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

Hoong Kun Fun; Suchada Chantrapromma; Patcharaporn Jansrisewangwong

doi:10.1107/S1600536810050944

. 2010 Dec 11;67(Pt 1):o105–o106. doi: 10.1107/S1600536810050944

(E)-4-[2-(4-Ethoxyphenyl)ethenyl]-1-methylpyridinium 4-bromobenzenesulfonate methanol hemisolvate¹

Hoong Kun Fun ^a,^*,^‡, Suchada Chantrapromma ^b,^§, Patcharaporn Jansrisewangwong ^b

PMCID: PMC3050231 PMID: 21522618

Abstract

In the title compound, C₁₆H₁₈NO⁺·C₆H₄BrO₃S⁻·0.5CH₃OH, the cation exists in the E configuration and the whole molecule of the cation, except for the O atom of the ethoxy group, is disordered with a site-occupancy ratio of 0.695 (5):0.305 (5). The cation is disordered in such a way that the ethenyl units of the major and minor components are related by 180° around the long molecular axis. In the major component, the cation is almost planar, the dihedral angle between the pyridinium and benzene rings being 0.8 (3)°, whereas in the minor component, the dihedral angle between the two aromatic rings is 4.2 (6)°. In the crystal, the cations are stacked in an antiparallel manner along the a axis, while the anions and methanol molecules are linked through O—H⋯O hydrogen bonds and Br⋯O short contacts [3.0248 (13) Å] into a tape along the same direction. The three components are further linked by weak C—H⋯O, C—H⋯Br and C—H⋯π interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Cheng, Tam, Marder et al. (1991 ▶); Cheng, Tam, Stevenson et al. (1991 ▶); Ogawa et al. (2008 ▶); Ruanwas et al. (2010 ▶); Yang et al. (2007 ▶). For related structures, see: Chantrapromma et al. (2006 ▶); Chantrapromma, Chanawanno & Fun (2009 ▶); Chantrapromma, Jansrisewangwong et al. (2009 ▶); Fun et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

2C₁₆H₁₈NO⁺·2C₆H₄BrO₃S⁻·CH₄O
M _r = 984.79
Triclinic,
a = 9.9270 (4) Å
b = 9.9813 (4) Å
c = 11.5293 (4) Å
α = 75.703 (2)°
β = 76.965 (2)°
γ = 88.395 (2)°
V = 1078.00 (7) Å³
Z = 1
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 100 K
0.58 × 0.41 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.383, T _max = 0.721
24757 measured reflections
6214 independent reflections
5389 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.086
S = 1.03
6214 reflections
354 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −0.54 e Å⁻³

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, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810050944/is2636sup1.cif

e-67-0o105-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050944/is2636Isup2.hkl

e-67-0o105-Isup2.hkl^{(304.1KB, hkl)}

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

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

Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of the N1A/C1A–C5A, C8A–C13A, N1B/C1B–C5B, C8B–C13B and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O3ⁱ	0.82	1.92	2.657 (4)	149
C1A—H1AA⋯O2ⁱⁱ	0.93	2.42	3.334 (4)	168
C2A—H2AA⋯O2ⁱⁱⁱ	0.93	2.38	3.237 (5)	153
C14A—H14A⋯O4^iv	0.96	2.36	3.180 (6)	143
C14A—H14B⋯O4ⁱⁱⁱ	0.96	2.41	3.343 (6)	163
C19—H19A⋯O5^v	0.93	2.53	3.385 (4)	153
C21—H21A⋯O2^vi	0.93	2.58	3.311 (2)	135
C23—H23C⋯Br1	0.96	2.77	3.724 (5)	173
C14A—H14C⋯Cg2ⁱⁱ	0.96	2.66	3.609 (6)	172
C14A—H14C⋯Cg4ⁱⁱ	0.96	2.63	3.572 (8)	167
C15A—H15A⋯Cg1^vii	0.97	2.84	3.639 (8)	140
C15A—H15A⋯Cg3^vii	0.97	2.84	3.611 (9)	137
C14B—H14D⋯Cg2ⁱⁱ	0.96	2.87	3.562 (15)	129
C14B—H14D⋯Cg4ⁱⁱ	0.96	2.80	3.564 (16)	137
C15B—H15C⋯Cg1^vii	0.97	2.81	3.65 (3)	145
C15B—H15C⋯Cg3^vii	0.97	2.81	3.62 (3)	141
C15B—H15D⋯Cg5^viii	0.97	2.98	3.60 (2)	123

