2-[(E)-2-(4-Chloro­phen­yl)ethen­yl]-1-methylpyridinium iodide monohydrate

Kullapa Chanawanno; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536808027724

. 2008 Sep 6;64(Pt 10):o1882–o1883. doi: 10.1107/S1600536808027724

2-[(E)-2-(4-Chlorophenyl)ethenyl]-1-methylpyridinium iodide monohydrate¹

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

PMCID: PMC2959251 PMID: 21201095

Abstract

In the title compound, C₁₄H₁₃ClN⁺·I⁻·H₂O, the cation is nearly planar and exists in an E configuration; the dihedral angle between the pyridinium and benzene rings is 0.98 (17)°. The cations stack in an anti-parallel manner along the a axis through two π–π interactions between the pyridinium and benzene rings [centroid–centroid distances 3.569 (2) and 3.6818 (13) Å, respectively]. The cation, anion and water molecule are linked into a chain along the a axis by weak C—H⋯O and C—H⋯I interactions together with O—H⋯I hydrogen bonds and the chains are further connected into a three-dimensional network.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related structures, see, for example: Chantrapromma et al. (2007a ▶,b ▶,c ▶). For background on non-linear optical properties, see, for example: Lakshmanaperumal et al. (2004 ▶); Marder et al. (1994 ▶); Qiu et al. (2007 ▶); Williams (1984 ▶); Zhai et al. (1999 ▶); Zhan et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₃ClN⁺·I⁻·H₂O
M _r = 375.62
Monoclinic,
a = 7.0876 (1) Å
b = 9.8096 (2) Å
c = 21.0940 (4) Å
β = 95.147 (1)°
V = 1460.68 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 100.0 (1) K
0.28 × 0.17 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.560, T _max = 0.845
18928 measured reflections
4241 independent reflections
3486 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.13
4241 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 2.13 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027724/is2329sup1.cif

e-64-o1882-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027724/is2329Isup2.hkl

e-64-o1882-Isup2.hkl^{(207.8KB, 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⋯I1	0.86	2.87	3.592 (4)	143
O1W—H2W1⋯I1ⁱ	0.85	2.87	3.567 (4)	141
C14—H14A⋯O1W	0.96	2.50	3.202 (5)	130
C14—H14D⋯O1Wⁱⁱ	0.96	2.56	3.460 (5)	157
C1—H1A⋯I1ⁱⁱⁱ	0.93	3.20	3.830 (4)	127
C2—H2A⋯I1^iv	0.93	3.17	3.825 (4)	129
C3—H3A⋯I1^iv	0.93	3.21	3.840 (4)	127

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

Acknowledgments

KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a study grant. Financial support from the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Commission on Higher Education, Ministry of Education, is gratefully acknowledged. The authors also thank Prince of Songkla University, the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

In the last two decades, many efforts were focused on the discovery of new organic materials which exhibit large nonlinear optical (NLO) properties and would have applications in the fields of optoelectronics and photonics (Lakshmanaperumal et al., 2004; Marder et al., 1994; Qiu et al., 2007; Zhai et al., 1999; Zhan et al., 2006). 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 (Williams, 1984). Among the known organic NLO materials, ionic chromophores are of great interest because they exhibit large first hyperpolarizabilities (β) and have high melting points and hardness of their crystals. At the molecular level, a generally popular approach towards NLO materials is to design and synthesize compounds with extended conjugated π-systems with donor and acceptor groups because such compounds are likely to exhibit large values of molecular hyperpolarizability (β) and to possess polarization. Styryl pyridinium derivatives are considered to be good conjugated π-systems. In continuation of our on-going research on nonlinear optical materials (Chantrapromma et al., 2007a,b,c), the title compound, (I), was synthesized and the X-ray structure analysis was carried out in order to obtain detailed information about the molecular packing. However, compound (I) crystallizes in monoclinic space group P2₁/c and doesn't exhibit second-order nonlinear optic properties.

The asymmetric unit of the title compound consists of C₁₄H₁₃ClN⁺ cation, I^- anion and one water molecule (Fig. 1). The conformation of the cation is essentially planar as indicated by the dihedral angle between the pyridinium (N1/C1—C5) and the benzene (C8—C13) rings, being 0.98 (17)°. The mean plane through C5/C6/C7/C8 plane makes dihedral angles of 6.1 (4)° and 6.4 (4)° with pyridinium and benzene rings, respectively. The cation exists in the E configuration and the torsion angle C5—C6—C7—C8 = -179.2 (3)°. The bond distances and angles in (I) have normal values (Allen et al., 1987) and comparable with closely related structures (Chantrapromma et al., 2007a,b,c).

The packing of the molecule down the c axis (Fig. 2), showing that the cation is linked with water molecule by weak C—H···O interactions (Table 1) and linked with I^- anions by weak C—H···I interactions (Table 1) whereas the I^- anion is linked with water molecule by O—H···I hydrogen bonds, forming one-dimensional chains along the a axis. These chains are further connected into a three-dimensional network (Fig. 2). π···π interactions involving pyridinium and benzene rings were also observed with Cg₁···Cg₂ distances of 3.662 (2) Å (symmetry code; 1 - x, -y, 1 - z) and 3.569 (2) Å (symmetry code; 2 - x, -y, 1 - z); Cg₁ and Cg₂ are the centroids of the N1/C1–C5 pyridinium and C8–C13 benzene rings, respectively. The crystal is stabilized by O—H···I hydrogen bond, weak C—H···O and C—H···I interactions.

Experimental

The title compound was prepared by mixing solutions of 1,2-dimethylpyridinium iodide, 4-chlorobenzaldehyde and piperidine (1:1:1 molar ratio) in methanol. The resulting solution was refluxed for 12 hr under a nitrogen atmosphere. The solid which formed was filtered and washed with chloroform. Orange plate-like single-crystal suitable for X-ray diffraction analysis was obtained by recrystallization from methanol by slow evaporation of the solvent at ambient temperature after several days, Mp. 492–493 K.