1-Methyl-4-[(E)-2-(2-thien­yl)­ethen­yl]­pyridinium 4-methyl­benzene­sulfonate

Chantrapromma, S.; Ruanwas, P.; Fun, H.-K.; Karalai, C.

doi:10.1107/S1600536808031401

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Pages o2072-o2073

doi:10.1107/S1600536808031401

Open

access

1-Methyl-4-[(E)-2-(2-thienyl)ethenyl]pyridinium 4-methylbenzenesulfonate †

Suchada Chantrapromma,^a ^* Pumsak Ruanwas,^a Hoong-Kun Fun ^b ‡ and Chatchanok Karalai ^a

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 19 September 2008; accepted 29 September 2008; online 4 October 2008)

In the title compound, C₁₂H₁₂NS⁺·C₇H₇O₃S⁻, the cation exists in an E configuration with respect to the ethenyl C=C bond. The cation is essentially planar with a dihedral angle of 1.94 (10)° between the pyridinium and thiophene rings. The benzene ring of the anion makes dihedral angles of 75.23 (10) and 76.83 (10)°, respectively, with the pyridinium and thiophene rings. In the crystal structure, cations and anions form alternate layers parallel to the bc plane. Within each layer, both cations and anions are arranged into chains directed along the b axis. The cation chain and the anion chain are interconnected by weak C—H⋯O interactions into a three-dimensional network. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

For bond lengths, see: Allen et al. (1987 ). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see, for example: Chantrapromma, Jindawong & Fun (2007 ); Chantrapromma, Jindawong, Fun & Patil (2007 ); Chantrapromma et al. (2008 ); Lakshmanaperumal et al. (2002 , 2004 ); Rahman et al. (2003 ); Ruanwas et al. (2008 ); Usman et al. (2000 , 2001 ).

Experimental

Crystal data

C₁₂H₁₂NS⁺·C₇H₇O₃S⁻
M_r = 373.49
Triclinic, $[P \overline 1]$
a = 9.2947 (1) Å
b = 9.6144 (1) Å
c = 10.7790 (1) Å
α = 87.817 (1)°
β = 64.702 (1)°
γ = 88.712 (1)°
V = 870.21 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100.0 (1) K
0.36 × 0.35 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.893, T_max = 0.945
18024 measured reflections
4606 independent reflections
4122 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.148
S = 1.04
4606 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3ⁱ	0.93	2.31	3.219 (3)	166
C3—H3A⋯O1ⁱⁱ	0.93	2.49	3.168 (2)	130
C6—H6A⋯O2	0.93	2.56	3.378 (3)	147
C11—H11A⋯O1ⁱⁱⁱ	0.93	2.54	3.303 (3)	139
C12—H12A⋯O1ⁱ	0.96	2.52	3.455 (3)	165
C12—H12C⋯O1ⁱⁱ	0.96	2.47	3.341 (3)	151
C15—H15A⋯O2^iv	0.93	2.42	3.272 (2)	152
C17—H17A⋯O3ⁱ	0.93	2.43	3.202 (2)	141
C4—H4A⋯Cg1^v	0.93	2.62	3.431 (2)	145
C10—H10A⋯Cg1^vi	0.93	2.95	3.666 (3)	135
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z+1; (iii) -x+1, -y+2, -z; (iv) -x+1, -y+1, -z; (v) -x, -y+1, -z+1; (vi) x-1, y+1, z. Cg1 is the centroid of the C13–C18 benzene ring.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808031401/is2338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031401/is2338Isup2.hkl

checkCIF report

Comment top

Pyridinium derivatives have been found to have nonlinear optical properties (Lakshmanaperumal et al., 2002, 2004; Usman et al., 2000, 2001). We have previously synthesized and crystallized several compounds of pyridinium and quinolinium derivatives to study their non-linear optical properties (Chantrapromma, Jindawong & Fun, 2007; Chantrapromma, Jindawong, Fun & Patil, 2007; Chantrapromma et al., 2008; Ruanwas et al., 2008). As part of our research on nonlinear optic materials, the title compound was synthesized.

