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

Murugavel, S.; SubbiahPandi, A.; Srikanth, C.; Kalainathan, S.

doi:10.1107/S1600536808041007

organic compounds

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Volume 65| Part 1| January 2009| Page o71

doi:10.1107/S1600536808041007

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

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

^aDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India, ^bDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^cSchool of Science & Humanities, VIT University, Vellore 632 014, India
^*Correspondence e-mail: a_spandian@yahoo.com

(Received 19 November 2008; accepted 4 December 2008; online 10 December 2008)

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, P 2₁ /n
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[F² > 2σ(F²)] = 0.057
wR(F²) = 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

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
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

For related structure, see: Zhang et al. (1997). For molecular compounds with non-linear

optical (NLO) properties, see: Bosshard et al. (1995); Nalwa & Miyata (1997); Lee & Kim (1999).

Experimental top

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.

Computing details top

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 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of title compound showing 30% probability displacement ellipsoids.
	Fig. 2. 2. π—π interactions (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) -x+1, -y, -z+1; (ii) x, y-1, z; (iii) x, y+1, z; (iv) -x+1, -y+1, -z+1.]

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

Crystal data top

C₁₆H₁₈NO₂⁺·C₇H₇O₃S⁻·H₂O	F(000) = 944
M_r = 445.52	D_x = 1.315 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5318 reflections
a = 13.7700 (4) Å	θ = 2.2–27.8°
b = 9.7125 (2) Å	µ = 0.18 mm⁻¹
c = 17.3394 (5) Å	T = 293 K
β = 104.059 (2)°	Block, orange
V = 2249.53 (10) Å³	0.25 × 0.17 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	5310 independent reflections
Radiation source: fine-focus sealed tube	3610 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 10 pixels mm^-1	θ_max = 27.8°, θ_min = 2.2°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
T_min = 0.961, T_max = 0.975	l = −22→22
48719 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)] = 0.057	Hydrogen site location: difference Fourier map
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0893P)² + 1.1253P] where P = (F_o² + 2F_c²)/3
5310 reflections	(Δ/σ)_max < 0.001
290 parameters	Δρ_max = 0.72 e Å⁻³
3 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₆H₁₈NO₂⁺·C₇H₇O₃S⁻·H₂O	V = 2249.53 (10) Å³
