4-(4-Bromo­styr­yl)-1-methylpyridinium tosyl­ate

M Krishna Kumar; S Sudhahar; B M Sornamurthy; G Chakkaravarthi; R Mohan Kumar

doi:10.1107/S1600536813009227

. 2013 Apr 10;69(Pt 5):o694. doi: 10.1107/S1600536813009227

4-(4-Bromostyryl)-1-methylpyridinium tosylate

M Krishna Kumar ^a, S Sudhahar ^a, B M Sornamurthy ^a, G Chakkaravarthi ^b,^*, R Mohan Kumar ^a,^*

PMCID: PMC3648231 PMID: 23723851

Abstract

In the cation of the title compound, C₁₄H₁₃BrN⁺·C₇H₇O₃S⁻, the dihedral angle between the benzene and pyridine rings is 8.34 (11)°. The Br atom is disordered over two positions with site occupancies of 0.74 (2) and 0.26 (2). The molecular structure is stabilized by a weak intramolecular C—H⋯O interactions. The crystal structure exhibits weak C—H⋯O and π–π [centroid–centroid distance = 3.7466 (17) Å] interactions, forming a three dimensional network.

Related literature

For molecular compounds with non-linear optical properties, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶). For similar structures, see: Krishnakumar et al. (2012 ▶); Okada et al. (1990 ▶); Sivakumar et al. (2012 ▶). graphic file with name e-69-0o694-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₃BrN⁺·C₇H₇O₃S⁻
M _r = 446.35
Monoclinic,
a = 9.0502 (2) Å
b = 6.4201 (1) Å
c = 33.9280 (7) Å
β = 94.469 (1)°
V = 1965.33 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.22 mm⁻¹
T = 295 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.575, T _max = 0.665
22764 measured reflections
5596 independent reflections
3012 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.130
S = 1.01
5596 reflections
256 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 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.^{(27.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009227/bt6900sup1.cif

e-69-0o694-sup1.cif^{(27.6KB, cif)}

Click here for additional data file.^{(268.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009227/bt6900Isup2.hkl

e-69-0o694-Isup2.hkl^{(268.5KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009227/bt6900Isup3.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
C10—H10⋯O1	0.93	2.57	3.415 (3)	151
C12—H12⋯O2ⁱ	0.93	2.39	3.247 (3)	153
C14—H14B⋯O1ⁱⁱ	0.96	2.53	3.438 (4)	157

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

Acknowledgments

MK would like to thank the Council of Scientific and Industrial Research, New Delhi, India, for providing financial support [project No. 03 (1200)/11/EMR-II)].

supplementary crystallographic information

Comment

In continuation of our studies of molecular compounds with non linear optical properties which are used in optoelectronic and photonic devices (Bosshard et al., 1995; Nalwa & Miyata, 1997), we herewith report the crystal structure of the title compound (I) (Fig. 1).

The asymmetric unit of the title compound consists of C₁₄H₁₃BrN⁺ cations and C₇H₇O₃S^- anios. The geometric parameters of the title compound are agree well with those of reported structures (Krishnakumar et al., 2012; Sivakumar et al., 2012; Okada et al., 1990). In the cation, the bromine atom is disordered over two positions, with the site occupancies of 0.74 (2) and 0.26 (2). The cation is planar [torision angle C4-C7=C8-C9 = 178.1 (3)°] about the double bond between the two rings in the cation. The dihedral angle between the benzene ring and pyridinium ring in the cation is 8.34 (11)°.

The molecular structure is stabilized by weak intramolecular C-H···O interactions. In the crystal structure, adjacent anions and cations are linked by weak C—H···O (Table 1 & Fig.2) and π···π [Cg1···Cg2 (x,-1/2-y,1/2+z) = 3.7466 (17)Å and Cg2···Cg1 (x,1+y,z) distance = 3.7468 (17)Å; Cg1 and Cg2 are the centroids of the rings (C9/C10/C11/N1/C12/C13) and (C1-C6), respectively] interactions.

Experimental

The title compound was synthesized by the condensation of 4-methyl-N-methyl pyridinium tosylate, which was prepared from 4-picoline (4.65g, 5 mmol) and methyl p-toluenesulfonate (9.31g, 5 mmol), and 4-bromobenzaldehyde (9.24 g, 5 mmol) in the presence of piperidine. The single crystals suitable for X-ray diffraction were grown by slow evaporation method in room temperature.