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

Kobkeatthawin, T.; Ruanwas, P.; Chantrapromma, S.; Fun, H.-K.

doi:10.1107/S1600536808005205

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Pages o642-o643

doi:10.1107/S1600536808005205

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

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

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 14 February 2008; accepted 24 February 2008; online 29 February 2008)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.052
wR(F²) = 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

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
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) -x+2, -y-1, -z+2. Cg1 is the centroid of the C21–C26 methoxyphenyl ring.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005205/sj2466sup1.cif

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

checkCIF report

Comment top

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).]

Related literature top

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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. The weak intramolecular C—H···O interaction is drawn as a dashed line.
	Fig. 2. The crystal packing of (I) viewed along the b axis. The O—H···O and weak C—H···O interactions are drawn as dashed lines.

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

Crystal data top

C₂₀H₂₁N₂⁺·C₇H₇O₄S⁻·H₂O	F(000) = 1048
M_r = 494.60	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 545–547 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.6064 (5) Å	Cell parameters from 6593 reflections
b = 10.4253 (4) Å	θ = 2.1–30.0°
c = 19.5025 (6) Å	µ = 0.18 mm⁻¹
β = 126.737 (2)°	T = 100 K
V = 2379.94 (16) Å³	Block, brown
Z = 4	0.58 × 0.27 × 0.19 mm

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	6953 independent reflections
Radiation source: fine-focus sealed tube	5445 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 8.33 pixels mm^-1	θ_max = 30.0°, θ_min = 2.1°
ω scans	h = −20→19
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→14
T_min = 0.904, T_max = 0.967	l = −24→27
33983 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0641P)² + 1.1852P] where P = (F_o² + 2F_c²)/3
6953 reflections	(Δ/σ)_max = 0.001
350 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₂₀H₂₁N₂⁺·C₇H₇O₄S⁻·H₂O	V = 2379.94 (16) Å³
M_r = 494.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.6064 (5) Å	µ = 0.18 mm⁻¹
b = 10.4253 (4) Å	T = 100 K
c = 19.5025 (6) Å	0.58 × 0.27 × 0.19 mm
β = 126.737 (2)°

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	6953 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5445 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.967	R_int = 0.045
33983 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.06	Δρ_max = 0.75 e Å⁻³
6953 reflections	Δρ_min = −0.42 e Å⁻³
350 parameters