The asymmetric unit of the title compound consists of the C₁₂H₁₂NS⁺ cation and the C₇H₇O₃S^- anion. The cation exists in an E configuration with respect to the ethenyl C═C bond [C6═C7 = 1.346 (3) Å]. The cation is essentially planar with a dihedral angle between the pyridinium and thiophene rings of 1.94 (10)°. The orientation of the anion with respect to the cation can be indicated by the interplanar angles between the benzene ring [C13–C18] with the pyridinium [C1–C5/N1] and thiophene [C8—C11/S1] rings of 75.23 (10) and 76.83 (10)°, respectively. The ethenyl unit is nearly coplanar with the pyridinium and thiophene rings with the torsion angles C4–C5–C6–C7 = 3.0 (3)° and C6–C7–C8–S1 = -3.7 (3)°. The atom O3 of the sulfonate and the S1 atom of the thiophene contribute to the weak intramolecular C—H···O and C—H···S interactions, forming S(5) ring motifs (Bernstein et al., 1995). The bond lengths and angles are normal (Allen et al., 1987) and are comparable with closely related structures (Chantrapromma, Jindawong & Fun, 2007; Chantrapromma, Jindawong, Fun & Patil, 2007; Chantrapromma et al., 2008; Ruanwas et al., 2008).

All the O atoms of 4-methylbenzenesulfonate anion are involved in the C—H···O weak interactions (Table 1). In the crystal packing (Fig. 2), the cations and anions form alternate layers parallel to the bc plane. Within each layer both cations and anions are arranged into chains directed along the b axis. The cations and anions chains are interconnected by C—H···O weak interactions into a three dimensional network. The crystal structure is further stabilized by the C4—H4A···π and C10—H10A···π interactions (Table 1); Cg₁ is the centroid of the C13–C18 benzene ring.

Related literature top

For bond lengths and angles, see: Allen et al. (1987). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see, for example: Chantrapromma, Jindawong & Fun (2007); Chantrapromma, Jindawong, Fun & Patil (2007); Chantrapromma et al. (2008); Lakshmanaperumal et al. (2002, 2004); Rahman et al. (2003); Ruanwas et al. (2008); Usman et al. (2000, 2001).

Experimental top

The title compound was synthesized by mixing 4-(2-thiophenestyryl)-1-methylpyridinium iodide (0.1 g, 0.3 mmol) which was prepared in a similar manner to that previously reported (Chantrapromma et al., 2008) in hot methanol (40 ml) and p-toluenesulfonate (0.09 g, 0.3 mmol) in hot methanol (30 ml) (Rahman et al., 2003). The mixture immediately yielded a yellow solid of silver iodide. After stirring the mixture for 30 min, the precipitate of silver iodide was removed and the resulting solution was evaporated and the green-yellow solid was obtained. Yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from the methanol/ethanol (1:1 v/v) solvent by slow evaporation of the solvent at room temperature after several weeks (m.p. 507–509 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (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 molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing diagram of the title compound, viewed along the c axis. The weak C—H···O and C—H···S interactions are drawn as dashed lines.

1-Methyl-4-[(E)-2-(2-thienyl)ethenyl]pyridinium 4-methylbenzenesulfonate top

Crystal data top

C₁₂H₁₂NS⁺·C₇H₇O₃S⁻	Z = 2
M_r = 373.49	F(000) = 392
Triclinic, P1	D_x = 1.425 Mg m⁻³
Hall symbol: -P 1	Melting point = 507–509 K
a = 9.2947 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6144 (1) Å	Cell parameters from 4606 reflections
c = 10.7790 (1) Å	θ = 2.4–29.0°
α = 87.817 (1)°	µ = 0.32 mm⁻¹
β = 64.702 (1)°	T = 100 K
γ = 88.712 (1)°	Block, yellow
V = 870.21 (2) Å³	0.36 × 0.35 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4606 independent reflections
Radiation source: fine-focus sealed tube	4122 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 8.33 pixels mm^-1	θ_max = 29.0°, θ_min = 2.4°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.893, T_max = 0.945	l = −14→14
18024 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0809P)² + 1.1333P] where P = (F_o² + 2F_c²)/3
4606 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₁₂H₁₂NS⁺·C₇H₇O₃S⁻	γ = 88.712 (1)°
M_r = 373.49	V = 870.21 (2) Å³
Triclinic, P1	Z = 2
a = 9.2947 (1) Å	Mo Kα radiation
b = 9.6144 (1) Å	µ = 0.32 mm⁻¹
c = 10.7790 (1) Å	T = 100 K
α = 87.817 (1)°	0.36 × 0.35 × 0.18 mm
β = 64.702 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4606 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4122 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.945	R_int = 0.023
18024 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.04	Δρ_max = 0.98 e Å⁻³
4606 reflections	Δρ_min = −0.71 e Å⁻³
228 parameters

