(E)-4-[4-(Dimethyl­amino)styr­yl]-1-methyl­pyridinium 4-bromo­benzene­sulfonate

Suchada Chantrapromma; Patcharaporn Jansrisewangwong; Rusmeenee Musor; Hoong-Kun Fun

doi:10.1107/S1600536808043547

. 2009 Jan 8;65(Pt 2):o217–o218. doi: 10.1107/S1600536808043547

(E)-4-[4-(Dimethylamino)styryl]-1-methylpyridinium 4-bromobenzenesulfonate¹

Suchada Chantrapromma ^a,^*, Patcharaporn Jansrisewangwong ^a, Rusmeenee Musor ^a, Hoong-Kun Fun ^b,^‡

PMCID: PMC2968146 PMID: 21581836

Abstract

In the title compound, C₁₆H₁₉N₂ ⁺·C₆H₄BrO₃S⁻, the cation is nearly planar, with a dihedral angle of 3.19 (15)° between the pyridinium and the dimethylaminophenyl rings, and exists in the trans configuration. In the crystal packing, the cations and anions are linked into chains parallel to the c axis. These chains are stacked along the b axis. The crystal is stabilized by weak C—H⋯O and C—H⋯π interactions, and a π–π interaction is also observed with a Cg⋯Cg distance of 3.5675 (19) Å.

Related literature

For background to NLO materials research, see: Chia et al. (1995 ▶); Sato et al. (1999 ▶); Nogi et al. (2000 ▶); Otero et al. (2002 ▶); Dittrich et al. (2003 ▶). For related structures, see, for example: Adachi et al. (1999 ▶); Chantrapromma et al. (2006 ▶; 2008 ▶); Jagannathan et al. (2007 ▶); Ogawa et al. (2008 ▶); Rahman et al. (2003 ▶); Yang et al. (2007 ▶). For comparison bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₉N₂ ⁺·C₆H₄BrO₃S⁻
M _r = 475.39
Monoclinic,
a = 10.3712 (4) Å
b = 10.9937 (5) Å
c = 17.9027 (8) Å
β = 92.442 (3)°
V = 2039.37 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.15 mm⁻¹
T = 100.0 (1) K
0.49 × 0.31 × 0.11 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.414, T _max = 0.787
13146 measured reflections
6479 independent reflections
4811 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.097
S = 1.02
6479 reflections
265 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −1.38 e Å⁻³
Absolute structure: Flack (1983 ▶), 1997 Friedel pairs
Flack parameter: 0.024 (7)

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/S1600536808043547/pk2136sup1.cif

e-65-0o217-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043547/pk2136Isup2.hkl

e-65-0o217-Isup2.hkl^{(317.1KB, 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⋯O1ⁱ	0.93	2.44	3.366 (4)	175
C4—H4A⋯O2ⁱⁱ	0.93	2.45	3.375 (4)	175
C6—H6A⋯O3ⁱⁱⁱ	0.93	2.44	3.175 (4)	136
C7—H7A⋯O2ⁱⁱ	0.93	2.36	3.285 (4)	173
C14—H14C⋯O3ⁱ	0.96	2.36	3.304 (4)	168
C15—H15A⋯O2	0.96	2.57	3.515 (4)	168
C19—H19A⋯O1^iv	0.93	2.47	3.306 (4)	149
C3—H3A⋯Cg3ⁱⁱ	0.93	2.76	3.601 (4)	151
C14—H14B⋯Cg2^v	0.96	2.55	3.468 (4)	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg2 and Cg3 are the centroids of the C8–C13 and C17–C22 rings.

Acknowledgments

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

supplementary crystallographic information

Comment

Organic crystals with extensive conjugated π systems are attractive candidates for non-linear optic (NLO) studies because of their large NLO coefficients (Chia et al., 1995; Dittrich et al., 2003; Otero et al., 2002; Nogi et al., 2000; Sato et al., 1999). 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) is one such promising NLO material (Adachi et al., 1999). Previous studies (Dittrich et al., 2003; Nogi et al., 2000; Sato et al., 1999) have shown that DAST and its analogues exhibit second-order non-linear optical properties. To investigate the effect of counter anion on the NLO properties of DAST, the title compound was prepared by changing the counter anion from 4-toluenesulfonate in DAST to 4-bromobenzenesulfonate. The title compound is found to crystallize with the non-centrosymmetric space group Cc and therefore has second order nonlinear optical properties.

The asymmetric unit of the title compound (Fig. 1), consists of the C₁₆H₁₉N₂⁺ cation and C₆H₄BrO₃S^- anion. The cation exists in the E configuration with respect to the C6=C7 double bond [1.342 (5) Å] and the cation is nearly planar as indicated by the dihedral angle between the pyridinium and the dimethylaminophenyl rings 3.19 (15)°, and by the torsion angles C4–C5–C6–C7 = 1.0 (5)° and C6–C7–C8–C13 = 2.4 (5)°. Both methyl groups of the dimethylamino group are co-planar with the C8–C13 ring with the torsion angle C15—N2–C11–C10 of 2.3 (5)° and C16–N2–C11–C12 = 1.5 (5)°. The relative arrangement of cation and anion is shown by the angles between the mean plane of the 4-bromophenyl ring and those of the pyridinium and dimethylaminophenyl systems which are 74.81 (16)° and 77.99 (16)°, respectively. The bond lengths and angles are normal (Allen et al., 1987) and the cation bond lengths and angles are comparable with related structures (Chantrapromma et al., 2008).

In the crystal packing, all O atoms of sulfonate group are involved in weak C—H···O interactions (Table 1). The cations and anions are linked by weak C—H···O interactions into chains along the c axis and these chains are stacked along the b axis (Fig. 2). The crystal structure is further stabilized by a C—H···π interactions (Table 1). π–π interactions with the distance Cg₁···Cg₂ = 3.5675 (19) Å (symmetry code -1/2 + x, -1/2 + y, z and 1/2 + x, 1/2 + y, z) are observed; Cg₁, Cg₂ and Cg₃ are the centroids of the N1/C1–C5, C8–C13 and C17–C22 rings.

Experimental

(E)-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide (compound A) was synthesized by mixing a solution (1:1:1 molar ratio) of 1,4-dimethylpyridinium iodide (2.00 g, 8.5 mmol), 4-dimethylaminobenzaldehyde (1.27 g, 8.5 mmol) and piperidine (0.84 ml, 8.5 mmol) in hot methanol (50 ml). The resulting solution was refluxed for 3 h under a nitrogen atmosphere. The resultant solid was filtered off, washed with diethylether to give red solid of compound A (2.86 g, 92%), Mp. 536–537 K). Silver(I) p-bromobenzenesulfonate (compound B) was synthesized according to our previously reported procedure (Chantrapromma et al., 2006). The title compound was synthesized by mixing compound A (0.20 g, 0.5 mmol) in hot methanol (25 ml) and a solution of compound B (0.17 g, 0.5 mmol) in hot methanol (50 ml). The mixture immediately yielded a grey precipitate of silver iodide. After stirring the mixture for 30 min, the precipitate of silver iodide was removed and the resulting solution was evaporated yielding a red solid. Red plate-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from methanol by slow evaporation of the solvent at room temperature over several days, Mp. 536–537 K.