1,1′-Dimethyl-4,4′-[(2,4-diphenyl­cyclo­butane-1,3-di­yl)dipyridinium–(E)-1-methyl-4-styrylpyridinium–benzene­sulfonate (0.15/1.70/2)

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

doi:10.1107/S1600536809034588

. 2009 Sep 5;65(Pt 10):o2346–o2347. doi: 10.1107/S1600536809034588

1,1′-Dimethyl-4,4′-[(2,4-diphenylcyclobutane-1,3-diyl)dipyridinium–(E)-1-methyl-4-styrylpyridinium–benzenesulfonate (0.15/1.70/2)

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

PMCID: PMC2970487 PMID: 21577816

Abstract

In the title compound, 1.70C₁₄H₁₄N⁺·0.15C₂₈H₂₈N₂ ²⁺·2C₆H₅O₃S⁻, the monocation exists in the E configuration with respect to the ethenyl C=C double bond and is close to planar, the dihedral angle between the pyridinium and phenyl ring being 5.20 (13)°. The dication lies about an inversion centre. In the crystal, the dication occupies almost the same site occupied by monocations at (x, y, z) and (2 − x, 1 − y, 1 − z). The O atoms of the anion are disordered over two positions with occupancies of 0.75 and 0.25. In the crystal, the cations are stacked in an antiparallel manner along the a axis, whereas the anions are linked into chains along the same direction by C—H⋯O hydrogen bonds. In addition, C—H⋯π and π–π interactions [centroid–centroid distance = 3.593 (9) or 3.6705 (16) Å] are observed.

Related literature

The title compound was synthesized in as part of our search for non-linear optical materials. For background to non-linear optical materials, see: Lin et al. (2002 ▶). For related structures, see: Chanawanno et al. (2008 ▶); Chantrapromma et al. (2009a ▶,b ▶); Fun et al. (2009a ▶,b ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

1.70C₁₄H₁₄N⁺·0.15C₂₈H₂₈N₂ ²⁺·2C₆H₅O₃S⁻
M _r = 353.43
Triclinic,
a = 8.4037 (1) Å
b = 9.8505 (1) Å
c = 11.0869 (1) Å
α = 68.677 (1)°
β = 88.968 (1)°
γ = 86.134 (1)°
V = 852.99 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.36 × 0.19 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.930, T _max = 0.982
19913 measured reflections
4962 independent reflections
4045 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.120
S = 1.03
4962 reflections
387 parameters
165 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.46 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/S1600536809034588/ci2884sup1.cif

e-65-o2346-sup1.cif^{(27.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034588/ci2884Isup2.hkl

e-65-o2346-Isup2.hkl^{(243KB, 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
C4—H4⋯O3ⁱ	0.96	2.41	3.361 (2)	169
C10—H10⋯Cg1	0.96	2.72	3.617 (3)	157
C16—H16⋯Cg1ⁱⁱ	0.96	2.93	3.787 (3)	149
C20—H20B⋯Cg2ⁱⁱⁱ	0.96	2.86	3.588 (3)	134
C20—H20B⋯Cg3ⁱⁱⁱ	0.96	2.65	3.343 (7)	130
C10A—H10A⋯Cg1	0.96	2.70	3.537 (18)	146

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1, Cg2 and Cg3 are centroids of the C1–C6, C14–C19 and C14A–C19A rings, respectively.

Acknowledgments

The authors thank the Prince of Songkla University for financial support and the Malaysian Government 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

Recently, there is considerable interest in the synthesis of new materials with large second-order optical nonlinearities. Such materials require both molecular hyperpolarizability and orientation in a noncentrosymmetric arrangement (Lin et al., 2002). Taking advantage of our previous experience in the crystal growth of some pyridinium derivatives (Chanawanno et al., 2008; Chantrapromma et al., 2009a,b; Fun et al., 2009a,b), we report the synthesis and crystal structure of the title compound in which the dication is resulted from the unexpected [2+2] cycloaddition of the monocation. The title compound crystallizes in the centrosymmetric space group P1 and does not exhibit second-order nonlinear optical properties.

Fig. 1 shows the molecular structure of the title compound which consists of 1.70 of C₁₄H₁₄N⁺ cation, 0.15 of C₂₈H₂₈N₂²⁺ dication and two C₆H₅O₃S^- anions. The monocation exists in the E configuration with respect to the C12═C13 double bond (C11—C12—C13—C14 = 179.2 (2)°) and is almost planar with the dihedral angle between pyridinium and C14–C19 phenyl ring being 5.20 (13)°. The dication lies on an inversion center. The dihedral angle between the pyridinium and C14A–C19A ring being 29.3 (7)°, with the C11A–C12A–C13A–C14A torsion angle being -122.2 (10)°. The O atoms of the anion are disordered over two positions with a site-occupancy ratio of 0.75:0.25. It is almost perpendicular to the monocation, with the dihedral angles between the mean plane through C1–C6 with N1/C7–C11 and C14–C19 being 87.56 (11) and 82.36 (12)°, respectively. Bond lengths are comparable with those in related structures (Chantrapromma et al., 2009a,b; Fun et al., 2009a,b).

In the crystal packing, the cations are stacked in an antiparallel manner along the a axis whereas the anions are linked into chains along the same direction by C—H···O hydrogen bonds. Weak C—H···π (Table 1) and π–π interactions [Cg4···Cg3^v = 3.593 (9) Å and Cg5···Cg2^v = 3.6705 (16) Å; symmetry code: (v) 2-x, 1-y, 1-z; Cg1, Cg2, Cg3, Cg4 and Cg5 are centroids of the C1–C6, C14–C19, C14A-C19A, N1A/C7A–C11A and N1/C7–C11 rings, respectively] are also observed.

Experimental

Silver(I) benzenesulfonate (compound A) was prepared by mixing a solution of benzenesulfonic acid (1.34 g, 8.5 mmol) in hot methanol (50 ml) with a solution of sodium hydroxide (0.34 g, 8.5 mmol) in methanol (30 ml), followed by addition of a solution of silver nitrate (1.44 g, 8.5 mmol) in methanol (30 ml). A colourless solution together with black solid of AgI was obtained which was then filtered. The colorless solid of compound A was collected after allowing the filtrate to stand in air for a few days. (E)-1-Methyl-4-styrylpyridinium iodide (compound B) was prepared by mixing 1:1:1 molar ratio solutions of 1,4-dimethylpyridinium iodide (2 g, 8.5 mmol), benzaldehyde (0.86 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 yellow solid compound formed was filtered and washed with diethylether. The title compound was prepared by mixing the solution of compound A (2.24 g, 8.5 mmol) in methanol (100 ml) and compound B (2.75 g, 8.5 mmol) in methanol (100 ml) and stirred for 30 minutes. The precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give a pale orange solid product. The pale orange solid was repeatedly recrystallized for several times by dissolving the solid in hot methanol (around 323 K) to get a clear solution. The [2+2] cycloaddition of the (E)-1-methyl-4-styrylpyridinium occurred upon heating. Pale 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 few weeks (m.p. 493-495 K).