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

Suchada Chantrapromma; Pumsak Ruanwas; Hoong-Kun Fun; Chatchanok Karalai

doi:10.1107/S1600536808031401

. 2008 Oct 4;64(Pt 11):o2072–o2073. doi: 10.1107/S1600536808031401

1-Methyl-4-[(E)-2-(2-thienyl)ethenyl]pyridinium 4-methylbenzenesulfonate¹

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

PMCID: PMC2959609 PMID: 21580938

Abstract

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,
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[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 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

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 ▶).

Supplementary Material

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

e-64-o2072-sup1.cif^{(20.9KB, cif)}

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

e-64-o2072-Isup2.hkl^{(225.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1 is the centroid of the C13–C18 benzene ring.

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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).