2-[(E)-2-(4-Ethoxy­phen­yl)ethen­yl]-1-methyl­pyridinium 4-bromo­benzene­sulfonate monohydrate

Hoong-Kun Fun; Kullapa Chanawanno; Suchada Chantrapromma

doi:10.1107/S1600536809055846

. 2010 Jan 9;66(Pt 2):o305–o306. doi: 10.1107/S1600536809055846

2-[(E)-2-(4-Ethoxyphenyl)ethenyl]-1-methylpyridinium 4-bromobenzenesulfonate monohydrate¹

Hoong-Kun Fun ^a,^*,^‡, Kullapa Chanawanno ^b, Suchada Chantrapromma ^b,^§

PMCID: PMC2979781 PMID: 21579738

Abstract

In the title compound, C₁₆H₁₈NO⁺·C₆H₄BrO₃S⁻·H₂O, the cation exists in an E configuration with respect to the ethenyl bond and is slightly twisted with a dihedral angle of 8.5 (2)° between pyridinium and benzene rings. In the crystal, the cations are arranged in layers parallel to (100), with π–π interactions between pyridinium and benzene rings [centroid–centroid distances = 3.651 (3) and 3.613 (3) Å]. The anions and water molecules are located between the cationic layers. The ions and water molecules are linked into a three-dimensional framework by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

The title compound was synthesized as part of an investigation of the influence of the counter-ions on non-linear optical (NLO) properties. For background to NLO materials research, see: Coe et al. (2002 ▶); Pan et al. (1996 ▶). For related structures, see: Chanawanno et al. (2009 ▶); Chantrapromma et al. (2006 ▶, 2009 ▶); Laksana et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₆H₁₈NO⁺·C₆H₄BrO₃S⁻·H₂O
M _r = 494.39
Monoclinic,
a = 9.8022 (5) Å
b = 6.5162 (3) Å
c = 34.9982 (17) Å
β = 105.102 (3)°
V = 2158.24 (18) Å³
Z = 4
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 100 K
0.34 × 0.31 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.547, T _max = 0.703
30564 measured reflections
6286 independent reflections
4937 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.224
S = 1.15
6286 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −1.36 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809055846/ci5012sup1.cif

e-66-0o305-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055846/ci5012Isup2.hkl

e-66-0o305-Isup2.hkl^{(307.7KB, 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
O1W—H2W1⋯O4	0.85	2.09	2.929 (6)	171
O1W—H1W1⋯O2ⁱ	0.85	1.99	2.827 (6)	168
C1—H1A⋯O1Wⁱⁱ	0.93	2.23	3.154 (7)	176
C2—H2A⋯O1Wⁱⁱⁱ	0.93	2.43	3.223 (7)	143
C4—H4A⋯O4	0.93	2.50	3.378 (7)	158
C6—H6A⋯O3^iv	0.93	2.56	3.442 (7)	159
C13—H13A⋯O3^iv	0.93	2.49	3.387 (7)	161
C14—H14A⋯O2^v	0.96	2.57	3.384 (7)	143
C14—H14C⋯O3^iv	0.96	2.51	3.129 (7)	122

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

Acknowledgments

The authors thank the Prince of Songkla University for a research grant and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a study grant.

supplementary crystallographic information

Comment

Ionic organic crystals are of special interest due to their high second order optical nonlinearities (Coe et al., 2002). The orientation of ionic chromophores can be arranged simply by changing the counter-ions (Pan et al., 1996). During the course of our NLO materials research, we have previously synthesized and reported crystal structures of related pyridinium salts containing the 2-[(E)-2-(4-ethoxyphenyl)ethenyl]-1-methylpyridinium cationic part (Chanawanno et al., 2009; Laksana et al., 2008). The title compound was synthesized by retaining the same cationic part but changing the anion counter part to 4-bromobenzenesulfonate in order to investigate the influence of the counter-ions on the NLO properties. However, it was found that the title compound crystallized in a centrosymmetric space group P2₁/c and hence no second-order nonlinear optical properties are observed.

In the title compound (Fig. 1), the cation exists in an E configuration with respect to the ethenyl bond [C5—C6—C7—C8 = -179.9 (5)°]. The cation is slightly twisted with a dihedral angle between the pyridinium and benzene rings of 8.5 (2)°. The pyridinium and benzene rings of the cation form dihedral angles of 79.2 (2) and 71.0 (2)°, respectively, with the benzene ring of the anion. Bond distances in both cation and anion have normal values (Allen et al., 1987) and are comparable to those observed in related structures (Chanawanno et al., 2009; Chantrapromma et al., 2009; Laksana et al., 2008).

In the crystal, the cations are stacked along the b axis and are arranged in layers parallel to the (100) with π–π interactions involving pyridinium (centroid Cg1) and benzene (centroid Cg2) rings [Cg1···Cg1ⁱⁱ = 3.651 (3) Å and Cg1···Cg2ⁱⁱⁱ = 3.613 (3) Å; symmetry codes as in Table 1]. The anions and water molecules are located between the cationic layers. The cations are linked with the water molecules and anions by C—H···O weak interactions (Table 1), whereas the anions are linked with water molecules by O—H···O hydrogen bonds (Table 1). These interactions connect the ionic units and water molecules into a three-dimensional network (Fig. 2).

Experimental

2-[(E)-2-(4-Ethoxyphenyl)ethenyl]-1-methylpyridinium iodide (0.21 g, 0.58 mmol) which was prepared according to the previous method (Laksana et al., 2008) was mixed with silver 4-bromobenzenesulfonate (Chantrapromma et al., 2006) (0.20 g, 0.58 mmol) in methanol (100 ml) and stirred for 0.5 h. The precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give the title compound as a yellow solid. Yellow block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from methanol by slow evaporation at room temperature over a few weeks (m.p. 463-465 K).