Special details top

Experimental. The 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	0.15733 (7)	0.99833 (6)	0.16005 (6)	0.02891 (16)
S2	0.55035 (5)	0.58728 (4)	0.20813 (4)	0.01428 (13)
O1	0.69298 (18)	0.61236 (15)	0.08113 (15)	0.0220 (3)
O2	0.40517 (17)	0.63620 (15)	0.19977 (15)	0.0194 (3)
O3	0.56449 (18)	0.63482 (14)	0.32920 (14)	0.0196 (3)
N1	−0.0092 (2)	0.50151 (17)	0.75333 (17)	0.0169 (3)
C1	0.1573 (2)	0.6066 (2)	0.5395 (2)	0.0221 (4)
H1A	0.2574	0.6145	0.4662	0.026*
C2	0.1351 (2)	0.5142 (2)	0.6456 (2)	0.0208 (4)
H2A	0.2199	0.4597	0.6437	0.025*
C3	−0.1335 (2)	0.5809 (2)	0.7588 (2)	0.0195 (4)
H3A	−0.2317	0.5721	0.8342	0.023*
C4	−0.1159 (2)	0.6742 (2)	0.6539 (2)	0.0206 (4)
H4A	−0.2025	0.7279	0.6586	0.025*
C5	0.0314 (2)	0.6894 (2)	0.5397 (2)	0.0196 (4)
C6	0.0632 (2)	0.7841 (2)	0.4220 (2)	0.0220 (4)
H6A	0.1643	0.7827	0.3497	0.026*
C7	−0.0453 (3)	0.8733 (2)	0.4121 (2)	0.0235 (4)
H7A	−0.1461	0.8719	0.4849	0.028*
C8	−0.0211 (3)	0.9713 (2)	0.2998 (2)	0.0225 (4)
C9	−0.1401 (2)	1.0515 (2)	0.29383 (19)	0.0151 (3)
H9A	−0.2454	1.0489	0.3591	0.018*
C10	−0.0793 (3)	1.1440 (2)	0.1689 (2)	0.0247 (4)
H10A	−0.1417	1.2086	0.1474	0.030*
C11	0.0787 (3)	1.1230 (2)	0.0896 (2)	0.0262 (4)
H11A	0.1367	1.1709	0.0070	0.031*
C12	−0.0343 (3)	0.3981 (2)	0.8657 (2)	0.0241 (4)
H12A	0.0649	0.3795	0.8710	0.036*
H12B	−0.0740	0.3134	0.8479	0.036*
H12C	−0.1099	0.4341	0.9510	0.036*
C13	0.4960 (2)	0.1137 (2)	0.2619 (2)	0.0178 (4)
C14	0.5220 (2)	0.1820 (2)	0.1374 (2)	0.0179 (4)
H14A	0.5273	0.1303	0.0643	0.021*
C15	0.5401 (2)	0.3257 (2)	0.12029 (19)	0.0161 (3)
H15A	0.5573	0.3694	0.0367	0.019*
C16	0.5323 (2)	0.40335 (18)	0.22945 (18)	0.0141 (3)
C17	0.5046 (2)	0.33792 (19)	0.35510 (19)	0.0158 (3)
H17A	0.4983	0.3899	0.4283	0.019*
C18	0.4864 (2)	0.1940 (2)	0.3702 (2)	0.0174 (4)
H18A	0.4674	0.1505	0.4543	0.021*
C19	0.4833 (3)	−0.0423 (2)	0.2771 (3)	0.0260 (4)
H19A	0.3967	−0.0675	0.3632	0.039*
H19B	0.5807	−0.0809	0.2744	0.039*
H19C	0.4644	−0.0779	0.2034	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0231 (3)	0.0296 (3)	0.0285 (3)	0.0008 (2)	−0.0063 (2)	0.0060 (2)
S2	0.0174 (2)	0.0119 (2)	0.0122 (2)	0.00110 (15)	−0.00523 (17)	0.00122 (15)
O1	0.0223 (7)	0.0188 (7)	0.0167 (7)	−0.0017 (5)	−0.0007 (6)	0.0020 (5)
O2	0.0224 (7)	0.0171 (6)	0.0200 (7)	0.0047 (5)	−0.0105 (6)	0.0004 (5)
O3	0.0284 (7)	0.0151 (6)	0.0183 (7)	0.0020 (5)	−0.0129 (6)	−0.0014 (5)
N1	0.0175 (7)	0.0161 (7)	0.0172 (7)	0.0001 (6)	−0.0076 (6)	−0.0002 (6)
C1	0.0187 (9)	0.0242 (10)	0.0180 (9)	−0.0016 (7)	−0.0028 (7)	−0.0009 (7)
C2	0.0163 (8)	0.0210 (9)	0.0229 (10)	0.0035 (7)	−0.0062 (7)	−0.0033 (7)
C3	0.0150 (8)	0.0234 (9)	0.0190 (9)	0.0000 (7)	−0.0061 (7)	−0.0007 (7)
C4	0.0182 (9)	0.0221 (9)	0.0235 (10)	0.0023 (7)	−0.0112 (8)	0.0002 (7)
C5	0.0252 (9)	0.0169 (9)	0.0181 (9)	−0.0040 (7)	−0.0104 (8)	0.0005 (7)
C6	0.0215 (9)	0.0222 (10)	0.0205 (9)	−0.0015 (7)	−0.0074 (8)	0.0003 (7)
C7	0.0218 (9)	0.0251 (10)	0.0218 (10)	−0.0018 (8)	−0.0077 (8)	0.0010 (8)
C8	0.0275 (10)	0.0195 (9)	0.0225 (10)	−0.0024 (8)	−0.0127 (8)	0.0015 (7)
C9	0.0091 (7)	0.0229 (9)	0.0135 (8)	0.0019 (6)	−0.0051 (6)	−0.0011 (7)
C10	0.0281 (10)	0.0218 (10)	0.0280 (11)	−0.0013 (8)	−0.0162 (9)	0.0061 (8)
C11	0.0295 (11)	0.0243 (10)	0.0242 (10)	−0.0038 (8)	−0.0115 (9)	0.0076 (8)
C12	0.0322 (11)	0.0195 (9)	0.0224 (10)	−0.0001 (8)	−0.0137 (9)	0.0034 (8)
C13	0.0158 (8)	0.0145 (8)	0.0243 (9)	0.0013 (6)	−0.0098 (7)	0.0004 (7)
C14	0.0181 (8)	0.0169 (9)	0.0187 (9)	0.0016 (7)	−0.0079 (7)	−0.0030 (7)
C15	0.0167 (8)	0.0172 (9)	0.0139 (8)	0.0014 (6)	−0.0061 (7)	0.0001 (6)
C16	0.0147 (8)	0.0123 (8)	0.0141 (8)	0.0012 (6)	−0.0051 (6)	0.0004 (6)
C17	0.0172 (8)	0.0160 (8)	0.0142 (8)	0.0013 (6)	−0.0069 (7)	0.0007 (6)
C18	0.0172 (8)	0.0165 (9)	0.0190 (9)	0.0000 (6)	−0.0086 (7)	0.0043 (7)
C19	0.0313 (11)	0.0141 (9)	0.0367 (12)	−0.0006 (8)	−0.0186 (10)	0.0020 (8)

