2-[(E)-2-(4-Ethoxy-phen-yl)ethen-yl]-1-methyl-pyridinium 4-bromo-benzene-sulfonate monohydrate.

In the title compound, C(16)H(18)NO(+)·C(6)H(4)BrO(3)S(-)·H(2)O, the cation exists in an E configuration with respect to the ethenyl bond and is slightly twisted with a dihedral angle of 8.5 (2)° between pyridinium and benzene rings. In the crystal, the cations are arranged in layers parallel to (100), with π-π inter-actions between pyridinium and benzene rings [centroid-centroid distances = 3.651 (3) and 3.613 (3) Å]. The anions and water mol-ecules are located between the cationic layers. The ions and water mol-ecules are linked into a three-dimensional framework by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

The title compound was synthesized as part of an investigation of the influence of the counter-ions on non-linear optical (NLO) properties. For background to NLO materials research, see: Coe et al. (2002 ▶); Pan et al. (1996 ▶). For related structures, see: Chanawanno et al. (2009 ▶); Chantrapromma et al. (2006 ▶, 2009 ▶); Laksana et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H18NO+·C6H4BrO3S−·H2O

M = 494.39

Monoclinic,

a = 9.8022 (5) Å

b = 6.5162 (3) Å

c = 34.9982 (17) Å

β = 105.102 (3)°

V = 2158.24 (18) Å3

Z = 4

Mo Kα radiation

μ = 2.04 mm−1

T = 100 K

0.34 × 0.31 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.547, T max = 0.703

30564 measured reflections

6286 independent reflections

4937 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.071

wR(F 2) = 0.224

S = 1.15

6286 reflections

275 parameters

H-atom parameters constrained

Δρmax = 1.26 e Å−3

Δρmin = −1.36 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809055846/ci5012sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055846/ci5012Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H18NO+·C6H4BrO3S−·H2O	F(000) = 1016
Mr = 494.39	Dx = 1.522 Mg m−3
Monoclinic, P21/c	Melting point = 463–465 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.8022 (5) Å	Cell parameters from 6286 reflections
b = 6.5162 (3) Å	θ = 2.4–30.0°
c = 34.9982 (17) Å	µ = 2.04 mm−1
β = 105.102 (3)°	T = 100 K
V = 2158.24 (18) Å3	Block, yellow
Z = 4	0.34 × 0.31 × 0.19 mm

Bruker APEXII CCD area-detector diffractometer	6286 independent reflections
Radiation source: sealed tube	4937 reflections with I > 2σ(I)
graphite	Rint = 0.076
φ and ω scans	θmax = 30.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→12
Tmin = 0.547, Tmax = 0.703	k = −7→9
30564 measured reflections	l = −49→49