M_r = 445.52	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.7700 (4) Å	µ = 0.18 mm⁻¹
b = 9.7125 (2) Å	T = 293 K
c = 17.3394 (5) Å	0.25 × 0.17 × 0.16 mm
β = 104.059 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5310 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3610 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.975	R_int = 0.034
48719 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	3 restraints
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.72 e Å⁻³
5310 reflections	Δρ_min = −0.30 e Å⁻³
290 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S	0.72581 (5)	0.48936 (6)	0.59449 (4)	0.0646 (2)
O1	0.92457 (12)	0.27591 (17)	0.20090 (10)	0.0589 (4)
H1O	0.9248	0.2213	0.1649	0.088*
O2	0.91242 (13)	0.42417 (17)	0.32358 (10)	0.0604 (4)
O3	0.62950 (16)	0.5133 (2)	0.61455 (17)	0.0998 (8)
O4	0.78329 (17)	0.3912 (2)	0.64784 (16)	0.0958 (8)
O5	0.7116 (2)	0.4619 (2)	0.51204 (15)	0.1024 (8)
O6	0.44858 (19)	0.3921 (3)	0.58789 (15)	0.0855 (6)
H6OA	0.399 (2)	0.427 (3)	0.5530 (19)	0.16 (2)*
H6OB	0.4608 (18)	0.4682 (16)	0.6128 (13)	0.050 (7)*
N	0.55785 (13)	−0.0896 (2)	0.63677 (11)	0.0514 (5)
C1	0.56915 (16)	−0.1585 (2)	0.57240 (14)	0.0515 (5)
H1	0.5445	−0.2477	0.5633	0.062*
C2	0.61625 (16)	−0.0993 (2)	0.52038 (13)	0.0484 (5)
H2	0.6230	−0.1481	0.4758	0.058*
C3	0.65447 (15)	0.0336 (2)	0.53320 (13)	0.0477 (5)
C4	0.64007 (18)	0.1008 (2)	0.60023 (15)	0.0565 (6)
H4	0.6637	0.1902	0.6110	0.068*
C5	0.59222 (18)	0.0384 (3)	0.65010 (15)	0.0571 (6)
H5	0.5832	0.0856	0.6945	0.069*
C6	0.5107 (2)	−0.1567 (4)	0.69445 (17)	0.0814 (9)
H6A	0.5615	−0.1870	0.7395	0.122*
H6B	0.4723	−0.2345	0.6699	0.122*
H6C	0.4673	−0.0924	0.7116	0.122*
C7	0.70733 (17)	0.1044 (2)	0.48149 (14)	0.0547 (6)
H7	0.7258	0.1957	0.4928	0.066*
C8	0.73041 (18)	0.0465 (3)	0.41971 (15)	0.0578 (6)
H8	0.7107	−0.0447	0.4098	0.069*
C9	0.78346 (17)	0.1085 (3)	0.36470 (14)	0.0545 (6)
C10	0.79432 (19)	0.0317 (3)	0.30061 (16)	0.0616 (6)
H10	0.7700	−0.0580	0.2944	0.074*
C11	0.84097 (18)	0.0864 (3)	0.24558 (15)	0.0581 (6)
H11	0.8466	0.0335	0.2022	0.070*
C12	0.87921 (16)	0.2176 (2)	0.25382 (13)	0.0486 (5)
C13	0.87119 (17)	0.2968 (2)	0.31965 (13)	0.0503 (5)
C14	0.82272 (17)	0.2423 (3)	0.37394 (13)	0.0541 (5)
H14	0.8161	0.2952	0.4171	0.065*
C15	0.9068 (2)	0.5061 (3)	0.39048 (17)	0.0719 (8)
H15A	0.9420	0.4613	0.4393	0.086*
H15B	0.8376	0.5191	0.3922	0.086*
C16	0.9543 (3)	0.6418 (4)	0.3816 (2)	0.1043 (13)
H16A	0.9518	0.6998	0.4259	0.156*
H16B	0.9189	0.6851	0.3332	0.156*
H16C	1.0228	0.6276	0.3801	0.156*
C17	0.78797 (16)	0.6487 (2)	0.61343 (14)	0.0476 (5)
C18	0.8387 (2)	0.7012 (3)	0.56113 (17)	0.0652 (7)
H18	0.8428	0.6513	0.5163	0.078*
C19	0.8839 (2)	0.8288 (3)	0.5755 (2)	0.0784 (9)
H19	0.9184	0.8637	0.5398	0.094*