Geometric parameters (Å, º) top

S1—C11	1.707 (2)	C9—C10	1.484 (3)
S1—C8	1.715 (2)	C9—H9A	0.9300
S2—O2	1.4569 (15)	C10—C11	1.362 (3)
S2—O3	1.4574 (14)	C10—H10A	0.9300
S2—O1	1.4587 (14)	C11—H11A	0.9300
S2—C16	1.7769 (18)	C12—H12A	0.9600
N1—C3	1.351 (2)	C12—H12B	0.9600
N1—C2	1.352 (3)	C12—H12C	0.9600
N1—C12	1.479 (3)	C13—C18	1.394 (3)
C1—C2	1.367 (3)	C13—C14	1.398 (3)
C1—C5	1.400 (3)	C13—C19	1.504 (3)
C1—H1A	0.9300	C14—C15	1.391 (3)
C2—H2A	0.9300	C14—H14A	0.9300
C3—C4	1.371 (3)	C15—C16	1.393 (3)
C3—H3A	0.9300	C15—H15A	0.9300
C4—C5	1.403 (3)	C16—C17	1.393 (3)
C4—H4A	0.9300	C17—C18	1.393 (3)
C5—C6	1.458 (3)	C17—H17A	0.9300
C6—C7	1.346 (3)	C18—H18A	0.9300
C6—H6A	0.9300	C19—H19A	0.9600
C7—C8	1.447 (3)	C19—H19B	0.9600
C7—H7A	0.9300	C19—H19C	0.9600
C8—C9	1.357 (3)

