4-{2-[4-(Dimethyl­amino)­phen­yl]ethen­yl}-1-methyl­pyridinium 3,5-dicarb­oxy­benzene­sulfonate methanol monosolvate

Liang Li; Huijuan Cui; Zhou Yang; Xutang Tao; Huai Yang

doi:10.1107/S1600536811054419

. 2012 Jan 7;68(Pt 2):o281. doi: 10.1107/S1600536811054419

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate methanol monosolvate

Liang Li ^a, Huijuan Cui ^a, Zhou Yang ^a,^*, Xutang Tao ^b, Huai Yang ^a

PMCID: PMC3274978 PMID: 22346923

Abstract

In the crystal structure of the title solvated salt, C₁₆H₁₉N₂ ⁺·C₈H₅O₇S⁻·CH₃OH, the anions and the methanol solvent molecules are linked by O—H⋯O hydrogen bonds. The cations and anions are packed as alternate layers parallel to (11 Inline graphic ). The crystal structure is further stabilized by a π–π interaction between the pyridinium and benzene rings of the cations, with a centroid–centroid distance of 3.5492 (4) Å.

Related literature

The title compound was synthesized as part of our continuing research on the nonlinear optical properties of DAS (4-N,N-dimethylamino-4′-N′-methylstilbazolium) derivatives. For the synthesis, see: Okada et al. (1990 ▶). For background to non-linear optical materials, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶); Yang, Mutter et al. (2007 ▶); Ruiz et al. (2006 ▶). For the effects of different substituents of benzene sulfonate on its non-linear optical properties, see: Okada et al. (2003 ▶); Yang, Wörle et al. (2007 ▶); Ogawa et al. (2008 ▶), Yang et al. (2005 ▶). For standard bond-lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₉N₂ ⁺·C₈H₅O₇S⁻·CH₄O
M _r = 516.55
Triclinic,
a = 7.5277 (12) Å
b = 10.5517 (17) Å
c = 16.467 (3) Å
α = 106.750 (7)°
β = 97.504 (8)°
γ = 100.273 (8)°
V = 1209.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 173 K
0.45 × 0.31 × 0.22 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.629, T _max = 1.000
15622 measured reflections
5523 independent reflections
5192 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.116
S = 1.13
5523 reflections
332 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811054419/ez2270sup1.cif

e-68-0o281-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054419/ez2270Isup2.hkl

e-68-0o281-Isup2.hkl^{(270.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811054419/ez2270Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811054419/ez2270Isup4.cml

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

Enhanced figure: interactive version of Fig. 1

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6ⁱ	0.84	1.89	2.6796 (18)	156
O4—H4A⋯O8ⁱⁱ	0.84	1.79	2.6156 (18)	168
O8—H8⋯O7ⁱⁱⁱ	0.84	1.86	2.6897 (18)	169

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

Acknowledgments

The authors thank the Natural Science Foundation (grant No. 50803005), the Fundamental Research Funds for the Central Universities, the Scientific Research Foundation for Returned Overseas Chinese Scholars and the National Natural Science Fund for Distinguished Young Scholars (grant No. 51025313).

supplementary crystallographic information

Comment

During the last three decades, nonlinear optical materials have been of considerable interest for their potential applications such as frequency conversion, electro-optic modulation and THz generation (Bosshard et al., 1995; Nalwa & Miyata, 1997; Yang, Mutter et al., 2007). In order to create efficient NLO materials, both the molecular and bulk properties must be optimized (Yang et al., 2005; Ruiz et al., 2006; Yang, Wörle et al., 2007). The title compound was synthesized as part of our continuing research on the nonlinear optical properties of DAS (4-N, N-dimethylamino-4'-N'-methyl-stilbazolium) derivatives.

Fig. 1 illustrates the molecular structure of the title compound together with the atomic numbering scheme. The unit cell of the title compound contains two asymmetric units, each consisting of one C₁₆H₁₉N₂⁺ cation, one C₈H₅O₇S^- anion and one methanol molecule. The bond distances and angles in both the cation and anion are in normal ranges (Allen et al., 1987). In the crystal structure, atoms O4, O6, O7 and O8 of the anion are involved in O—H···O interactions. The cations and anions are stacked in a parallel manner and form alternating layers parallel to the (112) plane. The crystal structure is further stabilized by a π···π interaction between the pyridinium and C3–C8 benzene rings with a centroid–centroid distance of 3.5492 (4) Å, which combine with the intermolecular O—H···O interactions to form a three-dimensional network.

Experimental

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate was prepared by the metathesization of 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium iodide (Okada et al., 1990) with the sodium salt of the 3,5-dicarboxybenzenesulfonic acid. The title compound was then recrystallized from methanol to get high purity material for crystal growth. 4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate: yield 72%; ¹H-NMR (400 MHz, DMSO-d₆): 8.67 (d, 2H, J= 6.8Hz, C₅H₄N), 8.39 (s, 1H, C₆H₃SO₃^-), 8.34 (d, 2H, C₆H₃SO₃^-), 8.03(d, 2H, J= 6.8Hz, C₅H₄N), 7.91 (d, 1H, J= 16.0Hz, CH), 7.59(d, 2H, J= 8.4Hz, C₆H₃SO₃^-), 7.17 (d, 1H, J= 16.0Hz, CH), 6.79 (d, 2H, J= 8.8Hz, C₆H₄), 4.16 (s, 3H, NMe), 3.01 (s, 6H, NMe₂). C, H, N analysis calcd. for C₂₄H₂₄N₂O₇S: C 59.49, H 4.99, N 5.78; found: C 59.39, H 5.02, N 5.79. Crystals were obtained by slow cooling method from 45°C to room temperature in methanol.