.0190 (8)	0.0198 (8)	0.0160 (7)	−0.0035 (7)	0.0053 (6)	0.0008 (6)
C9	0.0221 (8)	0.0183 (7)	0.0167 (7)	−0.0016 (7)	0.0091 (6)	0.0011 (6)
C10	0.0208 (8)	0.0149 (7)	0.0128 (6)	0.0026 (6)	0.0062 (6)	0.0008 (6)
C11	0.0186 (8)	0.0188 (8)	0.0162 (7)	−0.0019 (6)	0.0056 (6)	−0.0004 (6)
C12	0.0209 (8)	0.0234 (8)	0.0149 (7)	−0.0014 (7)	0.0078 (6)	0.0031 (6)
C13	0.0295 (9)	0.0212 (8)	0.0198 (8)	0.0024 (7)	0.0099 (7)	−0.0006 (7)
C14	0.0390 (11)	0.0283 (9)	0.0202 (8)	0.0112 (8)	0.0134 (8)	0.0051 (7)
C15	0.0343 (10)	0.0405 (11)	0.0160 (8)	0.0115 (9)	0.0029 (8)	−0.0023 (8)
C16	0.0279 (10)	0.0387 (11)	0.0238 (9)	0.0001 (9)	0.0028 (8)	−0.0087 (8)
C17	0.0252 (9)	0.0253 (9)	0.0220 (8)	−0.0001 (7)	0.0073 (7)	−0.0030 (7)
C18	0.0209 (8)	0.0195 (8)	0.0162 (7)	0.0054 (7)	0.0064 (6)	−0.0009 (6)
C19	0.0233 (9)	0.0189 (8)	0.0161 (7)	0.0021 (7)	0.0064 (6)	−0.0003 (6)
C20	0.0200 (8)	0.0204 (8)	0.0150 (7)	0.0006 (7)	0.0051 (6)	−0.0001 (6)

Geometric parameters (Å, º) top

S1—O2	1.4541 (12)	C5—H5	0.912 (18)
S1—O1	1.4612 (11)	C7—C8	1.397 (2)
S1—O3	1.4658 (12)	C7—C12	1.410 (2)
S1—C10	1.7474 (15)	C8—C9	1.387 (2)
S2—C20	1.7347 (16)	C8—H8	0.957 (19)
S2—C19	1.8208 (17)	C9—C10	1.387 (2)
N1—C7	1.3800 (19)	C9—H9	0.974 (18)
N1—C6	1.403 (2)	C10—C11	1.397 (2)
N1—H1N1	0.85 (2)	C11—C12	1.379 (2)
N2—C20	1.315 (2)	C11—H11	0.982 (17)
N2—H1N2	0.92 (3)	C12—H12	0.961 (18)
N2—H2N2	0.84 (2)	C13—C14	1.387 (2)
N3—C20	1.311 (2)	C13—C18	1.394 (2)
N3—H1N3	0.81 (2)	C13—H13	0.96 (2)
N3—H2N3	0.91 (2)	C14—C15	1.378 (3)
C1—C2	1.380 (2)	C14—H14	0.92 (2)
C1—C6	1.398 (2)	C15—C16	1.386 (3)
C1—H1	1.00 (2)	C15—H15	0.92 (2)
C2—C3	1.383 (3)	C16—C17	1.392 (2)
C2—H2	0.95 (2)	C16—H16	0.96 (2)
C3—C4	1.383 (3)	C17—C18	1.384 (2)
C3—H3	0.97 (2)	C17—H17	0.99 (2)
C4—C5	1.382 (2)	C18—C19	1.510 (2)
C4—H4	0.947 (19)	C19—H19A	0.955 (19)
C5—C6	1.389 (2)	C19—H19B	0.973 (18)

