1-Methyl-4-(4-methylstyryl)pyridinium 4-methylbenzenesulfonate

M Krishnakumar; S Sudhahar; A Silambarasan; G Chakkaravarthi; R Mohankumar

doi:10.1107/S1600536812044509

. 2012 Nov 3;68(Pt 12):o3268. doi: 10.1107/S1600536812044509

1-Methyl-4-(4-methylstyryl)pyridinium 4-methylbenzenesulfonate

M Krishnakumar ^a, S Sudhahar ^a, A Silambarasan ^a, G Chakkaravarthi ^b,^*, R Mohankumar ^c,^*

PMCID: PMC3588818 PMID: 23468783

Abstract

In the title salt, C₁₅H₁₆N⁺·C₇H₇O₃S⁻, the dihedral angle between the pyridine and benzene rings of the cation is 5.98 (18)°. In the crystal, adjacent anions and cations are linked by weak non-classical C—H⋯O hydrogen bonds and π–π interactions, with a centroid–centroid distance of 3.749 (2) Å.

Related literature

For molecular compounds with non-linear optical properties, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶). For related structures, see: Murugavel et al. (2009 ▶); Sivakumar et al. (2012 ▶); Okada et al. (1990 ▶).

Experimental

Crystal data

C₁₅H₁₆N⁺·C₇H₇O₃S⁻
M _r = 381.48
Monoclinic,
a = 9.1380 (6) Å
b = 6.4257 (5) Å
c = 33.884 (2) Å
β = 95.004 (4)°
V = 1982.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 295 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.950, T _max = 0.964
18512 measured reflections
4902 independent reflections
3850 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.075
wR(F ²) = 0.184
S = 1.13
4902 reflections
247 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(26.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044509/rk2384sup1.cif

e-68-o3268-sup1.cif^{(26.8KB, cif)}

Click here for additional data file.^{(235.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044509/rk2384Isup2.hkl

e-68-o3268-Isup2.hkl^{(235.3KB, hkl)}

Click here for additional data file.^{(7.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812044509/rk2384Isup3.cml

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
C3—H3⋯O2ⁱ	0.93	2.42	3.273 (4)	152
C14—H14B⋯O1ⁱⁱ	0.96	2.59	3.482 (4)	155

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors wish to acknowledge the SAIF, IIT Madras for the data collection. MK would also like to thank the Council of Scientific and Industrial Research (CSIR), New Delhi, for providing financial support (project No. 03 (1200)/EMR-II).

supplementary crystallographic information

Comment

In continuation of our studies of molecular compounds with non linear optical properties which are known to exhibit applications in optoelectronic and photonic devices (Bosshard et al., 1995; Nalwa & Miyata, 1997), we determined the crystal structure of the title compound I.

The asymmetric unit of I, (Fig. 1), contains C₁₅H₁₆N⁺ cation and C₇H₇O₃S^- anion. The geometric parameters of the title compound are comparable with the similar reported structures: Murugavel et al., 2009; Sivakumar et al., 2012; Okada et al., 1990. The cation is planar - torsion angle about the double bond between the two rings in the cation, C1–C6═C7–C8 is 178.2 (3)°. The benzene ring in the anion is almost planar, with the maximum deviation of 0.003 (3)Å.

In the crystal structure, the adjacent anions and cations are linked by weak non-classical C–H···O H bonds (Table 1 & Fig.2) and π–π interactions - Cg1···Cg2ⁱⁱⁱ = 3.749 (2)Å, where Cg1 and Cg2 are the centroids of the rings (C1-C5/N1) and (C8-C13), respectively. Symmetry code: (iii) x, -y-1/2, z+1/2.

Experimental

The title compound was synthesized by the condensation of 4-methyl-N-methyl pyridinium tosylate, which was prepared from 4-picoline (4.65 g, 5 mmol) and methyl p-toluenesulfonate (9.31 g, 5 mmol), and 4-methylbenzaldehyde (6 g, 5 mmol) in the presence of piperidine. The single crystals were grown by slow evaporation method in room temperature.