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.224	H-atom parameters constrained
S = 1.15	w = 1/[σ2(Fo2) + (0.0686P)2 + 18.6991P] where P = (Fo2 + 2Fc2)/3
6286 reflections	(Δ/σ)max = 0.001
275 parameters	Δρmax = 1.25 e Å−3
0 restraints	Δρmin = −1.36 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
Br1	0.61259 (6)	1.18042 (10)	0.235458 (16)	0.02660 (17)
S1	0.57829 (13)	0.5608 (2)	0.09005 (4)	0.0181 (3)
O1	0.0959 (4)	1.1839 (6)	0.19616 (10)	0.0174 (7)
O2	0.5793 (5)	0.6847 (7)	0.05563 (12)	0.0308 (9)
O3	0.6973 (4)	0.4215 (7)	0.10216 (13)	0.0288 (9)
O4	0.4420 (4)	0.4596 (6)	0.08582 (11)	0.0212 (7)
N1	−0.0521 (5)	0.0228 (7)	0.05416 (12)	0.0165 (8)
C1	−0.0322 (6)	−0.1561 (8)	0.03624 (14)	0.0190 (10)
H1A	−0.1099	−0.2379	0.0248	0.023*
C2	0.0992 (6)	−0.2181 (8)	0.03460 (14)	0.0200 (10)
H2A	0.1112	−0.3418	0.0226	0.024*
C3	0.2145 (6)	−0.0946 (8)	0.05103 (15)	0.0205 (10)
H3A	0.3045	−0.1329	0.0497	0.025*
C4	0.1943 (6)	0.0864 (9)	0.06946 (15)	0.0201 (10)
H4A	0.2718	0.1689	0.0807	0.024*
C5	0.0596 (5)	0.1481 (8)	0.07152 (14)	0.0159 (9)
C6	0.0314 (5)	0.3379 (8)	0.09094 (14)	0.0168 (9)
H6A	−0.0618	0.3793	0.0875	0.020*
C7	0.1350 (5)	0.4535 (8)	0.11338 (14)	0.0164 (9)
H7A	0.2272	0.4087	0.1163	0.020*
C8	0.1164 (5)	0.6439 (8)	0.13376 (14)	0.0160 (9)
C9	0.2375 (5)	0.7467 (8)	0.15528 (14)	0.0173 (9)
H9A	0.3262	0.6938	0.1559	0.021*
C10	0.2276 (5)	0.9264 (8)	0.17581 (14)	0.0175 (9)
H10A	0.3092	0.9922	0.1901	0.021*
C11	0.0950 (5)	1.0080 (7)	0.17496 (13)	0.0142 (8)
C12	−0.0272 (5)	0.9066 (8)	0.15352 (14)	0.0151 (9)
H12A	−0.1159	0.9596	0.1528	0.018*
C13	−0.0152 (5)	0.7263 (8)	0.13326 (14)	0.0161 (9)
H13A	−0.0967	0.6596	0.1191	0.019*
C14	−0.1979 (5)	0.0792 (9)	0.05387 (16)	0.0207 (10)
H14A	−0.2612	−0.0282	0.0415	0.031*
H14B	−0.2233	0.2044	0.0393	0.031*
H14C	−0.2042	0.0981	0.0806	0.031*
C15	−0.0362 (5)	1.2805 (8)	0.19457 (14)	0.0174 (9)
H15A	−0.1005	1.1843	0.2019	0.021*
H15B	−0.0792	1.3308	0.1681	0.021*
C16	−0.0034 (6)	1.4575 (8)	0.22382 (15)	0.0211 (10)
H16A	−0.0891	1.5296	0.2235	0.032*
H16B	0.0619	1.5497	0.2165	0.032*
H16C	0.0377	1.4051	0.2499	0.032*
C17	0.5949 (5)	0.7380 (8)	0.13010 (14)	0.0165 (9)
C18	0.5583 (5)	0.9431 (8)	0.12275 (15)	0.0194 (9)
H18A	0.5304	0.9911	0.0969	0.023*
C19	0.5634 (5)	1.0763 (8)	0.15409 (16)	0.0206 (10)
H19A	0.5389	1.2137	0.1495	0.025*
C20	0.6059 (5)	1.0000 (8)	0.19242 (15)	0.0187 (9)
C21	0.6451 (5)	0.7944 (9)	0.20045 (15)	0.0203 (10)
H21A	0.6745	0.7465	0.2263	0.024*
C22	0.6388 (5)	0.6640 (8)	0.16850 (15)	0.0194 (9)
H22A	0.6641	0.5268	0.1729	0.023*
O1W	0.2862 (4)	0.4509 (7)	0.00213 (12)	0.0272 (9)
H2W1	0.3391	0.4482	0.0256	0.06 (3)*
H1W1	0.3314	0.3960	−0.0129	0.04 (2)*

