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

Thawanrat Kobkeatthawin; Thitipone Suwunwong; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536808040671

. 2008 Dec 10;65(Pt 1):o76–o77. doi: 10.1107/S1600536808040671

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

Thawanrat Kobkeatthawin ^a, Thitipone Suwunwong ^a, Suchada Chantrapromma ^a,^*, Hoong-Kun Fun ^b,^‡

PMCID: PMC2967986 PMID: 21581715

Abstract

In the title compound, C₂₀H₂₁N₂ ⁺·C₇H₇O₃S⁻·H₂O, the cation is essentially planar, as indicated by the dihedral angle of 2.79 (13)° between the quinolinium and the dimethylaminophenyl rings, and exists in the E configuration. The π-conjugated planes of the cation and the anion are inclined to each other at a dihedral angle of 66.95 (12)°. The cation is linked to the anion through C—H⋯O hydrogen bonds and the anion is further linked with the water molecule by O—H⋯O hydrogen bonds, forming a three-molecule unit. These units are arranged in a face-to-face manner into a ribbon-like structure along the b axis. The ribbons are stacked along the c axis. The crystal structure is further stabilized by C—H⋯π interactions involving the dimethylaminophenyl and methylphenyl rings. A π–π interaction with a centroid–centroid distance of 3.6074 (19) Å is also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to NLO materials research, see: Dittrich et al. (2003 ▶); Nogi et al. (2000 ▶); Ogawa et al. (2008 ▶); Otero et al. (2002 ▶); Sato et al. (1999 ▶); Weir et al. (2003 ▶); Yang et al. (2007 ▶). For related structures, see, for example: Adachi et al. (1999 ▶); Chantrapromma et al. (2008 ▶); Ogawa et al. (2008 ▶); Rahman et al. (2003 ▶).

Experimental

Crystal data

C₂₀H₂₁N₂ ⁺·C₇H₇O₃S⁻·H₂O
M _r = 478.60
Triclinic,
a = 10.9739 (5) Å
b = 11.1789 (5) Å
c = 11.1923 (9) Å
α = 97.133 (5)°
β = 100.322 (5)°
γ = 117.021 (3)°
V = 1169.78 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100.0 (1) K
0.24 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.958, T _max = 0.986
17557 measured reflections
5390 independent reflections
3272 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.203
S = 1.05
5390 reflections
311 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.47 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040671/is2369sup1.cif

e-65-00o76-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040671/is2369Isup2.hkl

e-65-00o76-Isup2.hkl^{(263.9KB, 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—H1W⋯O2	0.90	1.96	2.839 (4)	164
O1W—H2W⋯O1ⁱ	0.88	2.01	2.893 (3)	179
C10—H10A⋯O3ⁱⁱ	0.93	2.57	3.460 (4)	162
C17—H17A⋯O3ⁱⁱ	0.93	2.45	3.344 (5)	163
C20—H20A⋯O3ⁱⁱ	0.96	2.33	3.204 (6)	151
C20—H20B⋯O1ⁱⁱⁱ	0.96	2.49	3.388 (4)	156
C26—H26A⋯O2	0.93	2.51	2.884 (5)	104
C7—H7A⋯Cg4^iv	0.93	2.97	3.615 (4)	128
C23—H23A⋯Cg3^v	0.93	2.82	3.594 (4)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg3 and Cg4 are the centroids of the C12–C17 and C21–C26 rings, respectively.

Acknowledgments

The authors thank the Prince of Songkla University for a research grant and also Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

There has been considerable interest in organic nonlinear optical materials that could be used for applications including telecommunications, optical computing and optical data storage. Organic crystals with extensive conjugated π systems are attractive candidates for nonlinear optic (NLO) studies because of their large hyperpolariability (β) and ease of preparation (Dittrich et al., 2003; Nogi et al., 2000; Ogawa et al., 2008; Otero et al., 2002; Sato et al., 1999; Weir et al., 2003; Yang et al., 2007). 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) is one of the promising NLO material (Adachi et al., 1999). Previous studies (Dittrich et al., 2003; Nogi et al., 2000; Sato et al., 1999) have shown that the DAST and its analogues exhibit second-order non-linear optical properties. One strategy to enhance the hyperpolariability of the cations is by elongation of its π-conjugation system. Based on these previous studies, we have synthesized the title compound which was designed by increasing the π-conjugate system with the replacement of the cationic pyridinium ring that is present in DAST by the quinolinium ring. The crystal structure of the title compound is reported in this study.

Figure 1 shows the asymmetric unit of the title compound (I) which consists of a C₂₀H₂₁N₂⁺ cation, a C₇H₇O₃S^- anion and one H₂O molecule. The cation exists in the E configuration with respect to the C10═C11 double bond [1.328 (4) Å, the corresponding value is 1.357 (2) Å in Chantrapromma et al., 2008]. The cation molecule is essentially planar as indicated by the dihedral angle between the quinolinium and the dimethylaminophenyl rings being 2.79 (13)° [9.26 (6) ° in Chantrapromma et al., 2008] with the torsion angles C8–C9–C10–C11 = -0.1 (5)° and C10–C11–C12–C17 = 2.4 (5)°. Both methyl groups of dimethylamino moiety are slightly twisted from the mean plane of the attached C12–C17 ring as indicated by the torsion angle C18—N2–C15–C14 = 3.6 (4)° and C19–N2–C15–C16 = -6.3 (4)°. The relative arrangement of cation and anion is shown by the interplanar angles between the mean plane of the 4-methylphenyl ring and those of the quinolinium and dimethylaminophenyl system which are 67.80 (13) and 67.19 (16)°, respectively. Besides the O—H···O hydrogen bonded to water molecule, the atom O2 of the sulfonate also contributed to a weak intramolecular C26—H26A···O2 interaction (Table 1) forming an S(5) ring motif (Bernstein et al., 1995). The bond lengths (Allen et al., 1987) and angles in (I) are in normal ranges and comparable with a related structure (Chantrapromma et al., 2008).

In the crystal packing, all O atoms of the sulfonate group are involved in weak C—H···O interactions (Table 1). The cation is linked to the anion by weak C—H···O interactions and the anion is further linked to the water molecule by O—H···O hydrogen bonds, forming a three-molecule unit (Table 1 and Fig. 2). These three-molecule units are arranged in a face-to-face manner into a ribbon-like structure along the b axis and these ribbons are stacked along the c axis (Fig. 2). The crystal structure is further stabilized by C—H···π interactions (Table 1). A π–π interaction with the distance Cg₁···Cg₂^iv = 3.6074 (19) Å [symmetry code: (iv) 1 - x, -y, 1 - z] is observed; Cg₁, Cg₂, Cg₃ and Cg₄ are the centroids of the N1/C1/C6–C9, C1–C6, C12–C17 and C21–C26 rings, respectively.

Experimental

(E)-2-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide (compound A) was synthesized according to our previously reported procedure (Chantrapromma et al., 2008). Silver(I) p-toluensulfonate (compound B) was synthesized according to a previous method (Rahman et al., 2003). The title compound was then prepared by mixing compound A (0.20 g, 0.5 mmol) in hot methanol (50 ml) and compound B (0.12 g, 0.5 mmol) in hot methanol (30 ml). The mixture immediately yielded a grey precipitate of silver iodide. After stirring the mixture for 30 min, the precipitate of silver iodide was removed and the resulting solution was evaporated yielding a green solid. Green block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from methanol by slow evaporation of the solvent at room temperature a few weeks (m.p. 557–558 K).