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

In the title compound, C(14)H(13)ClN(+)·C(6)H(4)BrO(3)S(-), the cation exists in an E configuration with respect to the ethenyl bond and is almost planar, the dihedral angle between the pyridinium and the benzene rings being 2.80 (7)°. The dihedral angles between the benzene ring of the anion and the pyridinium and benzene rings of the cation are 80.88 (7) and 79.05 (7)°, respectively. In the crystal, the cations are stacked into columns along the a axis as a result of π-π inter-actions between the pyridinium and chloro-benzene rings with a Cg⋯Cg distance of 3.6976 (8) Å. The anions are linked into chains along the a axis by weak C-H⋯O inter-actions. These anion chains are linked to adjacent cations by additional weak C-H⋯O and C-H⋯Br inter-actions, forming a two-dimensional network parallel to the ab plane. There are also short O⋯Br [3.2567 (11) Å] and C⋯O [2.9917 (18) Å] contacts. The crystal structure is further stabilized by C-H⋯π inter-actions involving the aromatic ring of the anion.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Andreu et al. (1999 ▶); Jagannathan et al. (2007 ▶); Cho et al. (2002 ▶); Lakshmanaperumal et al. (2003 ▶); Veiros (2001 ▶). For related structures, see: Chanawanno et al. (2008 ▶; 2009 ▶); Chantrapromma et al. (2006 ▶); Fun et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C14H13ClN+·C6H4BrO3S−

M = 466.77

Monoclinic,

a = 7.9476 (1) Å

b = 18.6099 (3) Å

c = 12.7173 (2) Å

β = 93.467 (1)°

V = 1877.50 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.46 mm−1

T = 100 K

0.51 × 0.26 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.368, T max = 0.586 (expected range = 0.348–0.554)

36425 measured reflections

8227 independent reflections

6744 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.02

8227 reflections

245 parameters

H-atom parameters constrained

Δρmax = 1.30 e Å−3

Δρmin = −0.73 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, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026968/sj2633sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026968/sj2633Isup2.hkl

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

C14H13ClN+·C6H4BrO3S−	F(000) = 944
Mr = 466.77	Dx = 1.651 Mg m−3
Monoclinic, P21/c	Melting point = 508–509 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9476 (1) Å	Cell parameters from 8227 reflections
b = 18.6099 (3) Å	θ = 2.2–35.0°
c = 12.7173 (2) Å	µ = 2.46 mm−1
β = 93.467 (1)°	T = 100 K
V = 1877.50 (5) Å3	Block, brown
Z = 4	0.51 × 0.26 × 0.24 mm

Bruker APEXII CCD area-detector diffractometer	8227 independent reflections
Radiation source: sealed tube	6744 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 35.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
Tmin = 0.368, Tmax = 0.586	k = −29→30
36425 measured reflections	l = −20→20

