Bis[(E)-1-methyl-4-styrylpyridinium] 4-bromo­benzene­sulfonate iodide

Chanasuk Surasit; Suchada Chantrapromma; Kullapa Chanawanno; Hoong-Kun Fun

doi:10.1107/S1600536810017277

. 2010 May 15;66(Pt 6):o1372–o1373. doi: 10.1107/S1600536810017277

Bis[(E)-1-methyl-4-styrylpyridinium] 4-bromobenzenesulfonate iodide

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

PMCID: PMC2979384 PMID: 21579454

Abstract

In the title compound, 2C₁₄H₁₄N⁺·C₆H₄BrO₃S⁻·I⁻, two crystallographically independent cations exist in an E configuration with respect to the C=C ethenyl bond. One cation is approximately planar, whereas the other is twisted slightly, the dihedral angles between the pyridinium and phenyl rings of each cation being 0.96 (15) and 7.05 (16)°. In the crystal structure, the cations are stacked in an antiparallel manner along the a axis through weak C—H⋯π interactions and π–π interactions, with centroid–centroid distances of 3.5544 (19) and 3.699 (2) Å. The 4-bromobenzenesulfonate anions and the cations are linked together by weak C—H⋯O interactions. A short Br⋯I contact [3.6373 (4) Å] and C—H⋯I interactions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Chia et al. (1995 ▶); Pan et al. (1996 ▶); Prasad & Williams (1991 ▶). For related structures, see: Chantrapromma et al. (2006 ▶); Fun, Chanawanno & Chantrapromma (2009a ▶,b ▶): Fun, Surasit et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

2C₁₄H₁₄N⁺·C₆H₄BrO₃S⁻·I⁻
M _r = 755.49
Monoclinic,
a = 7.7766 (2) Å
b = 32.2737 (9) Å
c = 12.8009 (4) Å
β = 96.097 (2)°
V = 3194.59 (16) Å³
Z = 4
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 100 K
0.50 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.383, T _max = 0.889
42790 measured reflections
9275 independent reflections
7161 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.089
S = 1.03
9275 reflections
381 parameters
H-atom parameters constrained
Δρ_max = 1.96 e Å⁻³
Δρ_min = −1.13 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/S1600536810017277/is2540sup1.cif

e-66-o1372-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017277/is2540Isup2.hkl

e-66-o1372-Isup2.hkl^{(453.6KB, hkl)}

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

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

Cg2 and Cg4 are the centroids of the C8A–C13A and C8B–C13B phenyl rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2A—H2AA⋯O2ⁱ	0.93	2.45	3.253 (3)	144
C3A—H3AA⋯O1	0.93	2.47	3.189 (3)	134
C2B—H2BA⋯O2ⁱⁱ	0.93	2.24	3.169 (4)	177
C4B—H4BA⋯O3	0.93	2.49	3.328 (4)	151
C11A—H11A⋯O1ⁱⁱⁱ	0.93	2.51	3.390 (4)	159
C7B—H7BA⋯O3	0.93	2.50	3.314 (4)	146
C14A—H14C⋯O1	0.96	2.44	3.171 (4)	133
C14B—H14D⋯O3ⁱⁱ	0.96	2.46	3.365 (4)	157
C1A—H1AA⋯I1ⁱ	0.93	3.26	3.841 (3)	123
C1B—H1BA⋯I1ⁱⁱ	0.93	3.35	3.787 (3)	111
C17—H17A⋯I1^iv	0.93	3.10	3.863 (3)	141
C14A—H14A⋯Cg2^v	0.96	2.72	3.475 (3)	136
C14B—H14E⋯Cg4^vi	0.96	2.73	3.520 (3)	140

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

Acknowledgments

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

supplementary crystallographic information

Comment

Organic molecules are promising candidates for the nonlinear optical (NLO) applications. Stilbene derivatives, especially the pyridinium stilbenes with Donor-π-Acceptor system, were recognized as a good organic NLO chromophore (Chia et al., 1995; Pan et al., 1996). We previously reported the systhesis and crystal structure of bis[(E)-1-methyl-4-styrylpyridinium] 4-chlorobenzenesulfonate iodide (I), a pyridinium stilbene derivative, which crystallizes in noncentrosymmetric P2₁ space group and exhibits second-order NLO properties (Fun et al., 2009; Prasad & Williams, 1991). In this work, the title compound (II) was synthesized by changing the 4-chlorobenzenesulfonate anionic part in (I) to the 4-bromobenzenesulfonate to study the different NLO properties. By changing this, it was found that the title compound (II) crystallizes in centrosymmetric P2₁/c space group and does not show second-order NLO properties.

The title molecule consists of two C₁₄H₁₄N⁺(A and B), one C₆H₄BrO₃S^- and one I^- ions (Fig. 1), the two cations exist in an E configuration with respect to the C6═C7 ethenyl bond with the torsion angle of C6–C7–C8–C9 = 179.9 (3)° in molecule A [178.5 (3)° in molecule B]. One cation [molecule A] is planar while the other [molecule B] is slightly twisted, with the dihedral angles between the pyridinium and phenyl rings of the cation being 0.96 (15) and 7.05 (16)°, respectively. The two cations lie nearly on the same plane but in anti-parallel fashion with the dihedral angle between the planes through the whole molecule of cations being 4.01 (8)°. The anion is equally inclined with respect to the cations with the dihedral angles between the benzene ring of the anion and the pyridinium rings of the two cations being 82.20 (14) [molecule A] and 82.19 (15)° [molecule B], respectively. The bond distances in both cations and anion have normal values (Allen et al., 1987) and comparable with the closely related compounds (Fun et al., 2009a,b; Fun et al., 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 are stacked in an antiparallel manner along the a axis. The anions and I^- ions are located in interstitial spaces between the cations, and the ions linked together through weak C—H···O, C—H···I and C—H···π interactions (Table 1) forming a 3D network. The crystal structure is further stabilized by π–π interactions with the distances of Cg₁···Cg₂^vi = 3.5544 (19) Å and Cg₃···Cg₄^{ii, vii} = 3.699 (2) Å [(vi) = 2-x, -y, 2-z; (vii) = x, 1/2-y, =1/2+z; Cg₁, Cg₂, Cg₃ and Cg₄ are the centroids of C1A–C5A/N1A, C8A–C13A, C1B–C5B/N1B and C8B–C13B, respectively]. In addition the crystal structure also shows short C···O [3.169 (4)–3.365 (4) Å] and Br···I [3.6373 (4) Å] contacts.

Experimental

(E)-1-methyl-4-styrylpyridinium iodide (compound A, 0.19 g, 0.58 mmol) which was prepared according the previous method (Fun et al., 2009) was mixed with silver (I) 4-bromobenzenesulfonate (0.20 g, 0.58 mmol) (Chantrapromma et al., 2006) in methanol solution and stirred for 30 minutes. The precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give the title compound as an orange solid. Orange 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 week (m.p. 472–473 K).