(E)-1-Methyl-4-[2-(1-naphth­yl)vin­yl]pyridinium 4-bromo­benzene­sulfonate

Suchada Chantrapromma; Kullapa Chanawanno; Hoong-Kun Fun

doi:10.1107/S1600536809014974

. 2009 Apr 30;65(Pt 5):o1144–o1145. doi: 10.1107/S1600536809014974

(E)-1-Methyl-4-[2-(1-naphthyl)vinyl]pyridinium 4-bromobenzenesulfonate¹

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

PMCID: PMC2977813 PMID: 21583950

Abstract

In the title compound, C₁₈H₁₆N⁺·C₆H₄BrO₃S⁻, the cation exists in the E configuration and the whole molecule of the cation is disordered with a refined site-occupancy ratio of 0.733 (1):0.267 (1). The naphthalene system is not planar, the interplanar angle between the two aromatic rings being 5.0 (5)° for the major component and 5.7 (10)° for the minor component. The cation is twisted with dihedral angles between the pyridinium ring and the two aromatic rings of the naphthalene system of 56.3 (5) and 51.4 (5)° (for the major component) and 52.2 (11) and 53.4 (11)° (for the minor component). The pyridinium ring and the benzene ring of the anion are inclined to each other at interplanar angles of 85.0 (4) and 71.5 (9)° for the major and minor components, respectively. In the crystal packing, the cations and anions are alternately arranged with the cations stacked in an antiparallel manner along the c axis and the anions linked together into chains along the same direction. The cations are linked to the anions into chains along [102] by weak C—H⋯O interactions. The crystal structure is further stabilized by C—H⋯π interactions and π–π contacts, with Cg⋯Cg distances of 3.502 (9) and 3.698 (6) Å. A short Br⋯O contact [3.029 (4) Å] is also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to NLO materials research, see: Cheng et al. (1991a ▶; 1991b ▶); Dittrich et al. (2003 ▶); Ogawa et al. (2008 ▶); Weir et al. (2003 ▶); Yang et al. (2007 ▶). For related structures, see, Chanawanno et al. (2008 ▶) and Chantrapromma et al. (2006 ▶; 2007 ▶; 2008 ▶; 2009 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₁₈H₁₆N⁺·C₆H₄BrO₃S⁻
M _r = 482.38
Orthorhombic,
a = 12.2195 (2) Å
b = 21.9907 (4) Å
c = 7.6256 (1) Å
V = 2049.12 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.14 mm⁻¹
T = 100 K
0.46 × 0.15 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.437, T _max = 0.753
15171 measured reflections
5563 independent reflections
3975 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.107
S = 1.03
5563 reflections
326 parameters
11 restraints
H-atom parameters constrained
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.49 e Å⁻³
Absolute structure: Flack (1983 ▶), 2373 Friedel pairs
Flack parameter: −0.003 (11)

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/S1600536809014974/sj2603sup1.cif

e-65-o1144-sup1.cif^{(29.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014974/sj2603Isup2.hkl

e-65-o1144-Isup2.hkl^{(272.4KB, 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
C2A—H2AA⋯O1ⁱ	0.95	2.53	3.392 (11)	151
C5A—H5AA⋯O2ⁱⁱ	0.95	2.47	3.362 (10)	157
C11A—H11A⋯O1ⁱ	0.95	2.34	3.282 (10)	175
C14A—H14A⋯O2ⁱⁱⁱ	0.95	2.44	3.373 (7)	169
C16A—H16A⋯O3^iv	0.95	2.49	3.361 (11)	153
C17A—H17A⋯O1ⁱ	0.95	2.35	3.227 (14)	153
C18A—H18A⋯O3^iv	0.98	2.57	3.501 (8)	159
C19—H19A⋯O2	0.95	2.56	2.930 (5)	103
C20—H20A⋯O1^iv	0.95	2.34	3.252 (5)	161
C22—H22A⋯O3^v	0.95	2.51	3.274 (6)	137
C4A—H4AA⋯Cg2^vi	0.95	2.84	3.659 (14)	145
C7A—H7AA⋯Cg4^vii	0.95	2.88	3.657 (9)	140
C4B—H4BA⋯Cg2^vi	0.95	2.90	3.59 (2)	130

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) . Cg2 and Cg4 are the centroids of the C1A–C6A and C19–C24 rings, respectively.