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0355P)2 + 1.227P] where P = (Fo2 + 2Fc2)/3
8227 reflections	(Δ/σ)max = 0.002
245 parameters	Δρmax = 1.30 e Å−3
0 restraints	Δρmin = −0.73 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	0.233790 (18)	0.807999 (8)	0.089929 (11)	0.01901 (4)
Cl1	0.39854 (5)	0.44980 (2)	−0.33199 (3)	0.02829 (8)
S1	0.87153 (4)	0.769209 (17)	0.42302 (2)	0.01344 (6)
N1	1.03961 (15)	0.57489 (6)	0.26973 (9)	0.0163 (2)
O1	1.01963 (13)	0.79162 (6)	0.36935 (9)	0.01957 (19)
O2	0.83179 (15)	0.81603 (6)	0.50948 (8)	0.0220 (2)
O3	0.87526 (14)	0.69338 (5)	0.45166 (8)	0.01917 (19)
C1	1.1310 (2)	0.57574 (8)	0.36310 (11)	0.0206 (3)
H1A	1.1703	0.6194	0.3904	0.025*
C2	1.1670 (2)	0.51371 (8)	0.41839 (11)	0.0219 (3)
H2A	1.2302	0.5150	0.4823	0.026*
C3	1.1070 (2)	0.44893 (8)	0.37682 (11)	0.0214 (3)
H3A	1.1279	0.4063	0.4134	0.026*
C4	1.01612 (19)	0.44842 (8)	0.28073 (11)	0.0195 (2)
H4A	0.9780	0.4050	0.2521	0.023*
C5	0.98054 (17)	0.51241 (7)	0.22572 (11)	0.0163 (2)
C6	0.88146 (18)	0.51613 (7)	0.12614 (11)	0.0180 (2)
H6A	0.8578	0.5612	0.0973	0.022*
C7	0.82227 (19)	0.45815 (7)	0.07362 (11)	0.0191 (2)
H7A	0.8488	0.4134	0.1027	0.023*
C8	0.71911 (18)	0.45944 (7)	−0.02595 (11)	0.0166 (2)
C9	0.6540 (2)	0.39406 (7)	−0.06589 (11)	0.0207 (3)
H9A	0.6790	0.3518	−0.0293	0.025*
C10	0.5528 (2)	0.39117 (8)	−0.15891 (12)	0.0225 (3)
H10A	0.5082	0.3477	−0.1836	0.027*
C11	0.51988 (19)	0.45417 (8)	−0.21391 (11)	0.0193 (2)
C12	0.58160 (19)	0.52002 (8)	−0.17711 (11)	0.0193 (2)
H12A	0.5572	0.5619	−0.2149	0.023*
C13	0.68025 (18)	0.52247 (7)	−0.08315 (11)	0.0184 (2)
H13A	0.7211	0.5664	−0.0578	0.022*
C14	1.0017 (2)	0.64493 (7)	0.21800 (11)	0.0202 (3)
H14A	1.0547	0.6828	0.2591	0.030*
H14B	0.8820	0.6524	0.2126	0.030*
H14C	1.0439	0.6449	0.1488	0.030*
C15	0.69849 (16)	0.77983 (7)	0.32849 (10)	0.0132 (2)
C16	0.53518 (17)	0.77816 (7)	0.36296 (10)	0.0166 (2)
H16A	0.5188	0.7707	0.4339	0.020*
C17	0.39682 (17)	0.78748 (7)	0.29222 (11)	0.0162 (2)
H17A	0.2879	0.7859	0.3150	0.019*
C18	0.42424 (17)	0.79926 (7)	0.18665 (10)	0.0146 (2)
C19	0.58535 (18)	0.80181 (7)	0.15040 (10)	0.0150 (2)
H19A	0.6012	0.8102	0.0796	0.018*
C20	0.72348 (17)	0.79154 (7)	0.22238 (10)	0.0139 (2)
H20A	0.8323	0.7925	0.1993	0.017*