C11—S1—C8	92.72 (11)	C11—C10—C9	112.07 (19)
O2—S2—O3	112.96 (8)	C11—C10—H10A	124.0
O2—S2—O1	113.06 (9)	C9—C10—H10A	124.0
O3—S2—O1	113.19 (9)	C10—C11—S1	111.84 (17)
O2—S2—C16	105.46 (9)	C10—C11—H11A	124.1
O3—S2—C16	105.73 (9)	S1—C11—H11A	124.1
O1—S2—C16	105.54 (8)	N1—C12—H12A	109.5
C3—N1—C2	120.63 (17)	N1—C12—H12B	109.5
C3—N1—C12	118.95 (17)	H12A—C12—H12B	109.5
C2—N1—C12	120.41 (17)	N1—C12—H12C	109.5
C2—C1—C5	120.85 (18)	H12A—C12—H12C	109.5
C2—C1—H1A	119.6	H12B—C12—H12C	109.5
C5—C1—H1A	119.6	C18—C13—C14	118.08 (18)
N1—C2—C1	120.52 (18)	C18—C13—C19	121.03 (18)
N1—C2—H2A	119.7	C14—C13—C19	120.87 (18)
C1—C2—H2A	119.7	C15—C14—C13	121.46 (18)
N1—C3—C4	120.49 (18)	C15—C14—H14A	119.3
N1—C3—H3A	119.8	C13—C14—H14A	119.3
C4—C3—H3A	119.8	C14—C15—C16	119.38 (17)
C3—C4—C5	120.62 (18)	C14—C15—H15A	120.3
C3—C4—H4A	119.7	C16—C15—H15A	120.3
C5—C4—H4A	119.7	C15—C16—C17	120.27 (17)
C1—C5—C4	116.87 (18)	C15—C16—S2	119.07 (14)
C1—C5—C6	117.82 (18)	C17—C16—S2	120.61 (14)
C4—C5—C6	125.30 (19)	C16—C17—C18	119.45 (17)
C7—C6—C5	123.75 (19)	C16—C17—H17A	120.3
C7—C6—H6A	118.1	C18—C17—H17A	120.3
C5—C6—H6A	118.1	C17—C18—C13	121.35 (18)
C6—C7—C8	126.6 (2)	C17—C18—H18A	119.3
C6—C7—H7A	116.7	C13—C18—H18A	119.3
C8—C7—H7A	116.7	C13—C19—H19A	109.5
C9—C8—C7	122.8 (2)	C13—C19—H19B	109.5
C9—C8—S1	112.58 (16)	H19A—C19—H19B	109.5
C7—C8—S1	124.57 (17)	C13—C19—H19C	109.5
C8—C9—C10	110.76 (17)	H19A—C19—H19C	109.5
C8—C9—H9A	124.6	H19B—C19—H19C	109.5
C10—C9—H9A	124.6

C3—N1—C2—C1	−0.7 (3)	C8—C9—C10—C11	1.8 (3)
C12—N1—C2—C1	177.87 (19)	C9—C10—C11—S1	−0.7 (3)
C5—C1—C2—N1	−0.3 (3)	C8—S1—C11—C10	−0.32 (19)
C2—N1—C3—C4	1.0 (3)	C18—C13—C14—C15	0.9 (3)
C12—N1—C3—C4	−177.58 (19)	C19—C13—C14—C15	−177.44 (18)
N1—C3—C4—C5	−0.3 (3)	C13—C14—C15—C16	0.0 (3)
C2—C1—C5—C4	0.9 (3)	C14—C15—C16—C17	−0.8 (3)
C2—C1—C5—C6	−179.05 (19)	C14—C15—C16—S2	−178.34 (14)
C3—C4—C5—C1	−0.6 (3)	O2—S2—C16—C15	69.43 (16)
C3—C4—C5—C6	179.3 (2)	O3—S2—C16—C15	−170.67 (14)
C1—C5—C6—C7	−177.1 (2)	O1—S2—C16—C15	−50.48 (17)
C4—C5—C6—C7	3.0 (3)	O2—S2—C16—C17	−108.10 (16)
C5—C6—C7—C8	178.9 (2)	O3—S2—C16—C17	11.80 (18)
C6—C7—C8—C9	175.6 (2)	O1—S2—C16—C17	131.99 (16)
C6—C7—C8—S1	−3.7 (3)	C15—C16—C17—C18	0.7 (3)
C11—S1—C8—C9	1.40 (18)	S2—C16—C17—C18	178.16 (14)
C11—S1—C8—C7	−179.3 (2)	C16—C17—C18—C13	0.3 (3)
C7—C8—C9—C10	178.64 (19)	C14—C13—C18—C17	−1.0 (3)
S1—C8—C9—C10	−2.0 (2)	C19—C13—C18—C17	177.30 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.93	2.31	3.219 (3)	166
C3—H3A···O1ⁱⁱ	0.93	2.49	3.168 (2)	130
C6—H6A···O2	0.93	2.56	3.378 (3)	147
C11—H11A···O1ⁱⁱⁱ	0.93	2.54	3.303 (3)	139
C12—H12A···O1ⁱ	0.96	2.52	3.455 (3)	165
C12—H12C···O1ⁱⁱ	0.96	2.47	3.341 (3)	151
C15—H15A···O2^iv	0.93	2.42	3.272 (2)	152
C17—H17A···O3ⁱ	0.93	2.43	3.202 (2)	141
C4—H4A···Cg1^v	0.93	2.62	3.431 (2)	145
C10—H10A···Cg1^vi	0.93	2.95	3.666 (3)	135