Acknowledgments

KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a study grant. Partial financial support from the Graduate School, Prince of Songkla University is gratefully acknowledged. The authors also thank Prince of Songkla University for financial support through the Crystal Materials Research Unit and the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Nonlinear optics has been recognized for several decades as a promising field with important applications in the domain of opto-electronics and photonics. Hence, a variety of materials have been investigated for their nonlinear optical (NLO) properties. In order to obtain second-order NLO single crystals, the main requirements should be the choice of molecules with large hyperpolarizability (β) and the alignment of these molecules with optimal orientation into a noncentrosymmetric space group in the crystal. Organic crystals with extensive conjugated π systems with large hyperpolarizability which exhibit NLO properties have been reported (Dittrich et al., 2003; Ogawa et al., 2008; Weir et al., 2004; Yang et al., 2007). Styryl pyridinium derivatives are considered to be good conjugated π-systems (Cheng et al., 1991a, 1991b). We have previously synthesized and reported the crystal structures of several pyridinium salts (Chanawanno et al., 2008; Chantrapromma et al., 2006, 2007, 2008, 2009) in order to study their NLO properties. The title compound (I) was synthesized by introducing a naphthalenyl group into the cation in order to increase the extent of π-conjugation in the system. The title compound crystallizes in the orthorhombic non-centrosymmetric space group Pna2₁ therefore it should exhibit second-order nonlinear optical properties.

Fig. 1 shows the asymmetric unit of (I) which consists of a C₁₈H₁₆N⁺ cation and a C₆H₄BrO₃S^- anion. The whole molecule of the cation is disordered over two sites; the major component A and the minor component B (Fig. 1 ), with the refined site-occupancy ratio of 0.733 (1)/0.267 (1). The cation exists in the E configuration with respect to the C11═C12 double bond. The naphthalenyl moiety is not planar as indicated by the interplanar angle between the two aromatic C1–C6 and C1/C6–C10 rings being 5.0 (5)° (for the major component A) and 5.7 (10)° (for the minor component B). The cation is twisted with the dihedral angle between the pyridinium and the two aromatic C1–C6 and C1/C6–C10 rings being 56.3 (5)° and 51.4 (5)°, respectively (for the major component A); 52.2 (11)° and 53.4 (11)°, respectively (for the minor component B) and the torsion angles C19–C10–C11–C12 = -26.5 (14)° and C11–C12–C13–C17 = -9.3 (15)° for the major component A; whereas the corresponding values are -6(2)° and 4(3)° for the minor component B. The cation and anion are inclined to each other with interplanar angles of 85.0 (4)° and 71.5 (9)° respectively between the benzene ring and the pyridinium units of the major and minor disorder components. The bond lengths in (I) are in normal ranges (Allen et al., 1987) and comparable to those in related structures (Chanawanno et al., 2008; Chantrapromma et al., 2006, 2007, 2008, 2009).

In the crystal packing (Fig. 2), all O atoms of the sulfonate group are involved in weak C—H···O interactions (Table 1). The cations and anions are alternately arranged with the cations (both the major A and minor B components) stacked in an antiparallel manner along the c axis and the anions linked together into chains along the same direction. The cations are linked to the anions into chains along the [1 0 2] direction by weak C—H···O interactions (Table 1). The crystal structure is further stabilized by C—H···π interactions (Table 1). π–π interaction with the distances Cg₁···Cg₂ = 3.698 (6) Å and Cg₁···Cg₃ = 3.502 (9) Å are also observed (symmetry code for both Cg···Cg interactions: 1-x, 1-y,-1/2+z); Cg₁, Cg₂, Cg₃ and Cg₄ are the centroids of the N1A/C13A–C17A, C1A–C6A, C1B–C6B and C19–C24 rings, respectively. A short Br1···O3 [3.029 (4) Å] contact is also present.

Experimental

(E)-1-methyl-4-(2-(naphthalen-1-yl)vinyl)pyridinium iodide (compound A) was prepared by mixing solutions of 1,4-dimethylpyridinium iodide (2 g, 8.5 mmol), 1-naphthaldehyde (1.16 ml, 8.5 mmol) and piperidine 0.84 ml, 8.5 mmol) in methanol (40 ml). The resulting solution was refluxed for 3 h under a nitrogen atmosphere. The solid which formed was filtered and washed with chloroform. After purification, the yellow solid of compound A (0.22 g, 0.58 mmol) 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 was filtered and the filtrate was evaporated to give the title compound as a yellow solid. Yellow needle-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, Mp. 495-496 K.