(E)-2-[4-(Dimethyl­amino)styr­yl]-1-methyl­quinolinium 4-methoxy­benzene­sulfonate monohydrate

Thawanrat Kobkeatthawin; Pumsak Ruanwas; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536808005205

. 2008 Feb 29;64(Pt 3):o642–o643. doi: 10.1107/S1600536808005205

(E)-2-[4-(Dimethylamino)styryl]-1-methylquinolinium 4-methoxybenzenesulfonate monohydrate¹

Thawanrat Kobkeatthawin ^a, Pumsak Ruanwas ^a, Suchada Chantrapromma ^a,^*, Hoong-Kun Fun ^b,^‡

PMCID: PMC2960777 PMID: 21201973

Abstract

In the title compound, C₂₀H₂₁N₂ ⁺·C₇H₇O₄S⁻·H₂O, the cation is nearly planar and exists in the E configuration. The cations and anions form individual chains along the b axis and are interconnected by weak C—H⋯O interactions. The 4-methoxybenzensulfonate anions are linked to water molecules through O—H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by a C—H⋯π interaction involving the methoxyphenyl ring. The sulfonate anion is also involved in a weak intramolecular C—H⋯O interaction which generates an S(5) ring motif.

Related literature

For bond lengths and angles, see: Allen (2002 ▶); Allen et al. (1987 ▶). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to NLO materials research, see: Chia et al., (1995 ▶); Otero et al., (2002 ▶). For related structures, see for example: Chantrapromma et al. (2006 ▶, 2007 ▶, 2007a ▶,b ▶); Jindawong et al. (2005 ▶); Dittrich et al. (2003 ▶); Nogi et al. (2000 ▶); Sato et al. (1999 ▶).

Experimental

Crystal data

C₂₀H₂₁N₂ ⁺·C₇H₇O₄S⁻·H₂O
M _r = 494.60
Monoclinic,
a = 14.6064 (5) Å
b = 10.4253 (4) Å
c = 19.5025 (6) Å
β = 126.737 (2)°
V = 2379.94 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100.0 (1) K
0.58 × 0.27 × 0.19 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.904, T _max = 0.967
33983 measured reflections
6953 independent reflections
5445 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.139
S = 1.06
6953 reflections
350 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.42 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/S1600536808005205/sj2466sup1.cif

e-64-0o642-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005205/sj2466Isup2.hkl

e-64-0o642-Isup2.hkl^{(340.3KB, 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—H1W⋯O2ⁱ	0.84	2.04	2.875 (3)	169
O1W—H2W⋯O4ⁱⁱ	0.85	2.10	2.926 (2)	161
C7—H7A⋯O3ⁱⁱⁱ	0.93	2.49	3.015 (3)	116
C8—H8A⋯O3ⁱⁱⁱ	0.93	2.57	3.049 (3)	113
C20—H20A⋯O4^iv	0.96	2.46	3.325 (2)	151
C23—H23A⋯O1W^v	0.93	2.44	3.365 (2)	176
C26—H26A⋯O4	0.93	2.56	2.921 (2)	104
C27—H27A⋯O1W^vi	0.96	2.58	3.160 (3)	119
C27—H27A⋯O1^vii	0.96	2.55	3.282 (2)	133
C16—H16A⋯Cg1^iv	0.93	2.81	3.6513 (19)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) . Cg1 is the centroid of the C21–C26 methoxyphenyl ring.

Acknowledgments

The authors thank Prince of Songkla University for financial support. The authors also thank the Malaysian Government and Universiti Sains Malaysia for Scientific Advancement Grant Allocation (SAGA) No. 304/PFIZIK/653003/A118.

