4-(3-Eth­oxy-4-hydroxy­styr­yl)-1-methyl­pyridinium tosyl­ate monohydrate

S Murugavel; A SubbiahPandi; C Srikanth; S Kalainathan

doi:10.1107/S1600536808041007

. 2008 Dec 10;65(Pt 1):o71. doi: 10.1107/S1600536808041007

4-(3-Ethoxy-4-hydroxystyryl)-1-methylpyridinium tosylate monohydrate

S Murugavel ^a, A SubbiahPandi ^b,^*, C Srikanth ^c, S Kalainathan ^c

PMCID: PMC2967981 PMID: 21581710

Abstract

In the title compound, C₁₆H₁₈NO₂ ⁺·C₇H₇O₃S⁻·H₂O, the dihedral angle between the pyridyl and benzene rings of the pyridinium cation is 0.2 (1)°. The benzene ring of the tosylate anion makes a dihedral angle of 4.8 (2)° with the best mean plane of the pyridinium cation. The pyridinium cation and the tosylate anion are hydrogen bonded to the water molecule, and the crystal packing is further stabilized by intermolecular C—H⋯O and π–π interactions [centroid–centroid separations of 3.648 (3) and 3.594 (2) Å.

Related literature

For a related structure, see: Zhang et al. (1997 ▶). For molecular compounds with non-linear optical properties, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶); Lee & Kim (1999 ▶).

Experimental

Crystal data

C₁₆H₁₈NO₂ ⁺·C₇H₇O₃S⁻·H₂O
M _r = 445.52
Monoclinic,
a = 13.7700 (4) Å
b = 9.7125 (2) Å
c = 17.3394 (5) Å
β = 104.059 (2)°
V = 2249.53 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 (2) K
0.25 × 0.17 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.961, T _max = 0.975
48719 measured reflections
5310 independent reflections
3610 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.187
S = 1.03
5310 reflections
290 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041007/lx2079sup1.cif

e-65-00o71-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041007/lx2079Isup2.hkl

e-65-00o71-Isup2.hkl^{(260KB, 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
O1—H1O⋯O6ⁱ	0.82	1.82	2.632 (3)	170
O6—H6OB⋯O3	0.85 (1)	2.36 (2)	2.692 (3)	103.9 (19)
O6—H6OA⋯O5ⁱⁱ	0.86 (3)	1.98 (3)	2.832 (4)	169 (3)
C4—H4⋯O4	0.93	2.53	3.426 (3)	161
C5—H5⋯O1ⁱⁱⁱ	0.93	2.59	3.217 (3)	125

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

Acknowledgments

SM and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray data collection.

supplementary crystallographic information

Comment

The synthesis and study of molecular compounds with non linear optical (NLO) properties has attracted much attention, because such materials hold promise for applications in optoelectronic and photonic devices (Bosshard et al., 1995; Nalwa & Miyata, 1997). In order to create efficient quadratic (second–order) NLO materials, both the molecular and bulk properties must be optimized. Within the diverse range of existing NLO compounds, styrylpyridinium salts are particularly attractive for device applications (Lee & Kim, 1999). Against this background, and in order to obtain detailed information on molecular conformations in the solid state, X-ray studies of the title compounds (I) have been carried out.

X-Ray analysis confirms the molecular structure and atom connectivity for (I), as illustrated in Fig. 1. The dihedral angle between the pyridyl and phenyl rings of the pyridinium cation is 0.2 (1)°. The benzene ring of the tosylate anion makes a dihedral angle of 4.8 (2)° with the best mean plane of the pyridinium cation. The bond lengths N1–C7, C13–O25 and C14–O26 are normal and comparable with the corresponding values observed in the related structure. (Zhang et al., 1997)

The presence of water molecules in the crystal structure of (I) leads to a three dimensional network of hydrogen bonds invoving water, the tosylate anion and the pyridinium cation (Table 1). In addition, the crystal packing is further stabilized by intermolecular C—H···O (Table.1) and π—π interactions with a Cg1···Cg1ⁱ and a Cg1—Cg2ⁱⁱ separation of 3.648 (3) Å and 3.594 Å, respectively (Fig. 2; Cg1 and Cg2 are the centroids of the N/C1-C5 pyridine ring and C17-C22 benzene ring, respectively, symmetry code as in Fig. 2).

Experimental

HEST (4-[2-(4-hydroxy-3-ethoxyphenyl) ethenyl]-1-methylpyridinium 4-tolylsulfonate hydrate ) was synthesized by the condensation of 4-methyl N-methyl pyridinum Tosylate, which is prepared from 4-Picoline (Merck, 99%) , methyl toluene sulphonate (Merck, 98%) and 4-hydroxy-3-ethoxy-Benzaldehyde (High Media, 98%) in the presence of piperidine as catalyst. The step by step synthesis procedure of HEST is as follows: Picoline (10.31 ml, 0.105 mol %) and methyl toluene sulphonate (15.88 ml, 0.105 mol %) is added into toluene (200ml) (Merck, 98%) is taken in a round bottom flask (500 ml) of Dean-stark apparatus. This mixture is heated until formation of white salt, which is insoluble in toluene. While boiling Di-methyl formamide (DMF) (Merck, 98%) is added until the white salt are dissolved. Now 4-hydroxy-3-ethoxy-Benzaldehyde (0.105 mol %) is added. Few drops of Piperidine also added as catalyst. The mixture is then refluxed with Dean-stark trap to remove water. After more than equivalent amount of water is collected, the reactants are cooled to room temperature and synthesized orange color HEST is collected. To prevent the absorption of water from the atmosphere, the synthesized material is placed in the oven at 100°C for 1 hour. Purified single crystals suitable for X-ray diffraction was obtained by successive recrystallization process of a methonal solution.