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

Acknowledgments

The authors thank the Prince of Songkla University for a research grant. They also thank Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Organic crystals with extensive conjugated π systems with large hyperpolarizability which exhibit NLO properties have been reported (Ogawa et al., 2008; Ruanwas et al., 2010; Yang et al., 2007). Styryl pyridinium derivatives are considered to be good conjugated π-systems (Cheng, Tam, Marder et al., 1991; Cheng, Tam, Stevenson et al., 1991). In our on-going research in searching for NLO materials (Chantrapromma et al., 2006; Chantrapromma, Chanawanno & Fun, 2009; Chantrapromma, Jansrisewangwong et al., 2009; Ruanwas et al., 2010), the title compound (I) was synthesized. Unfortunately (I) crystallizes in the triclinic centrosymmetric space group P-1 and did not exhibit second-order nonlinear optical properties.

The asymmetric unit of (I) consists of one C₁₆H₁₈NO⁺ cation, one C₆H₄BrO₃S^- anion and one-half of the CH₃OH molecule. The whole molecule except the O atom of the ethoxy group (O1) of the cation is disordered over two sites with the major component A and the minor B components having refined site-occupancy ratio of 0.695 (5):0.305 (5) (Fig. 1). The cation exists in the E configuration with respect to the C6═C7 double bond and the torsion angle C5–C6–C7–C8 = -179.6 (2)° for major component A and 179.5 (6)° for minor component B indicating that the orientation of the ethenyl moiety in major and minor components is related by 180° rotation. In the major component A, the cation is planar with the dihedral angle between the pyridinium and benzene rings being 0.8 (3)°, whereas in the minor component B, the dihedral angle between the two aromatic rings is 4.2 (6)°. The anion is inclined to the cation with the dihedral angle between the C17–C22 benzene ring of the anion and the mean plane of the conjugated π system (C1–C13/N1) [r.m.s = 0.013 (2) and 0.033 (2) Å for major and minor components, respectively] of the cation being 79.73 (12) and 79.2 (2)° for major and minor components, respectively. The ethoxy group is co-planar with the attached benzene ring as indicated by the torsion angle C11A–O1–C15A–C16A = 178.8 (8)° for major component and C11B–O1–C15B–C16B = -175 (2)° for minor component. The bond lengths in (I) are in normal ranges (Allen et al., 1987) and comparable to those in related structures (Chantrapromma et al., 2006; Chantrapromma, Chanawanno & Fun, 2009; Chantrapromma, Jansrisewangwong et al., 2009; Fun et al., 2009).

In the crystal packing (Fig. 2), the cations and anions are individually arranged into chains along the a axis. The methanol molecules are linked to the anions by C—H···Br weak interactions and O—H···O hydrogen bonds, respectively (Table 1). The cations, anions and methanol molecules are linked together by O—H···O hydrogen bonds and C—H···O weak interactions forming sheets parallel to the bc plane. The crystal structure is further stabilized by C—H···π interactions (Table 1). A Br···O short contact [3.0248 (13) Å; symmetry code: 1 + x, y, z] was observed.

Experimental

(E)-4-(4-Ethoxystyryl)-1-methylpyridinium iodide (compound A) was prepared by mixing 1:1:1 molar ratio solutions of 1,4-dimethylpyridinium iodide (2.00 g, 8.5 mmol), 4-ethoxybenzaldehyde (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 and washed with diethylether to give oranged-yellow solid of compound A (2.18 g, 69%), M.p. 491-492 K. Silver (I) 4-bromobenzenesulfonate (compound B) was synthesized according to our previously reported procedure (Chantrapromma et al., 2006). The title compound was synthesized by mixing a solution of 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 yellow solid of the title compound. Yellow plate-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation of the solvent at room temperature over several days, M.p. 513-515 K.