	U11	U22	U33	U12	U13	U23
Br1	0.01657 (7)	0.02094 (6)	0.01858 (6)	0.00174 (5)	−0.00664 (5)	0.00000 (5)
Cl1	0.02706 (18)	0.0357 (2)	0.02110 (15)	0.00237 (15)	−0.00652 (13)	−0.00412 (14)
S1	0.01243 (13)	0.01367 (12)	0.01385 (12)	0.00116 (10)	−0.00235 (10)	−0.00005 (9)
N1	0.0170 (5)	0.0155 (5)	0.0163 (5)	0.0024 (4)	0.0002 (4)	−0.0001 (4)
O1	0.0124 (4)	0.0235 (5)	0.0225 (5)	−0.0018 (4)	−0.0013 (4)	0.0022 (4)
O2	0.0244 (5)	0.0241 (5)	0.0169 (4)	0.0055 (4)	−0.0041 (4)	−0.0065 (4)
O3	0.0203 (5)	0.0150 (4)	0.0215 (4)	0.0013 (4)	−0.0043 (4)	0.0040 (3)
C1	0.0247 (7)	0.0205 (6)	0.0162 (5)	0.0026 (5)	−0.0010 (5)	−0.0015 (4)
C2	0.0251 (7)	0.0248 (6)	0.0154 (5)	0.0050 (5)	−0.0009 (5)	0.0015 (5)
C3	0.0249 (7)	0.0205 (6)	0.0190 (6)	0.0057 (5)	0.0023 (5)	0.0034 (5)
C4	0.0209 (6)	0.0164 (5)	0.0212 (6)	0.0017 (5)	0.0007 (5)	0.0013 (4)
C5	0.0153 (6)	0.0161 (5)	0.0173 (5)	0.0026 (4)	−0.0003 (4)	0.0000 (4)
C6	0.0196 (6)	0.0169 (5)	0.0171 (5)	0.0012 (5)	−0.0020 (5)	0.0007 (4)
C7	0.0226 (6)	0.0170 (6)	0.0176 (5)	0.0008 (5)	0.0003 (5)	0.0013 (4)
C8	0.0169 (6)	0.0146 (5)	0.0183 (5)	−0.0003 (4)	−0.0001 (4)	−0.0001 (4)
C9	0.0261 (7)	0.0141 (5)	0.0217 (6)	−0.0008 (5)	−0.0021 (5)	−0.0002 (4)
C10	0.0278 (7)	0.0174 (6)	0.0220 (6)	−0.0026 (5)	−0.0016 (5)	−0.0034 (5)
C11	0.0186 (6)	0.0221 (6)	0.0170 (5)	0.0015 (5)	−0.0004 (5)	−0.0023 (4)
C12	0.0197 (6)	0.0176 (6)	0.0203 (6)	0.0012 (5)	−0.0014 (5)	0.0018 (4)
C13	0.0182 (6)	0.0144 (5)	0.0223 (6)	−0.0009 (4)	−0.0008 (5)	0.0004 (4)
C14	0.0268 (7)	0.0143 (5)	0.0191 (6)	0.0023 (5)	−0.0032 (5)	0.0006 (4)
C15	0.0131 (5)	0.0127 (5)	0.0137 (5)	0.0005 (4)	−0.0008 (4)	0.0000 (4)
C16	0.0145 (5)	0.0206 (6)	0.0146 (5)	0.0016 (5)	0.0002 (4)	0.0018 (4)
C17	0.0126 (5)	0.0194 (5)	0.0166 (5)	0.0012 (4)	−0.0004 (4)	0.0010 (4)
C18	0.0136 (5)	0.0140 (5)	0.0156 (5)	0.0011 (4)	−0.0036 (4)	−0.0003 (4)
C19	0.0175 (6)	0.0146 (5)	0.0127 (5)	0.0004 (4)	−0.0011 (4)	−0.0006 (4)
C20	0.0132 (5)	0.0143 (5)	0.0141 (5)	0.0006 (4)	0.0003 (4)	−0.0002 (4)

