(E)-2-[4-(Di­ethyl­amino)­styr­yl]-1-methyl­quinolin-1-ium 4-chloro­benzene­sulfonate monohydrate

Suchada Chantrapromma; Narissara Kaewmanee; Nawong Boonnak; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536814004577

. 2014 Mar 5;70(Pt 4):o395–o396. doi: 10.1107/S1600536814004577

(E)-2-[4-(Diethylamino)styryl]-1-methylquinolin-1-ium 4-chlorobenzenesulfonate monohydrate

Suchada Chantrapromma ^a,^*,^‡, Narissara Kaewmanee ^a, Nawong Boonnak ^b, Ching Kheng Quah ^c, Hoong-Kun Fun ^c,^§

PMCID: PMC3998564 PMID: 24826116

Abstract

The asymmetric unit of the title hydrated salt, C₂₂H₂₅N₂ ⁺·C₆H₄ClO₃S⁻·H₂O, comprises two 2-[4-(diethylamino)styryl]-1-methylquinolin-1-ium cations, two 4-chlorobenzenesulfonate anions and two solvent water molecules. One ethyl group of both cations displays disorder over two positions in a 0.659 (2):0.341 (2) ratio in one molecule and in a 0.501 (2):0.499 (2) ratio in the other. The sulfonate group of one anion is also disordered over two positions in a 0.893 (7):0.107 (7) ratio. The dihedral angle between the mean plane of the quinolinium ring system and that of benzene ring is 10.57 (18)° in one cation and 14.4 (2)° in the other. In the crystal, cations, anions and water molecules are linked into chains along the [010] direction by O—H⋯O_sulfonate hydrogen bonds, together with weak C—H⋯O_sulfonate and C—H⋯Cl interactions. The cations are stacked by π–π interactions, with centroid–centroid distances in the range 3.675 (2)–4.162 (3) Å.

Related literature

For standard bond lengths, see: Allen et al. (1987 ▶). For background to and applications of quarternary ammonium compounds, see: Barchéchath et al. (2005 ▶); Chanawanno et al. (2010a ▶,b ▶); Bolden et al. (2013 ▶). For related structures, see: Chantrapromma et al. (2012 ▶); Fun, Kaewmanee et al. (2011 ▶, 2013 ▶); Kaewmanee et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₂₅N₂ ⁺·C₆H₄ClO₃S⁻·H₂O
M _r = 527.07
Monoclinic,
a = 25.814 (4) Å
b = 10.5563 (16) Å
c = 20.333 (3) Å
β = 110.883 (2)°
V = 5176.8 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.31 × 0.19 × 0.15 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.923, T _max = 0.961
28821 measured reflections
10657 independent reflections
6269 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.201
S = 1.04
10657 reflections
708 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2009 ▶); 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, PLATON (Spek, 2009 ▶), Mercury (Macrae et al., 2008 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814004577/sj5390sup1.cif

e-70-0o395-sup1.cif^{(61.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814004577/sj5390Isup2.hkl

e-70-0o395-Isup2.hkl^{(521.1KB, hkl)}

Click here for additional data file.^{(9.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814004577/sj5390Isup3.cml

CCDC reference: 988937

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1WB—H1WB⋯O1B ⁱ	0.85	2.36	2.815 (7)	114
O1WB—H2WB⋯O2B ⁱⁱ	0.83	2.12	2.953 (7)	177
O1WA—H1WA⋯O2A ⁱⁱⁱ	0.84	2.07	2.891 (5)	166
O1WA—H2WA⋯O1A	0.76	2.10	2.844 (4)	169
C8A—H8AA⋯O3A ^iv	0.93	2.54	3.146 (5)	123
C2B—H2BA⋯O3B ^v	0.93	2.57	3.314 (7)	137
C11B—H11B⋯O1B ^vi	0.93	2.41	3.237 (6)	148
C18Y—H18E⋯Cl1A ^vii	0.97	2.72	3.673 (19)	169
C19B—H19D⋯Cl1B ^viii	0.96	2.73	3.531 (14)	142
C22B—H22D⋯O2B ^viii	0.96	2.55	3.259 (7)	131
C25A—H25A⋯O3A ⁱⁱ	0.93	2.56	3.359 (5)	144

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors thank the Prince of Songkla University for a research grant. An antibacterial assay by Dr Teerasak Anantapong, Department of Biotechnology, Faculty of Agro-Industry, Prince of Songkla University, is gratefully acknowledged. The authors extend their appreciation to the Universiti Sains Malaysia for the APEX DE2012 grant No. 1002/PFIZIK/910323.

supplementary crystallographic information

1. Comment

The bioactivity of compounds containing the quinolinium chemophore has been the subject of a number of reports (Barchéchath et al., 2005; Chanawanno et al., 2010a, 2010b and Bolden et al., 2013). The title quinolinium derivative (I) was synthesized and tested for antibacterial activities against gram positive bacteria including Bacillus subtilis, Enterococcus faecalis, Staphylococcus aureus, Methicillin-Resistant Staphylococcus aureus and Vancomycin-Resistant Enterococcus faecalis, and gram negative bacteria including Pseudomonas aeruginosa, Shigella sonnei and Salmonella typhi. Our antibacterial assay has shown that (I) is strongly active against B. subtilis and P. aeruginosa with a minimum inhibition concentration (MIC) of 9.37 µg/ml for both strains. In addition (I) also showed moderate activity against E. faecalis with an MIC value of 37.5 µg/ml. Herein the crystal structure of (I) is reported.