	U11	U22	U33	U12	U13	U23
Br1	0.0304 (3)	0.0266 (3)	0.0250 (3)	−0.0038 (2)	0.0113 (2)	−0.0113 (2)
S1	0.0172 (5)	0.0182 (6)	0.0201 (5)	−0.0051 (4)	0.0070 (4)	−0.0055 (4)
O1	0.0171 (16)	0.0143 (16)	0.0206 (16)	−0.0004 (13)	0.0045 (13)	−0.0053 (13)
O2	0.043 (2)	0.029 (2)	0.0243 (19)	−0.011 (2)	0.0162 (18)	−0.0062 (17)
O3	0.0190 (18)	0.028 (2)	0.038 (2)	0.0020 (16)	0.0049 (16)	−0.0159 (18)
O4	0.0161 (16)	0.0216 (19)	0.0256 (18)	−0.0063 (14)	0.0049 (14)	−0.0051 (15)
N1	0.020 (2)	0.014 (2)	0.0161 (18)	−0.0013 (16)	0.0057 (15)	−0.0011 (15)
C1	0.028 (3)	0.015 (2)	0.015 (2)	−0.0033 (19)	0.0065 (18)	−0.0008 (17)
C2	0.030 (3)	0.014 (2)	0.016 (2)	0.0012 (19)	0.0053 (19)	−0.0025 (17)
C3	0.024 (2)	0.019 (2)	0.019 (2)	0.005 (2)	0.0057 (18)	−0.0003 (19)
C4	0.021 (2)	0.021 (3)	0.018 (2)	−0.0006 (19)	0.0046 (18)	−0.0046 (18)
C5	0.020 (2)	0.013 (2)	0.0142 (19)	−0.0031 (17)	0.0036 (16)	−0.0017 (16)
C6	0.018 (2)	0.015 (2)	0.018 (2)	0.0004 (18)	0.0046 (17)	−0.0012 (17)
C7	0.018 (2)	0.016 (2)	0.016 (2)	0.0005 (18)	0.0070 (17)	−0.0011 (17)
C8	0.018 (2)	0.016 (2)	0.0148 (19)	−0.0022 (17)	0.0051 (16)	−0.0016 (17)
C9	0.018 (2)	0.016 (2)	0.018 (2)	−0.0004 (17)	0.0060 (17)	−0.0034 (17)
C10	0.016 (2)	0.019 (2)	0.017 (2)	−0.0034 (18)	0.0034 (16)	−0.0048 (18)
C11	0.017 (2)	0.013 (2)	0.0131 (19)	−0.0020 (16)	0.0043 (16)	−0.0019 (16)
C12	0.014 (2)	0.016 (2)	0.0152 (19)	0.0006 (17)	0.0043 (16)	−0.0012 (17)
C13	0.017 (2)	0.016 (2)	0.015 (2)	−0.0011 (17)	0.0040 (16)	−0.0018 (17)
C14	0.017 (2)	0.018 (2)	0.027 (2)	−0.0029 (18)	0.0048 (18)	−0.0055 (19)
C15	0.022 (2)	0.012 (2)	0.018 (2)	0.0016 (18)	0.0047 (17)	−0.0020 (17)
C16	0.025 (2)	0.017 (2)	0.021 (2)	0.006 (2)	0.0044 (19)	−0.0040 (18)
C17	0.014 (2)	0.017 (2)	0.019 (2)	−0.0039 (17)	0.0065 (17)	−0.0058 (17)
C18	0.018 (2)	0.020 (2)	0.020 (2)	−0.0010 (19)	0.0049 (18)	−0.0013 (19)
C19	0.018 (2)	0.016 (2)	0.026 (2)	−0.0003 (18)	0.0045 (19)	−0.0038 (19)
C20	0.017 (2)	0.020 (2)	0.020 (2)	−0.0020 (18)	0.0061 (17)	−0.0057 (18)
C21	0.020 (2)	0.021 (3)	0.019 (2)	−0.001 (2)	0.0047 (18)	−0.0016 (19)
C22	0.019 (2)	0.017 (2)	0.023 (2)	−0.0015 (18)	0.0068 (18)	−0.0037 (19)
O1W	0.0217 (18)	0.036 (2)	0.0234 (19)	−0.0020 (17)	0.0056 (15)	−0.0065 (17)