O2—S1—O1	112.06 (7)	C10—C9—C8	120.73 (14)
O2—S1—O3	111.18 (7)	C10—C9—H9	120.8 (11)
O1—S1—O3	111.84 (7)	C8—C9—H9	118.5 (11)
O2—S1—C10	107.66 (7)	C9—C10—C11	119.74 (14)
O1—S1—C10	106.02 (7)	C9—C10—S1	119.82 (11)
O3—S1—C10	107.76 (7)	C11—C10—S1	120.28 (12)
C20—S2—C19	106.38 (8)	C12—C11—C10	119.63 (15)
C7—N1—C6	128.35 (14)	C12—C11—H11	120.9 (10)
C7—N1—H1N1	113.6 (13)	C10—C11—H11	119.5 (10)
C6—N1—H1N1	116.2 (13)	C11—C12—C7	121.22 (14)
C20—N2—H1N2	117.4 (16)	C11—C12—H12	119.7 (11)
C20—N2—H2N2	122.1 (14)	C7—C12—H12	119.1 (11)
H1N2—N2—H2N2	120 (2)	C14—C13—C18	120.14 (17)
C20—N3—H1N3	118.7 (14)	C14—C13—H13	118.8 (12)
C20—N3—H2N3	121.6 (14)	C18—C13—H13	121.1 (12)
H1N3—N3—H2N3	120 (2)	C15—C14—C13	120.46 (18)
C2—C1—C6	120.70 (16)	C15—C14—H14	118.7 (12)
C2—C1—H1	121.4 (11)	C13—C14—H14	120.9 (13)
C6—C1—H1	117.9 (11)	C14—C15—C16	119.74 (17)
C1—C2—C3	120.23 (17)	C14—C15—H15	121.8 (14)
C1—C2—H2	118.2 (13)	C16—C15—H15	118.4 (14)
C3—C2—H2	121.6 (13)	C15—C16—C17	120.03 (18)
C4—C3—C2	119.27 (17)	C15—C16—H16	119.3 (12)
C4—C3—H3	121.7 (12)	C17—C16—H16	120.7 (12)
C2—C3—H3	118.9 (11)	C18—C17—C16	120.40 (17)
C5—C4—C3	120.97 (17)	C18—C17—H17	120.7 (11)
C5—C4—H4	119.0 (12)	C16—C17—H17	118.9 (11)
C3—C4—H4	120.0 (12)	C17—C18—C13	119.20 (15)
C4—C5—C6	120.13 (16)	C17—C18—C19	120.36 (15)
C4—C5—H5	119.3 (12)	C13—C18—C19	120.44 (15)
C6—C5—H5	120.6 (12)	C18—C19—S2	105.09 (11)
C5—C6—C1	118.68 (15)	C18—C19—H19A	112.0 (11)
C5—C6—N1	123.27 (15)	S2—C19—H19A	106.8 (11)
C1—C6—N1	118.01 (15)	C18—C19—H19B	112.3 (11)
N1—C7—C8	124.05 (15)	S2—C19—H19B	108.1 (11)
N1—C7—C12	117.57 (14)	H19A—C19—H19B	112.0 (15)
C8—C7—C12	118.37 (14)	N3—C20—N2	121.75 (15)
C9—C8—C7	120.28 (15)	N3—C20—S2	114.84 (12)
C9—C8—H8	117.7 (11)	N2—C20—S2	123.36 (12)
C7—C8—H8	121.9 (11)