The asymmetric unit of the title compound (I) (Fig. 1) consists of two C₂₂H₂₅N₂⁺ cations, two C₆H₄ClO₃S^- anions and two solvent H₂O molecules [the two molecules are denoted as molecules A and B]. One ethyl unit of diethylamino group of both cation molecules displays disorder over two positions with refined site occupancy ratios of 0.659 (2):0.341 (2) and 0.501 (2):0.499 (2) for molecules A and B, respectively. The sulfonate group of the anion B also shows disorder over two positions with a refined site occupancy ratio of 0.893 (7):0.107 (7). The cations exist in the E configuration with respect to the C10═C11 double bond [1.343 (6) Å] and the torsion angle is C9–C10–C11–C12 of 174.6 (4)° for molecule A [the corresponding values are 1.324 (6) Å and -172.5 (4)° for molecule B]. The C1–C9/N1 quinolinium ring system is essentially planar with r.m.s. deviations of 0.0293 (4) and 0.0198 (5) Å for molecules A and B, respectively. The dihedral angle between the mean-plane of the quinolinium ring system and that of C12–C17 benzene ring is 10.57 (18) and 14.4 (2) ° for molecules A and B, respectively. The disorder of the ethyl groups in each cation result in the diethylamino substituents having two different configurations in which the two ethyl groups either point away from one another (Fig. 1 and Fig. 2), or towards one another (Fig. 1 and Fig. 3). The diethylamino substituents also deviate from the planes of the benzene rings to which they are attached as indicated by the torsion angles C15A–N2A–C18A–C19A = -84.1 (7)° and C15A–N2A–C20A–C21A = -96.3 (8)° (major component A) and C15A–N2A–C20X–C21X = 100.0 (11)° (minor component X). In molecule B, the torsion angles C15B–N2B–C20B–C21B = 79.0 (8)° and C15B–N2B–C18B–C19B = -83.7 (10)° (major component B) and C15B–N2B–C18Y–C19Y = 112.6 (10)° (minor component Y). The bond lengths are in normal ranges (Allen et al., 1987) and comparable to those found in some closely related structures (Chantrapromma et al., 2012; Fun, Kaewmanee et al., 2011, 2013 and Kaewmanee et al., 2010).

In the crystal packing, the cations, anions and water molecules are linked into chains along the [0 1 0] direction by O—H···O_sulfonate hydrogen bonds together with weak C—H···O_sulfonate and C—H···Cl interactions (Fig. 4 and Table 1). The cations are stacked through π–π interactions with the centroid distances Cg₁···Cg₁^iv = 3.675 (2) Å, Cg₁···Cg₂^iv = 4.106 (3) Å, Cg₁···Cg₃^ix = 4.018 (3) Å, Cg₁₆···Cg₁₆^x = 3.687 (3) Å, Cg₁₆···Cg₁₇^x = 3.714 (3) Å and Cg₁₆···Cg₁₈^xi = 4.162 (3) Å [symmetry codes are as in in Table 1 and (ix) = 1-x, -y, -z; (x) = 2-x, 2-y, 2-z and (xi) = 2-x, 1-y, 2-z]; Cg₁, Cg₂, Cg₃, Cg₁₆, Cg₁₇ and Cg₁₈ are the centroids of the N1A/C1A/C6A–C9A, C1A–C6A, C12A–C17A, N1B/C1B/C6B–C9B, C1B–C6B and C12B–C17B rings, respectively. Fig. 5 shows these π···π interactions only for the major disorder components.

2. Experimental

The title compound was prepared by stirring silver (I) 4-chlorobenzenesulfonate (0.95 g, 3.16 mmol) and (E)-2-(4-(diethylamino)styryl)-1-methylquinolinium iodide (1.44 g, 3.16 mmol) in methanol (100 ml) for ca. 0.5 h. The precipitate of silver iodide which formed was filtered out and the filtrate was evaporated to give the title compound as a brown solid. Brown block-shaped single crystals of the title compound suitable for X-ray structure determination was recrystallized from ethanol by slow evaporation at room temperature over a few weeks, Mp. 471-473 K.