C20	0.8792 (2)	0.9043 (3)	0.6399 (2)	0.0763 (9)
C21	0.8292 (2)	0.8499 (3)	0.69306 (18)	0.0749 (9)
H21	0.8265	0.8996	0.7383	0.090*
C22	0.78351 (19)	0.7234 (3)	0.67996 (14)	0.0592 (6)
H22	0.7496	0.6884	0.7160	0.071*
C23	0.9251 (3)	1.0473 (3)	0.6528 (3)	0.133 (2)
H23A	0.9759	1.0560	0.6237	0.200*
H23B	0.9543	1.0611	0.7084	0.200*
H23C	0.8740	1.1151	0.6343	0.200*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0666 (4)	0.0422 (3)	0.0802 (5)	−0.0071 (3)	0.0084 (3)	0.0070 (3)
O1	0.0698 (10)	0.0593 (9)	0.0532 (9)	−0.0040 (8)	0.0257 (8)	−0.0002 (7)
O2	0.0762 (11)	0.0561 (9)	0.0528 (9)	−0.0154 (8)	0.0230 (8)	−0.0076 (7)
O3	0.0602 (12)	0.0806 (14)	0.156 (2)	−0.0146 (10)	0.0220 (13)	0.0169 (14)
O4	0.0885 (14)	0.0532 (11)	0.133 (2)	0.0007 (10)	0.0020 (13)	0.0301 (12)
O5	0.140 (2)	0.0646 (12)	0.0956 (17)	−0.0186 (13)	0.0156 (15)	−0.0220 (12)
O6	0.0890 (16)	0.0924 (16)	0.0747 (14)	−0.0218 (13)	0.0189 (12)	0.0171 (13)
N	0.0447 (10)	0.0609 (11)	0.0485 (11)	0.0068 (8)	0.0112 (8)	0.0105 (9)
C1	0.0492 (12)	0.0417 (10)	0.0614 (14)	0.0022 (9)	0.0090 (10)	0.0038 (10)
C2	0.0493 (11)	0.0485 (11)	0.0476 (12)	0.0041 (9)	0.0124 (9)	−0.0017 (9)
C3	0.0425 (11)	0.0489 (11)	0.0498 (12)	0.0038 (9)	0.0074 (9)	0.0055 (9)
C4	0.0575 (13)	0.0452 (11)	0.0642 (15)	0.0007 (10)	0.0101 (11)	−0.0056 (10)
C5	0.0561 (13)	0.0622 (14)	0.0523 (13)	0.0067 (11)	0.0121 (11)	−0.0102 (11)
C6	0.0753 (18)	0.109 (2)	0.0651 (18)	0.0012 (17)	0.0274 (14)	0.0299 (16)
C7	0.0548 (13)	0.0484 (11)	0.0597 (14)	−0.0057 (10)	0.0116 (11)	0.0003 (10)
C8	0.0580 (14)	0.0521 (12)	0.0621 (15)	−0.0083 (10)	0.0120 (11)	−0.0001 (11)
C9	0.0495 (12)	0.0610 (13)	0.0528 (13)	−0.0070 (10)	0.0125 (10)	0.0046 (10)
C10	0.0634 (15)	0.0551 (13)	0.0673 (16)	−0.0108 (11)	0.0179 (12)	−0.0025 (11)
C11	0.0614 (14)	0.0585 (13)	0.0563 (14)	−0.0046 (11)	0.0181 (11)	−0.0078 (11)
C12	0.0448 (11)	0.0556 (12)	0.0451 (12)	0.0015 (9)	0.0105 (9)	0.0028 (9)
C13	0.0499 (12)	0.0525 (12)	0.0463 (12)	−0.0036 (9)	0.0072 (9)	−0.0002 (9)
C14	0.0550 (13)	0.0624 (13)	0.0453 (12)	−0.0024 (10)	0.0131 (10)	−0.0032 (10)
C15	0.094 (2)	0.0704 (16)	0.0586 (15)	−0.0280 (14)	0.0324 (14)	−0.0164 (12)
C16	0.163 (3)	0.077 (2)	0.098 (2)	−0.052 (2)	0.079 (2)	−0.0346 (18)
C17	0.0463 (11)	0.0381 (10)	0.0570 (13)	0.0030 (8)	0.0101 (9)	0.0011 (9)
C18	0.0755 (16)	0.0488 (12)	0.0830 (18)	−0.0006 (11)	0.0420 (14)	−0.0084 (12)
C19	0.0653 (16)	0.0535 (14)	0.127 (3)	−0.0044 (12)	0.0430 (17)	0.0067 (16)
C20	0.0515 (14)	0.0437 (12)	0.119 (3)	0.0022 (11)	−0.0074 (15)	−0.0091 (15)
C21	0.0733 (17)	0.0632 (15)	0.0715 (18)	0.0183 (14)	−0.0146 (14)	−0.0236 (14)
C22	0.0603 (14)	0.0656 (14)	0.0489 (13)	0.0136 (11)	0.0076 (11)	0.0035 (11)
C23	0.083 (2)	0.0527 (17)	0.234 (6)	−0.0123 (16)	−0.021 (3)	−0.023 (3)

Geometric parameters (Å, º) top

S—O5	1.420 (3)	C9—C10	1.377 (4)
S—O4	1.427 (2)	C9—C14	1.401 (3)
S—O3	1.469 (2)	C10—C11	1.380 (3)
S—C17	1.760 (2)	C10—H10	0.9300
O1—C12	1.353 (3)	C11—C12	1.373 (3)
O1—H1O	0.8200	C11—H11	0.9300
O2—C13	1.356 (3)	C12—C13	1.403 (3)
O2—C15	1.424 (3)	C13—C14	1.385 (3)
O6—H6OA	0.86 (3)	C14—H14	0.9300
O6—H6OB	0.85 (1)	C15—C16	1.496 (4)
N—C5	1.330 (3)	C15—H15A	0.9700
N—C1	1.342 (3)	C15—H15B	0.9700
N—C6	1.471 (3)	C16—H16A	0.9600
C1—C2	1.360 (3)	C16—H16B	0.9600
C1—H1	0.9300	C16—H16C	0.9600
C2—C3	1.391 (3)	C17—C18	1.371 (3)
C2—H2	0.9300	C17—C22	1.377 (3)
C3—C4	1.389 (3)	C18—C19	1.382 (4)
C3—C7	1.457 (3)	C18—H18	0.9300
C4—C5	1.351 (4)	C19—C20	1.351 (5)
C4—H4	0.9300	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.383 (5)
C6—H6A	0.9600	C20—C23	1.519 (4)
C6—H6B	0.9600	C21—C22	1.373 (4)
C6—H6C	0.9600	C21—H21	0.9300
C7—C8	1.315 (3)	C22—H22	0.9300
C7—H7	0.9300	C23—H23A	0.9600
C8—C9	1.465 (3)	C23—H23B	0.9600
C8—H8	0.9300	C23—H23C	0.9600

O5—S—O4	116.5 (2)	C10—C11—H11	119.4
O5—S—O3	110.9 (2)	O1—C12—C11	123.1 (2)
O4—S—O3	110.04 (15)	O1—C12—C13	117.6 (2)
O5—S—C17	107.1 (1)	C11—C12—C13	119.3 (2)
O4—S—C17	107.4 (1)	O2—C13—C14	125.4 (2)
O3—S—C17	104.1 (1)	O2—C13—C12	115.2 (2)
C12—O1—H1O	109.5	C14—C13—C12	119.3 (2)
C13—O2—C15	116.5 (2)	C13—C14—C9	120.9 (2)
H6OA—O6—H6OB	92 (1)	C13—C14—H14	119.6
C5—N—C1	120.1 (2)	C9—C14—H14	119.6
C5—N—C6	119.6 (2)	O2—C15—C16	107.3 (2)
C1—N—C6	120.2 (2)	O2—C15—H15A	110.3
N—C1—C2	120.7 (2)	C16—C15—H15A	110.3
N—C1—H1	119.6	O2—C15—H15B	110.3
C2—C1—H1	119.6	C16—C15—H15B	110.3
C1—C2—C3	120.6 (2)	H15A—C15—H15B	108.5
C1—C2—H2	119.7	C15—C16—H16A	109.5
C3—C2—H2	119.7	C15—C16—H16B	109.5
C4—C3—C2	116.4 (2)	H16A—C16—H16B	109.5
C4—C3—C7	119.2 (2)	C15—C16—H16C	109.5
C2—C3—C7	124.5 (2)	H16A—C16—H16C	109.5
C5—C4—C3	121.0 (2)	H16B—C16—H16C	109.5
C5—C4—H4	119.5	C18—C17—C22	119.4 (2)
C3—C4—H4	119.5	C18—C17—S	120.46 (18)
N—C5—C4	121.1 (2)	C22—C17—S	120.07 (19)
N—C5—H5	119.5	C17—C18—C19	119.6 (3)
C4—C5—H5	119.5	C17—C18—H18	120.2
N—C6—H6A	109.5	C19—C18—H18	120.2
N—C6—H6B	109.5	C20—C19—C18	121.8 (3)
H6A—C6—H6B	109.5	C20—C19—H19	119.1
N—C6—H6C	109.5	C18—C19—H19	119.1
H6A—C6—H6C	109.5	C19—C20—C21	118.3 (2)
H6B—C6—H6C	109.5	C19—C20—C23	121.1 (4)
C8—C7—C3	123.7 (2)	C21—C20—C23	120.6 (3)
C8—C7—H7	118.2	C22—C21—C20	121.0 (3)
C3—C7—H7	118.2	C22—C21—H21	119.5
C7—C8—C9	127.7 (2)	C20—C21—H21	119.5
C7—C8—H8	116.1	C21—C22—C17	119.9 (3)
C9—C8—H8	116.1	C21—C22—H22	120.1
C10—C9—C14	118.7 (2)	C17—C22—H22	120.1
C10—C9—C8	118.1 (2)	C20—C23—H23A	109.5
C14—C9—C8	123.1 (2)	C20—C23—H23B	109.5
C9—C10—C11	120.6 (2)	H23A—C23—H23B	109.5
C9—C10—H10	119.7	C20—C23—H23C	109.5
C11—C10—H10	119.7	H23A—C23—H23C	109.5
C12—C11—C10	121.1 (2)	H23B—C23—H23C	109.5
C12—C11—H11	119.4

C5—N—C1—C2	0.5 (3)	O1—C12—C13—C14	178.16 (19)
C6—N—C1—C2	−177.3 (2)	C11—C12—C13—C14	−1.6 (3)
N—C1—C2—C3	0.5 (3)	O2—C13—C14—C9	−179.4 (2)
C1—C2—C3—C4	−1.1 (3)	C12—C13—C14—C9	1.2 (3)
C1—C2—C3—C7	179.0 (2)	C10—C9—C14—C13	0.3 (4)
C2—C3—C4—C5	0.6 (3)	C8—C9—C14—C13	−179.2 (2)
C7—C3—C4—C5	−179.4 (2)	C13—O2—C15—C16	−178.7 (3)
C1—N—C5—C4	−0.9 (3)	O5—S—C17—C18	−19.3 (2)
C6—N—C5—C4	176.9 (2)	O4—S—C17—C18	106.6 (2)
C3—C4—C5—N	0.3 (4)	O3—S—C17—C18	−136.8 (2)
C4—C3—C7—C8	175.4 (2)	O5—S—C17—C22	158.9 (2)
C2—C3—C7—C8	−4.7 (4)	O4—S—C17—C22	−75.3 (2)
C3—C7—C8—C9	−179.7 (2)	O3—S—C17—C22	41.4 (2)
C7—C8—C9—C10	−175.9 (2)	C22—C17—C18—C19	−0.6 (4)
C7—C8—C9—C14	3.5 (4)	S—C17—C18—C19	177.6 (2)
C14—C9—C10—C11	−1.4 (4)	C17—C18—C19—C20	−0.2 (4)
C8—C9—C10—C11	178.0 (2)	C18—C19—C20—C21	1.2 (4)
C9—C10—C11—C12	1.1 (4)	C18—C19—C20—C23	−177.1 (3)
C10—C11—C12—O1	−179.3 (2)	C19—C20—C21—C22	−1.3 (4)
C10—C11—C12—C13	0.4 (4)	C23—C20—C21—C22	176.9 (3)
C15—O2—C13—C14	1.6 (4)	C20—C21—C22—C17	0.6 (4)
C15—O2—C13—C12	−179.0 (2)	C18—C17—C22—C21	0.4 (4)
O1—C12—C13—O2	−1.3 (3)	S—C17—C22—C21	−177.75 (18)
C11—C12—C13—O2	179.0 (2)

Hydrogen-bond geometry (Å, º) top

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)	104 (2)
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

Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈NO₂⁺·C₇H₇O₃S⁻·H₂O
M_r	445.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.7700 (4), 9.7125 (2), 17.3394 (5)
β (°)	104.059 (2)
V (Å³)	2249.53 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.25 × 0.17 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	48719, 5310, 3610
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.187, 1.03
No. of reflections	5310
No. of parameters	290
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.30

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O6ⁱ	0.82	1.82	2.632 (3)	169.9
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)	160.8
C5—H5···O1ⁱⁱⁱ	0.93	2.59	3.217 (3)	125.2

Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z+1/2.

Acknowledgements

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

References

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