C6—C1—C2—C3	0.0 (3)	O1—S1—C10—C11	−174.82 (12)
C1—C2—C3—C4	−0.9 (3)	O3—S1—C10—C11	−54.93 (15)
C2—C3—C4—C5	0.3 (3)	C9—C10—C11—C12	0.9 (2)
C3—C4—C5—C6	1.2 (3)	S1—C10—C11—C12	−174.38 (12)
C4—C5—C6—C1	−2.1 (3)	C10—C11—C12—C7	0.1 (2)
C4—C5—C6—N1	−179.60 (16)	N1—C7—C12—C11	177.74 (15)
C2—C1—C6—C5	1.6 (3)	C8—C7—C12—C11	−1.5 (2)
C2—C1—C6—N1	179.16 (16)	C18—C13—C14—C15	1.1 (3)
C7—N1—C6—C5	−46.7 (3)	C13—C14—C15—C16	0.0 (3)
C7—N1—C6—C1	135.84 (18)	C14—C15—C16—C17	−1.2 (3)
C6—N1—C7—C8	4.1 (3)	C15—C16—C17—C18	1.3 (3)
C6—N1—C7—C12	−175.08 (16)	C16—C17—C18—C13	−0.2 (3)
N1—C7—C8—C9	−177.33 (16)	C16—C17—C18—C19	−179.89 (16)
C12—C7—C8—C9	1.8 (2)	C14—C13—C18—C17	−1.0 (2)
C7—C8—C9—C10	−0.8 (2)	C14—C13—C18—C19	178.70 (15)
C8—C9—C10—C11	−0.6 (2)	C17—C18—C19—S2	118.32 (15)
C8—C9—C10—S1	174.76 (12)	C13—C18—C19—S2	−61.34 (17)
O2—S1—C10—C9	−110.24 (13)	C20—S2—C19—C18	−177.78 (11)
O1—S1—C10—C9	9.86 (15)	C19—S2—C20—N3	−167.79 (13)
O3—S1—C10—C9	129.75 (13)	C19—S2—C20—N2	14.60 (17)
O2—S1—C10—C11	65.08 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.85 (2)	1.99 (2)	2.836 (2)	173.0 (18)
N2—H1N2···O3ⁱⁱ	0.92 (3)	2.04 (3)	2.9561 (19)	172 (3)
N3—H1N3···O1	0.809 (19)	2.015 (19)	2.8204 (19)	174 (2)
N2—H2N2···O3ⁱⁱⁱ	0.839 (19)	2.015 (19)	2.8069 (19)	157.2 (19)
N3—H2N3···O2ⁱⁱ	0.91 (2)	1.96 (2)	2.8633 (17)	173 (2)
C9—H9···O1	0.97 (2)	2.463 (18)	2.8563 (18)	103.8 (13)
C19—H19B···O2^iv	0.97 (2)	2.57 (2)	3.332 (2)	134.8 (14)
C4—H4···Cg2^v	0.947 (19)	3.22 (2)	3.943 (2)	134.7 (14)
C17—H17···Cg1ⁱⁱⁱ	0.99 (2)	2.92 (2)	3.471 (2)	116.0 (15)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀NO₃S⁺·C₈H₁₁N₂S⁻
M_r	415.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.4918 (4), 9.2024 (2), 16.3944 (4)
β (°)	113.529 (1)
V (Å³)	2004.57 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.24 × 0.07 × 0.03

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.879, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	45812, 5838, 4320
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.107, 1.07
No. of reflections	5838
No. of parameters	337
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.43

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.85 (2)	1.99 (2)	2.836 (2)	173.0 (18)
N2—H1N2···O3ⁱⁱ	0.92 (3)	2.04 (3)	2.9561 (19)	172 (3)
N3—H1N3···O1	0.809 (19)	2.015 (19)	2.8204 (19)	174 (2)
N2—H2N2···O3ⁱⁱⁱ	0.839 (19)	2.015 (19)	2.8069 (19)	157.2 (19)
N3—H2N3···O2ⁱⁱ	0.91 (2)	1.96 (2)	2.8633 (17)	173 (2)
C9—H9···O1	0.97 (2)	2.463 (18)	2.8563 (18)	103.8 (13)
C19—H19B···O2^iv	0.97 (2)	2.57 (2)	3.332 (2)	134.8 (14)
C4—H4···Cg2^v	0.947 (19)	3.22 (2)	3.943 (2)	134.7 (14)
C17—H17···Cg1ⁱⁱⁱ	0.99 (2)	2.92 (2)	3.471 (2)	116.0 (15)

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

Footnotes

‡Additional correspondence author, e-mail: suchada.c@psu.ac.th.

§Department of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India.

Acknowledgements

This work is supported by the Department of Science and Technology (DST), Government of India, under grant No. SR/S2/LOP-17/2006. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

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