supplementary crystallographic information

Comment

A lot of research have been done to search for second-order nonlinear optic (NLO) materials. Organic crystals with the required conjugated π electrons are attractive candidates because of their large NLO coefficients (Chia et al., 1995; Dittrich et al., 2003; Otero et al., 2002; Nogi et al., 2000; Sato et al., 1999). In our research on this kind of materials, we have previously synthesized and crystallized several organic ionic salts of quinolinium derivatives to study their non-linear optical properties (Chantrapromma et al., 2006; 2007a,b; 2007; Jindawong et al., 2005). Previous studies (Dittrich et al., 2003; Nogi et al., 2000; Sato et al., 1999) have shown that the 1-methyl-4-(2-(4-(dimethylamino)phenyl)ethynyl)pyridinium p-toluenesulfonate (DAST) and its analogues exhibit second-order non-linear optical properties. Based on these previous studies, we have synthesized the title compound which was designed to increase the π-conjugation in the system with the replacement of the cationic 4-hydroxy-3-methoxyphenyl ring that is present in 2-[(E)-(4-Hydroxy-3-methoxyphenyl)ethenyl]-1-methylquinolinium 4-methoxybenzenesulfonate (Chantrapromma et al., 2007a) by the 4-dimethylaminophenyl ring. The synthesis and crystal structure of the title compound, (I), Fig 1, are reported in this study. Unfortunately this crystal does not have second-order NLO properties because it crystallized out in a centrosymmetric space group.

The asymmetric unit of the title compound consists of the C₂₀H₂₁N₂⁺ cation, C₇H₇O₄S^- anion and one H₂O molecule. The cation exists in the E configuration with respect to the C10?C11 double bond [1.350 (2) Å] and is nearly planar as indicated by the dihedral angle between the quinolinium and the dimethylaminophenyl rings being 3.41 (7)° and the torsion angles C8–C9–C10–C11 = -8.7 (2)° and C10–C11–C12–C17 = 3.2 (3)°. The relative arrangement of cation and anion is shown by the angles between the mean plane of the methoxyphenyl ring and those of the quinolinium and dimethylaminophenyl systems which are 81.29 (7)° and 78.29 (8)°, respectively.

The atom O4 of the sulfonate contributes to a weak intramolecular C—H···O interaction (Fig. 1 and Table 1) forming an S(5) ring motif (Bernstein et al., 1995). The bond lengths and angles are normal (Allen et al., 1987) and are comparable with closely related structures (Chantrapromma et al., 2006; 2007a; 2007b; 2007c).

In the crystal packing, the O2 and O4 atoms of 4-methoxybenzenesulfonate anion are involved in the O—H···O hydrogen bonds whereas O3 and O4 atoms are involved in weak C—H···O interactions (Table 1). The cations and anions form individual chains along the b axis and are interconnected by weak C—H···O interactions. The 4-methoxybenzensulfonate anions are linked to water molecules through O—H···O hydrogen bonds forming a three dimensional network (Fig. 2). The crystal structure is further stabilized by a C16—H16A···π interaction to the methoxyphenyl ring [C21–C26]: C16—H16A=0.93; H16A···Cgⁱ=2.8096; C16—Cg₁ⁱ=3.6513 (19) Å; C16—H16A···Cg₁ⁱ= 151°. [Cg₁ⁱ is the centroid of the C21–C26 methoxyphenyl ring (symmetry code: (i): 1 - x, 1 - y, 1 - z).]

Experimental

2-(4-dimethylaminostyryl)-1-methylquinolinium iodide (compound A) was synthesized by mixing a solution (1:1:1 molar ratio) of 1,2-dimethylquinolinium iodide (2.00 g, 7.01 mmol), dimethylaminobenzaldehyde (1.05 g, 7.01 mmol) and piperidine (0.70 g, 7.01 mmol) in hot methanol (50 ml). The resulting solution was refluxed for 6 h under a nitrogen atmosphere. The resultant solid was filtered off, washed with methanol and recrystallized from methanol to give green crystals of compound A. Silver(I) 4-methoxybenzenesulfonate (compound B) was synthesized according to our previously reported procedure (Chantrapromma et al., 2007a). The title compound was synthesized by mixing compound A (0.2 g, 0.48 mmol) in hot methanol (50 ml) and compound B (0.14 g, 0.48 mmol) in hot methanol (20 ml). The mixture immediately yielded a grey precipitate of silver iodide. After stirring the mixture for ca 30 min, the precipitate was removed and the resulting solution was evaporated yielding a brown solid. Brown block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from methanol/ethanol solvent (3:1 v/v) by slow evaporation of the solvent at room temperature after a few weeks. (Mp. 545–547 K).