Br1—C20	1.898 (5)	C10—C11	1.397 (7)
S1—O3	1.451 (4)	C10—H10A	0.93
S1—O2	1.452 (4)	C11—C12	1.402 (6)
S1—O4	1.462 (4)	C12—C13	1.393 (7)
S1—C17	1.790 (5)	C12—H12A	0.93
O1—C11	1.365 (6)	C13—H13A	0.93
O1—C15	1.427 (6)	C14—H14A	0.96
N1—C1	1.361 (6)	C14—H14B	0.96
N1—C5	1.374 (6)	C14—H14C	0.96
N1—C14	1.473 (7)	C15—C16	1.520 (7)
C1—C2	1.366 (8)	C15—H15A	0.97
C1—H1A	0.93	C15—H15B	0.97
C2—C3	1.385 (8)	C16—H16A	0.96
C2—H2A	0.93	C16—H16B	0.96
C3—C4	1.383 (7)	C16—H16C	0.96
C3—H3A	0.93	C17—C22	1.387 (7)
C4—C5	1.401 (7)	C17—C18	1.390 (8)
C4—H4A	0.93	C18—C19	1.390 (7)
C5—C6	1.471 (7)	C18—H18A	0.93
C6—C7	1.341 (7)	C19—C20	1.389 (7)
C6—H6A	0.93	C19—H19A	0.93
C7—C8	1.466 (7)	C20—C21	1.402 (8)
C7—H7A	0.93	C21—C22	1.393 (7)
C8—C13	1.393 (7)	C21—H21A	0.93
C8—C9	1.400 (7)	C22—H22A	0.93
C9—C10	1.390 (7)	O1W—H2W1	0.85
C9—H9A	0.93	O1W—H1W1	0.85
O3—S1—O2	114.3 (3)	C13—C12—C11	119.7 (4)
O3—S1—O4	113.0 (3)	C13—C12—H12A	120.1
O2—S1—O4	111.7 (3)	C11—C12—H12A	120.1
O3—S1—C17	105.8 (2)	C12—C13—C8	121.3 (5)
O2—S1—C17	105.8 (3)	C12—C13—H13A	119.4
O4—S1—C17	105.3 (2)	C8—C13—H13A	119.4
C11—O1—C15	118.2 (4)	N1—C14—H14A	109.5
C1—N1—C5	121.3 (4)	N1—C14—H14B	109.5
C1—N1—C14	117.7 (4)	H14A—C14—H14B	109.5
C5—N1—C14	121.0 (4)	N1—C14—H14C	109.5
N1—C1—C2	121.5 (5)	H14A—C14—H14C	109.5
N1—C1—H1A	119.2	H14B—C14—H14C	109.5
C2—C1—H1A	119.2	O1—C15—C16	106.1 (4)
C1—C2—C3	119.2 (5)	O1—C15—H15A	110.5
C1—C2—H2A	120.4	C16—C15—H15A	110.5
C3—C2—H2A	120.4	O1—C15—H15B	110.5
C4—C3—C2	119.3 (5)	C16—C15—H15B	110.5
C4—C3—H3A	120.4	H15A—C15—H15B	108.7
C2—C3—H3A	120.4	C15—C16—H16A	109.5
C3—C4—C5	121.3 (5)	C15—C16—H16B	109.5
C3—C4—H4A	119.3	H16A—C16—H16B	109.5
C5—C4—H4A	119.3	C15—C16—H16C	109.5
N1—C5—C4	117.4 (4)	H16A—C16—H16C	109.5
N1—C5—C6	118.7 (4)	H16B—C16—H16C	109.5
C4—C5—C6	123.9 (4)	C22—C17—C18	120.9 (5)
C7—C6—C5	122.6 (5)	C22—C17—S1	118.5 (4)
C7—C6—H6A	118.7	C18—C17—S1	120.6 (4)
C5—C6—H6A	118.7	C19—C18—C17	120.0 (5)
C6—C7—C8	126.1 (5)	C19—C18—H18A	120.0
C6—C7—H7A	116.9	C17—C18—H18A	120.0
C8—C7—H7A	116.9	C20—C19—C18	118.6 (5)
C13—C8—C9	118.4 (5)	C20—C19—H19A	120.7
C13—C8—C7	123.5 (4)	C18—C19—H19A	120.7
C9—C8—C7	118.1 (4)	C19—C20—C21	122.2 (5)
C10—C9—C8	121.2 (5)	C19—C20—Br1	119.0 (4)