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂NS⁺·C₇H₇O₃S⁻
M_r	373.49
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.2947 (1), 9.6144 (1), 10.7790 (1)
α, β, γ (°)	87.817 (1), 64.702 (1), 88.712 (1)
V (Å³)	870.21 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.36 × 0.35 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.893, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	18024, 4606, 4122
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.149, 1.04
No. of reflections	4606
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.71

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
C2—H2A···O3ⁱ	0.93	2.3077	3.219 (3)	166
C3—H3A···O1ⁱⁱ	0.93	2.4896	3.168 (2)	130
C6—H6A···O2	0.93	2.5588	3.378 (3)	147
C11—H11A···O1ⁱⁱⁱ	0.93	2.5423	3.303 (3)	139
C12—H12A···O1ⁱ	0.96	2.5180	3.455 (3)	165
C12—H12C···O1ⁱⁱ	0.96	2.4713	3.341 (3)	151
C15—H15A···O2^iv	0.93	2.4231	3.272 (2)	152
C17—H17A···O3ⁱ	0.93	2.4258	3.202 (2)	141
C4—H4A···Cg1^v	0.93	2.6236	3.431 (2)	145
C10—H10A···Cg1^vi	0.93	2.9488	3.666 (3)	135

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

Footnotes

†This paper is dedicated to the late Her Royal Highness Princess Galyani Vadhana Krom Luang Naradhiwas Rajanagarindra for her patronage of science in Thailand.

‡Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

The authors thank the Prince of Songkla University for a research grant. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chantrapromma, S., Jindawong, B. & Fun, H.-K. (2007). Acta Cryst. E63, o2020–o2022. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K. & Patil, P. S. (2007). Acta Cryst. E63, o2321–o2323. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Laksana, C., Ruanwas, P. & Fun, H.-K. (2008). Acta Cryst. E64, o574–o575. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lakshmanaperumal, C. K., Arulchakkaravarthi, A., Balamurugan, N., Santhanaraghavan, P. & Ramasamy, P. (2004). J. Cryst. Growth, 265, 260–265. Web of Science CrossRef CAS Google Scholar
Lakshmanaperumal, C. K., Arulchakkaravarthi, A., Rajesh, N. P., Santhana Raghavan, P., Huang, Y. C., Ichimura, M. & Ramasamy, P. (2002). J. Cryst. Growth, 240, 212–217. CAS Google Scholar
Rahman, A. A., Razak, I. A., Fun, H.-K., Saenee, P., Jindawong, B., Chantrapromma, S. & Karalai, C. (2003). Acta Cryst. E59, o1798–o1800. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ruanwas, P., Kobkeatthawin, T., Chantrapromma, S., Fun, H.-K. & Karalai, C. (2008). Acta Cryst. E64, o1453–o1454. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Usman, A., Kosuge, H., Okada, S., Oikawa, H. & Nakanishi, H. (2001). Jpn. J. Appl. Phys. 40, 4213–4216. Google Scholar
Usman, A., Okada, S., Oikawa, H. & Nakanishi, H. (2000). Chem. Mater. 12, 1162–1170. Google Scholar