Special details top

Experimental. The low-temparture data was collected with the Oxford Cryosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.61826 (3)	0.05907 (4)	0.76956 (2)	0.02112 (11)
O1	0.95438 (10)	−0.35916 (12)	0.95862 (7)	0.0250 (3)
O2	0.53003 (10)	0.00579 (13)	0.68519 (7)	0.0275 (3)
O3	0.57692 (12)	0.08820 (15)	0.81913 (8)	0.0360 (3)
O4	0.67900 (11)	0.16597 (13)	0.76497 (8)	0.0301 (3)
O1W	0.66931 (11)	0.09083 (15)	0.33524 (10)	0.0429 (4)
H1W	0.6058	0.0660	0.3224	0.058 (8)*
H2W	0.6633	0.1682	0.3187	0.050 (7)*
N1	0.56771 (11)	0.67419 (14)	0.49475 (8)	0.0215 (3)
N2	0.05342 (12)	1.30700 (15)	0.29537 (8)	0.0235 (3)
C1	0.64527 (13)	0.57400 (17)	0.54367 (9)	0.0217 (3)
C2	0.70847 (15)	0.51470 (19)	0.52077 (11)	0.0277 (4)
H2A	0.7021	0.5417	0.4726	0.038 (6)*
C3	0.77995 (16)	0.4162 (2)	0.56969 (11)	0.0322 (4)
H3A	0.8227	0.3772	0.5545	0.055 (7)*
C4	0.79097 (16)	0.37240 (19)	0.64227 (11)	0.0304 (4)
H4A	0.8393	0.3040	0.6737	0.043 (6)*
C5	0.73095 (14)	0.42956 (18)	0.66701 (10)	0.0268 (4)
H5A	0.7384	0.4009	0.7153	0.024 (5)*
C6	0.65650 (13)	0.53407 (17)	0.61789 (10)	0.0229 (3)
C7	0.59337 (14)	0.59648 (18)	0.64128 (10)	0.0237 (3)
H7A	0.5989	0.5687	0.6889	0.026 (5)*
C8	0.52447 (14)	0.69699 (18)	0.59453 (10)	0.0241 (3)
H8A	0.4857	0.7396	0.6120	0.024 (5)*
C9	0.51057 (13)	0.73831 (17)	0.51874 (9)	0.0216 (3)
C10	0.43701 (13)	0.84531 (17)	0.46835 (10)	0.0220 (3)
H10A	0.4384	0.8763	0.4243	0.032 (6)*
C11	0.36646 (13)	0.90197 (17)	0.48240 (9)	0.0211 (3)
H11A	0.3685	0.8710	0.5280	0.033 (6)*
C12	0.28800 (13)	1.00599 (16)	0.43337 (9)	0.0197 (3)
C13	0.22320 (13)	1.05721 (17)	0.45820 (9)	0.0218 (3)
H13A	0.2324	1.0239	0.5062	0.039 (6)*
C14	0.14611 (13)	1.15578 (17)	0.41354 (9)	0.0215 (3)
H14A	0.1048	1.1876	0.4321	0.029 (5)*
C15	0.12911 (12)	1.20908 (16)	0.33990 (9)	0.0188 (3)
C16	0.19398 (13)	1.15699 (17)	0.31446 (9)	0.0202 (3)
H16A	0.1845	1.1893	0.2661	0.025 (5)*
C17	0.27101 (13)	1.05893 (17)	0.36003 (9)	0.0206 (3)
H17A	0.3128	1.0270	0.3419	0.023 (5)*
C18	−0.01161 (15)	1.3601 (2)	0.32301 (11)	0.0292 (4)
H18A	0.0396	1.3844	0.3821	0.029 (5)*
H18B	−0.0642	1.2968	0.3162	0.034 (6)*
H18C	−0.0532	1.4341	0.2890	0.054 (8)*
C19	0.03078 (15)	1.35334 (19)	0.21618 (10)	0.0260 (4)
H19A	0.1000	1.3866	0.2277	0.036 (6)*
H19B	−0.0257	1.4200	0.1926	0.043 (7)*
H19C	0.0031	1.2839	0.1760	0.028 (5)*
C20	0.54745 (16)	0.7057 (2)	0.41323 (11)	0.0288 (4)
H20A	0.4713	0.7384	0.3738	0.051 (7)*
H20B	0.5564	0.6299	0.3898	0.044 (7)*
H20C	0.6014	0.7695	0.4228	0.048 (7)*
C21	0.72090 (13)	−0.06494 (16)	0.82541 (9)	0.0190 (3)
C22	0.68657 (13)	−0.19286 (17)	0.81620 (9)	0.0210 (3)
H22A	0.6094	−0.2136	0.7793	0.024 (5)*
C23	0.76655 (14)	−0.28880 (17)	0.86144 (9)	0.0218 (3)
H23A	0.7432	−0.3737	0.8553	0.032 (6)*
C24	0.88269 (13)	−0.25763 (16)	0.91662 (9)	0.0198 (3)
C25	0.91782 (13)	−0.13092 (16)	0.92572 (9)	0.0209 (3)
H25A	0.9950	−0.1102	0.9623	0.030 (5)*
C26	0.83634 (13)	−0.03516 (17)	0.87967 (9)	0.0207 (3)
H26A	0.8596	0.0497	0.8853	0.021 (5)*
C27	1.07377 (14)	−0.33401 (19)	1.02041 (11)	0.0272 (4)
H27A	1.1131	−0.4129	1.0475	0.024 (5)*
H27B	1.0848	−0.2755	1.0628	0.031 (5)*
H27C	1.1035	−0.2968	0.9924	0.038 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02159 (18)	0.0248 (2)	0.01629 (17)	0.00406 (15)	0.01098 (14)	0.00242 (14)
O1	0.0220 (5)	0.0216 (6)	0.0234 (5)	0.0026 (5)	0.0093 (4)	0.0033 (5)
O2	0.0230 (6)	0.0336 (7)	0.0176 (5)	0.0029 (5)	0.0077 (5)	0.0016 (5)
O3	0.0390 (7)	0.0486 (9)	0.0284 (6)	0.0158 (7)	0.0244 (6)	0.0072 (6)
O4	0.0289 (6)	0.0248 (7)	0.0309 (6)	0.0018 (5)	0.0148 (5)	0.0054 (5)
O1W	0.0259 (7)	0.0310 (8)	0.0591 (9)	0.0033 (6)	0.0186 (7)	0.0143 (7)
N1	0.0211 (6)	0.0261 (8)	0.0164 (6)	0.0002 (5)	0.0107 (5)	0.0007 (5)
N2	0.0241 (6)	0.0285 (8)	0.0181 (6)	0.0070 (6)	0.0128 (5)	0.0032 (5)
C1	0.0180 (7)	0.0230 (8)	0.0167 (6)	−0.0035 (6)	0.0065 (5)	−0.0007 (6)
C2	0.0264 (8)	0.0331 (10)	0.0228 (7)	0.0006 (7)	0.0143 (7)	−0.0013 (7)
C3	0.0326 (9)	0.0343 (11)	0.0284 (8)	0.0044 (8)	0.0175 (7)	−0.0010 (7)
C4	0.0309 (9)	0.0274 (10)	0.0274 (8)	0.0069 (7)	0.0145 (7)	0.0042 (7)
C5	0.0231 (7)	0.0299 (10)	0.0210 (7)	0.0015 (7)	0.0097 (6)	0.0015 (7)
C6	0.0194 (7)	0.0258 (9)	0.0205 (7)	−0.0050 (6)	0.0102 (6)	−0.0058 (6)
C7	0.0238 (7)	0.0290 (9)	0.0165 (6)	−0.0025 (7)	0.0109 (6)	−0.0001 (6)
C8	0.0213 (7)	0.0291 (9)	0.0210 (7)	0.0012 (7)	0.0121 (6)	0.0021 (6)
C9	0.0176 (6)	0.0240 (9)	0.0205 (7)	−0.0033 (6)	0.0099 (6)	−0.0048 (6)
C10	0.0205 (7)	0.0253 (9)	0.0177 (6)	0.0007 (6)	0.0101 (6)	−0.0001 (6)
C11	0.0207 (7)	0.0237 (8)	0.0171 (6)	−0.0009 (6)	0.0103 (6)	−0.0007 (6)
C12	0.0179 (6)	0.0217 (8)	0.0173 (6)	−0.0011 (6)	0.0094 (5)	−0.0020 (6)
C13	0.0215 (7)	0.0276 (9)	0.0169 (6)	−0.0001 (6)	0.0117 (6)	0.0012 (6)
C14	0.0211 (7)	0.0278 (9)	0.0174 (6)	0.0014 (6)	0.0126 (6)	−0.0017 (6)
C15	0.0169 (6)	0.0208 (8)	0.0158 (6)	−0.0003 (6)	0.0082 (5)	−0.0020 (5)
C16	0.0202 (7)	0.0256 (8)	0.0160 (6)	−0.0007 (6)	0.0114 (6)	−0.0005 (6)
C17	0.0180 (6)	0.0275 (9)	0.0178 (6)	0.0009 (6)	0.0114 (5)	−0.0027 (6)
C18	0.0274 (8)	0.0354 (10)	0.0247 (8)	0.0099 (8)	0.0156 (7)	0.0014 (7)
C19	0.0251 (8)	0.0296 (9)	0.0191 (7)	0.0019 (7)	0.0110 (6)	0.0039 (6)
C20	0.0325 (9)	0.0341 (10)	0.0243 (8)	0.0077 (8)	0.0195 (7)	0.0077 (7)
C21	0.0202 (7)	0.0234 (8)	0.0139 (6)	0.0012 (6)	0.0105 (5)	0.0017 (6)
C22	0.0188 (7)	0.0259 (9)	0.0162 (6)	−0.0012 (6)	0.0093 (6)	0.0004 (6)
C23	0.0247 (7)	0.0210 (8)	0.0178 (6)	−0.0019 (6)	0.0118 (6)	0.0006 (6)
C24	0.0221 (7)	0.0222 (8)	0.0156 (6)	0.0028 (6)	0.0115 (6)	0.0020 (6)
C25	0.0187 (7)	0.0239 (8)	0.0157 (6)	−0.0011 (6)	0.0080 (6)	0.0000 (6)
C26	0.0221 (7)	0.0210 (8)	0.0175 (6)	−0.0016 (6)	0.0110 (6)	−0.0006 (6)
C27	0.0216 (7)	0.0300 (10)	0.0230 (7)	0.0039 (7)	0.0095 (6)	0.0039 (7)

Geometric parameters (Å, º) top

S1—O3	1.4455 (13)	C11—H11A	0.9299
S1—O4	1.4602 (14)	C12—C13	1.401 (2)
S1—O2	1.4628 (12)	C12—C17	1.410 (2)
S1—C21	1.7754 (16)	C13—C14	1.382 (2)
O1—C24	1.3644 (19)	C13—H13A	0.9301
O1—C27	1.431 (2)	C14—C15	1.417 (2)
O1W—H1W	0.8450	C14—H14A	0.9297
O1W—H2W	0.8529	C15—C16	1.415 (2)
N1—C9	1.353 (2)	C16—C17	1.380 (2)
N1—C1	1.411 (2)	C16—H16A	0.9299
N1—C20	1.470 (2)	C17—H17A	0.9299
N2—C15	1.368 (2)	C18—H18A	0.9600
N2—C18	1.453 (2)	C18—H18B	0.9600
N2—C19	1.455 (2)	C18—H18C	0.9600
C1—C2	1.388 (2)	C19—H19A	0.9600
C1—C6	1.418 (2)	C19—H19B	0.9600
C2—C3	1.365 (3)	C19—H19C	0.9600
C2—H2A	0.9299	C20—H20A	0.9600
C3—C4	1.402 (3)	C20—H20B	0.9600
C3—H3A	0.9301	C20—H20C	0.9600
C4—C5	1.365 (3)	C21—C26	1.387 (2)
C4—H4A	0.9300	C21—C22	1.398 (2)
C5—C6	1.429 (2)	C22—C23	1.382 (2)
C5—H5A	0.9301	C22—H22A	0.9300
C6—C7	1.409 (2)	C23—C24	1.399 (2)
C7—C8	1.358 (2)	C23—H23A	0.9301
C7—H7A	0.9300	C24—C25	1.390 (2)
C8—C9	1.433 (2)	C25—C26	1.393 (2)
C8—H8A	0.9301	C25—H25A	0.9300
C9—C10	1.450 (2)	C26—H26A	0.9301
C10—C11	1.350 (2)	C27—H27A	0.9600
C10—H10A	0.9299	C27—H27B	0.9600
C11—C12	1.447 (2)	C27—H27C	0.9600

O3—S1—O4	113.13 (9)	C13—C14—H14A	119.6
O3—S1—O2	113.11 (8)	C15—C14—H14A	119.6
O4—S1—O2	112.31 (8)	N2—C15—C16	121.37 (14)
O3—S1—C21	106.25 (7)	N2—C15—C14	121.43 (14)
O4—S1—C21	105.80 (7)	C16—C15—C14	117.20 (14)
O2—S1—C21	105.44 (8)	C17—C16—C15	121.17 (14)
C24—O1—C27	118.33 (14)	C17—C16—H16A	119.4
H1W—O1W—H2W	109.3	C15—C16—H16A	119.4
C9—N1—C1	122.94 (14)	C16—C17—C12	121.62 (15)
C9—N1—C20	119.79 (14)	C16—C17—H17A	119.2
C1—N1—C20	117.24 (14)	C12—C17—H17A	119.2
C15—N2—C18	120.55 (14)	N2—C18—H18A	109.5
C15—N2—C19	120.40 (14)	N2—C18—H18B	109.5
C18—N2—C19	118.91 (14)	H18A—C18—H18B	109.5
C2—C1—N1	122.11 (15)	N2—C18—H18C	109.5
C2—C1—C6	120.29 (16)	H18A—C18—H18C	109.5
N1—C1—C6	117.60 (15)	H18B—C18—H18C	109.5
C3—C2—C1	119.21 (17)	N2—C19—H19A	109.5
C3—C2—H2A	120.4	N2—C19—H19B	109.5
C1—C2—H2A	120.4	H19A—C19—H19B	109.5
C2—C3—C4	121.91 (18)	N2—C19—H19C	109.5
C2—C3—H3A	119.0	H19A—C19—H19C	109.5
C4—C3—H3A	119.1	H19B—C19—H19C	109.5
C5—C4—C3	120.31 (18)	N1—C20—H20A	109.5
C5—C4—H4A	119.8	N1—C20—H20B	109.5
C3—C4—H4A	119.8	H20A—C20—H20B	109.5
C4—C5—C6	119.22 (16)	N1—C20—H20C	109.5
C4—C5—H5A	120.5	H20A—C20—H20C	109.5
C6—C5—H5A	120.3	H20B—C20—H20C	109.5
C7—C6—C1	119.76 (16)	C26—C21—C22	119.36 (15)
C7—C6—C5	121.21 (16)	C26—C21—S1	120.01 (13)
C1—C6—C5	119.03 (16)	C22—C21—S1	120.63 (11)
C8—C7—C6	120.31 (16)	C23—C22—C21	120.46 (14)
C8—C7—H7A	119.8	C23—C22—H22A	119.7
C6—C7—H7A	119.9	C21—C22—H22A	119.8
C7—C8—C9	121.03 (16)	C22—C23—C24	119.73 (16)
C7—C8—H8A	119.5	C22—C23—H23A	120.1
C9—C8—H8A	119.5	C24—C23—H23A	120.2
N1—C9—C8	118.18 (15)	O1—C24—C25	124.66 (14)
N1—C9—C10	120.42 (14)	O1—C24—C23	115.07 (15)
C8—C9—C10	121.40 (15)	C25—C24—C23	120.28 (15)
C11—C10—C9	123.04 (15)	C24—C25—C26	119.41 (14)
C11—C10—H10A	118.5	C24—C25—H25A	120.3
C9—C10—H10A	118.5	C26—C25—H25A	120.3
C10—C11—C12	126.36 (15)	C21—C26—C25	120.74 (16)
C10—C11—H11A	116.8	C21—C26—H26A	119.6
C12—C11—H11A	116.9	C25—C26—H26A	119.7
C13—C12—C17	117.13 (15)	O1—C27—H27A	109.5
C13—C12—C11	119.28 (14)	O1—C27—H27B	109.5
C17—C12—C11	123.58 (15)	H27A—C27—H27B	109.5
C14—C13—C12	121.99 (15)	O1—C27—H27C	109.5
C14—C13—H13A	119.0	H27A—C27—H27C	109.5
C12—C13—H13A	119.0	H27B—C27—H27C	109.5
C13—C14—C15	120.88 (15)

C9—N1—C1—C2	−175.88 (16)	C12—C13—C14—C15	0.3 (2)
C20—N1—C1—C2	5.9 (2)	C18—N2—C15—C16	−179.39 (16)
C9—N1—C1—C6	4.6 (2)	C19—N2—C15—C16	5.0 (2)
C20—N1—C1—C6	−173.66 (15)	C18—N2—C15—C14	0.4 (2)
N1—C1—C2—C3	−178.39 (16)	C19—N2—C15—C14	−175.14 (15)
C6—C1—C2—C3	1.1 (3)	C13—C14—C15—N2	−179.73 (15)
C1—C2—C3—C4	0.4 (3)	C13—C14—C15—C16	0.1 (2)
C2—C3—C4—C5	−1.1 (3)	N2—C15—C16—C17	179.42 (15)
C3—C4—C5—C6	0.3 (3)	C14—C15—C16—C17	−0.4 (2)
C2—C1—C6—C7	178.90 (16)	C15—C16—C17—C12	0.4 (2)
N1—C1—C6—C7	−1.6 (2)	C13—C12—C17—C16	0.0 (2)
C2—C1—C6—C5	−1.9 (2)	C11—C12—C17—C16	179.05 (15)
N1—C1—C6—C5	177.59 (14)	O3—S1—C21—C26	−97.34 (14)
C4—C5—C6—C7	−179.62 (17)	O4—S1—C21—C26	23.18 (15)
C4—C5—C6—C1	1.2 (2)	O2—S1—C21—C26	142.35 (13)
C1—C6—C7—C8	−1.9 (2)	O3—S1—C21—C22	81.83 (14)
C5—C6—C7—C8	178.93 (16)	O4—S1—C21—C22	−157.66 (13)
C6—C7—C8—C9	2.7 (3)	O2—S1—C21—C22	−38.48 (15)
C1—N1—C9—C8	−3.9 (2)	C26—C21—C22—C23	0.8 (2)
C20—N1—C9—C8	174.28 (15)	S1—C21—C22—C23	−178.35 (12)
C1—N1—C9—C10	176.41 (14)	C21—C22—C23—C24	−0.2 (2)
C20—N1—C9—C10	−5.4 (2)	C27—O1—C24—C25	3.9 (2)
C7—C8—C9—N1	0.2 (2)	C27—O1—C24—C23	−175.95 (14)
C7—C8—C9—C10	179.86 (16)	C22—C23—C24—O1	179.57 (14)
N1—C9—C10—C11	170.96 (15)	C22—C23—C24—C25	−0.3 (2)
C8—C9—C10—C11	−8.7 (2)	O1—C24—C25—C26	−179.62 (14)
C9—C10—C11—C12	−177.83 (15)	C23—C24—C25—C26	0.2 (2)
C10—C11—C12—C13	−177.82 (16)	C22—C21—C26—C25	−0.9 (2)
C10—C11—C12—C17	3.2 (3)	S1—C21—C26—C25	178.29 (12)
C17—C12—C13—C14	−0.3 (2)	C24—C25—C26—C21	0.4 (2)
C11—C12—C13—C14	−179.40 (15)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x, −y−1/2, z+1/2; (vi) −x+2, y−1/2, −z+3/2; (vii) −x+2, −y−1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₁N₂⁺·C₇H₇O₄S⁻·H₂O
M_r	494.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.6064 (5), 10.4253 (4), 19.5025 (6)
β (°)	126.737 (2)
V (Å³)	2379.94 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.58 × 0.27 × 0.19

Data collection
Diffractometer	Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.904, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	33983, 6953, 5445
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.139, 1.06
No. of reflections	6953
No. of parameters	350
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.42

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2ⁱ	0.84	2.0413	2.875 (3)	169
O1W—H2W···O4ⁱⁱ	0.85	2.1040	2.926 (2)	161
C7—H7A···O3ⁱⁱⁱ	0.93	2.4859	3.015 (3)	116
C8—H8A···O3ⁱⁱⁱ	0.93	2.5694	3.049 (3)	113
C20—H20A···O4^iv	0.96	2.4557	3.325 (2)	151
C23—H23A···O1W^v	0.93	2.4366	3.365 (2)	176
C26—H26A···O4	0.93	2.5553	2.921 (2)	104
C27—H27A···O1W^vi	0.96	2.5763	3.160 (3)	119
C27—H27A···O1^vii	0.96	2.5479	3.282 (2)	133
C16—H16A···Cg1^iv	0.93	2.8096	3.6513 (19)	151

Footnotes

†This paper is dedicated to the late Her Royal Highness Princess Galyani Vadhana Krom Luang Naradhiwas Rajanagarindra for her patronage of science in Thailand.

‡Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

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.

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