C10—C9—H9A	119.4	C21—C20—Br1	118.8 (4)
C8—C9—H9A	119.4	C22—C21—C20	118.0 (5)
C9—C10—C11	119.9 (4)	C22—C21—H21A	121.0
C9—C10—H10A	120.0	C20—C21—H21A	121.0
C11—C10—H10A	120.0	C17—C22—C21	120.2 (5)
O1—C11—C10	115.7 (4)	C17—C22—H22A	119.9
O1—C11—C12	124.7 (4)	C21—C22—H22A	119.9
C10—C11—C12	119.5 (4)	H2W1—O1W—H1W1	107.7
C5—N1—C1—C2	−0.3 (7)	O1—C11—C12—C13	−179.3 (4)
C14—N1—C1—C2	178.9 (5)	C10—C11—C12—C13	−0.2 (7)
N1—C1—C2—C3	−1.0 (8)	C11—C12—C13—C8	−0.1 (7)
C1—C2—C3—C4	1.4 (8)	C9—C8—C13—C12	0.1 (7)
C2—C3—C4—C5	−0.6 (8)	C7—C8—C13—C12	179.2 (5)
C1—N1—C5—C4	1.1 (7)	C11—O1—C15—C16	174.6 (4)
C14—N1—C5—C4	−178.1 (5)	O3—S1—C17—C22	−39.4 (5)
C1—N1—C5—C6	−179.1 (4)	O2—S1—C17—C22	−161.1 (4)
C14—N1—C5—C6	1.8 (7)	O4—S1—C17—C22	80.5 (4)
C3—C4—C5—N1	−0.6 (7)	O3—S1—C17—C18	143.5 (4)
C3—C4—C5—C6	179.5 (5)	O2—S1—C17—C18	21.8 (5)
N1—C5—C6—C7	170.2 (5)	O4—S1—C17—C18	−96.6 (4)
C4—C5—C6—C7	−10.0 (8)	C22—C17—C18—C19	−1.0 (7)
C5—C6—C7—C8	−179.9 (5)	S1—C17—C18—C19	176.0 (4)
C6—C7—C8—C13	2.2 (8)	C17—C18—C19—C20	0.2 (7)
C6—C7—C8—C9	−178.7 (5)	C18—C19—C20—C21	0.8 (8)
C13—C8—C9—C10	0.1 (7)	C18—C19—C20—Br1	−179.8 (4)
C7—C8—C9—C10	−179.0 (5)	C19—C20—C21—C22	−0.9 (8)
C8—C9—C10—C11	−0.4 (8)	Br1—C20—C21—C22	179.7 (4)
C15—O1—C11—C10	176.5 (4)	C18—C17—C22—C21	0.9 (7)
C15—O1—C11—C12	−4.3 (7)	S1—C17—C22—C21	−176.2 (4)
C9—C10—C11—O1	179.6 (4)	C20—C21—C22—C17	0.1 (7)
C9—C10—C11—C12	0.4 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W1···O4	0.85	2.09	2.929 (6)	171
O1W—H1W1···O2i	0.85	1.99	2.827 (6)	168
C1—H1A···O1Wii	0.93	2.23	3.154 (7)	176
C2—H2A···O1Wiii	0.93	2.43	3.223 (7)	143
C4—H4A···O4	0.93	2.50	3.378 (7)	158
C6—H6A···O3iv	0.93	2.56	3.442 (7)	159
C13—H13A···O3iv	0.93	2.49	3.387 (7)	161
C14—H14A···O2v	0.96	2.57	3.384 (7)	143
C14—H14C···O3iv	0.96	2.51	3.129 (7)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W1⋯O4	0.85	2.09	2.929 (6)	171
O1W—H1W1⋯O2i	0.85	1.99	2.827 (6)	168
C1—H1A⋯O1Wii	0.93	2.23	3.154 (7)	176
C2—H2A⋯O1Wiii	0.93	2.43	3.223 (7)	143
C4—H4A⋯O4	0.93	2.50	3.378 (7)	158
C6—H6A⋯O3iv	0.93	2.56	3.442 (7)	159
C13—H13A⋯O3iv	0.93	2.49	3.387 (7)	161
C14—H14A⋯O2v	0.96	2.57	3.384 (7)	143
C14—H14C⋯O3iv	0.96	2.51	3.129 (7)	122

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .