(E)-1-Methyl-4-styrylpyridinium iodide monohydrate

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

doi:10.1107/S1600536809040446

. 2009 Oct 10;65(Pt 11):o2676–o2677. doi: 10.1107/S1600536809040446

(E)-1-Methyl-4-styrylpyridinium iodide monohydrate

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

PMCID: PMC2971221 PMID: 21578284

Abstract

In the title compound, C₁₄H₁₄N⁺·I⁻·H₂O, the cation is essentially planar, with a dihedral angle of 2.55 (7)° between the pyridinium and phenyl rings, and exists in an E configuration with respect to the ethenyl bond. In the crystal structure, the cations are stacked in an antiparallel manner along the a axis. The cation is linked to the water molecule by a weak C—H⋯O interaction, and the water molecule is further linked to the I⁻ ion by O—H⋯I hydrogen bonds. The crystal structure is consolidated by these interactions and is further stabilized by a π–π interaction between the pyridinium and phenyl rings with a centroid–centroid distance of 3.6850 (8) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Chemla & Zyss (1987 ▶); Chia et al. (1995 ▶); Dittrich et al. (2003 ▶); Lin et al. (2002 ▶); Prasad & Williams (1991 ▶). For related structures, see: Chanawanno et al. (2008 ▶); Chantrapromma, Jindawong & Fun (2007 ▶); Chantrapromma, Jindawong, Fun & Patil (2007 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₄H₁₄N⁺·I⁻·H₂O
M _r = 341.18
Monoclinic,
a = 7.3636 (1) Å
b = 10.5929 (1) Å
c = 18.2807 (2) Å
β = 106.770 (1)°
V = 1365.29 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.33 mm⁻¹
T = 100 K
0.32 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.524, T _max = 0.649
27548 measured reflections
6004 independent reflections
5307 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.058
S = 1.05
6004 reflections
163 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.32 e Å⁻³
Δρ_min = −0.56 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/S1600536809040446/is2467sup1.cif

e-65-o2676-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040446/is2467Isup2.hkl

e-65-o2676-Isup2.hkl^{(293.9KB, 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—H1W1⋯I1ⁱ	0.94 (3)	2.70 (3)	3.6458 (14)	177 (3)
O1W—H2W1⋯I1ⁱⁱ	0.93 (3)	2.66 (2)	3.5826 (12)	174 (2)
C14—H14A⋯O1Wⁱⁱ	0.96	2.52	3.3775 (19)	149

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank 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. The authors also thank the Prince of Songkla University for financial support.

supplementary crystallographic information

Comment

The design and synthesis of nonlinear optical (NLO) materials have been receiving much attention due to their numerous applications (Chemla & Zyss, 1987; Prasad & Williams, 1991). In the search for new organic NLO materials, aromatic compounds with extended π-conjugation system are extensively studied (Chia et al., 1995; Dittrich et al., 2003). Such materials require molecular hyperpolarizability and orientation in a noncentrosymmetric arrangement of the bulk material (Lin et al., 2002; Prasad & Williams, 1991). During the course of our systematic studies of organic NLO materials, we have previously synthesized and reported the crystal structures of pyridinium and quinolinium iodide (Chanawanno et al., 2008; Chantrapromma, Jindawong & Fun, 2007; Chantrapromma, Jindawong, Fun & Patil, 2007). Herein we report the crystal structure of the title pyridinium derivative (I). However (I) crystallizes in centrosymmetric P2₁/c space group which precludes the second-order nonlinear optical properties.

The title compound consists of a C₁₄H₁₄N⁺ cation, an I^- anion and one water molecule (Fig. 1). The cation exists in an E configuration with respect to the C6═C7 ethenyl bond [1.3429 (18) Å] with the torsion angle of C5–C6–C7–C8 = -179.95 (13)°. The cation is essentially planar with the dihedral angles between the pyridinium [C1–C5/N1] and benzene rings being 2.55 (7)°. The ethenyl unit is co-planar with the pyridinium and benzene rings as indicated by the torsion angles C1–C5–C6–C7 = -1.4 (2)° and C6–C7–C8–C9 = 1.6 (2)°. The rms deviation from the plane through the cation is 0.027 (15) Å. The bond distances in the cation have normal values (Allen et al., 1987) and comparable with the closely related compounds (Chanawanno et al., 2008; Chantrapromma, Jindawong & Fun, 2007; Chantrapromma, Jindawong, Fun & Patil, 2007).

In the crystal packing (Fig. 2), the cations are stacked in an antiparallel manner along the a axis. The cation is linked with the water molecule by a C—H···O weak interaction. The water molecule is further linked with the I^- ion by O—H···I hydrogen bonds, forming a 3D network (Table 1). The crystal is consolidated by these interactions and further stabilized by π–π interactions with a distance of Cg₁···Cg₂ⁱⁱⁱ = 3.6850 (8) Å [symmetry code: (iii) -x, 1-y, 2-z]; Cg₁ and Cg₂ are the centroids of the C1–C5/N1 and C8–C13 rings, respectively.

Experimental

(E)-1-Methyl-4-styrylpyridinium iodide 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 which formed was filtered and washed with diethylether. 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. 489-490 K).