Br1—C18	1.8988 (13)	C8—C9	1.4052 (19)
Cl1—C11	1.7368 (14)	C9—C10	1.390 (2)
S1—O2	1.4525 (11)	C9—H9A	0.9300
S1—O1	1.4569 (11)	C10—C11	1.382 (2)
S1—O3	1.4572 (10)	C10—H10A	0.9300
S1—C15	1.7820 (13)	C11—C12	1.390 (2)
N1—C1	1.3540 (18)	C12—C13	1.390 (2)
N1—C5	1.3615 (18)	C12—H12A	0.9300
N1—C14	1.4828 (17)	C13—H13A	0.9300
C1—C2	1.373 (2)	C14—H14A	0.9600
C1—H1A	0.9300	C14—H14B	0.9600
C2—C3	1.389 (2)	C14—H14C	0.9600
C2—H2A	0.9300	C15—C20	1.3930 (18)
C3—C4	1.381 (2)	C15—C16	1.3952 (19)
C3—H3A	0.9300	C16—C17	1.3889 (18)
C4—C5	1.4013 (19)	C16—H16A	0.9300
C4—H4A	0.9300	C17—C18	1.3905 (19)
C5—C6	1.4518 (19)	C17—H17A	0.9300
C6—C7	1.3393 (19)	C18—C19	1.3877 (19)
C6—H6A	0.9300	C19—C20	1.3993 (18)
C7—C8	1.4665 (19)	C19—H19A	0.9300
C7—H7A	0.9300	C20—H20A	0.9300
C8—C13	1.4048 (19)
O2—S1—O1	113.69 (7)	C11—C10—C9	118.67 (13)
O2—S1—O3	113.19 (7)	C11—C10—H10A	120.7
O1—S1—O3	112.92 (7)	C9—C10—H10A	120.7
O2—S1—C15	104.47 (6)	C10—C11—C12	121.67 (13)
O1—S1—C15	105.34 (6)	C10—C11—Cl1	118.43 (11)
O3—S1—C15	106.22 (6)	C12—C11—Cl1	119.90 (11)
C1—N1—C5	121.59 (12)	C13—C12—C11	119.18 (13)
C1—N1—C14	117.56 (12)	C13—C12—H12A	120.4
C5—N1—C14	120.84 (11)	C11—C12—H12A	120.4
N1—C1—C2	121.57 (14)	C12—C13—C8	120.85 (13)
N1—C1—H1A	119.2	C12—C13—H13A	119.6
C2—C1—H1A	119.2	C8—C13—H13A	119.6
C1—C2—C3	118.61 (13)	N1—C14—H14A	109.5
C1—C2—H2A	120.7	N1—C14—H14B	109.5
C3—C2—H2A	120.7	H14A—C14—H14B	109.5
C4—C3—C2	119.44 (13)	N1—C14—H14C	109.5
C4—C3—H3A	120.3	H14A—C14—H14C	109.5
C2—C3—H3A	120.3	H14B—C14—H14C	109.5
C3—C4—C5	120.98 (13)	C20—C15—C16	119.85 (12)
C3—C4—H4A	119.5	C20—C15—S1	121.43 (10)
C5—C4—H4A	119.5	C16—C15—S1	118.70 (9)
N1—C5—C4	117.80 (12)	C17—C16—C15	120.59 (12)
N1—C5—C6	118.24 (12)	C17—C16—H16A	119.7
C4—C5—C6	123.95 (13)	C15—C16—H16A	119.7
C7—C6—C5	123.52 (13)	C16—C17—C18	118.74 (13)
C7—C6—H6A	118.2	C16—C17—H17A	120.6
C5—C6—H6A	118.2	C18—C17—H17A	120.6
C6—C7—C8	125.35 (13)	C19—C18—C17	121.86 (12)
C6—C7—H7A	117.3	C19—C18—Br1	119.82 (10)
C8—C7—H7A	117.3	C17—C18—Br1	118.27 (10)
C13—C8—C9	118.10 (12)	C18—C19—C20	118.76 (12)
C13—C8—C7	123.69 (12)	C18—C19—H19A	120.6
C9—C8—C7	118.20 (12)	C20—C19—H19A	120.6
C10—C9—C8	121.50 (13)	C15—C20—C19	120.19 (12)
C10—C9—H9A	119.3	C15—C20—H20A	119.9
C8—C9—H9A	119.3	C19—C20—H20A	119.9
C5—N1—C1—C2	−0.7 (2)	C10—C11—C12—C13	0.6 (2)
C14—N1—C1—C2	177.66 (14)	Cl1—C11—C12—C13	−179.20 (11)
N1—C1—C2—C3	−0.2 (2)	C11—C12—C13—C8	0.6 (2)
C1—C2—C3—C4	1.2 (2)	C9—C8—C13—C12	−0.7 (2)
C2—C3—C4—C5	−1.4 (2)	C7—C8—C13—C12	−179.97 (14)
C1—N1—C5—C4	0.5 (2)	O2—S1—C15—C20	132.62 (11)
C14—N1—C5—C4	−177.77 (13)	O1—S1—C15—C20	12.55 (12)
C1—N1—C5—C6	179.13 (13)	O3—S1—C15—C20	−107.47 (11)
C14—N1—C5—C6	0.8 (2)	O2—S1—C15—C16	−45.68 (12)
C3—C4—C5—N1	0.5 (2)	O1—S1—C15—C16	−165.75 (11)
C3—C4—C5—C6	−178.01 (14)	O3—S1—C15—C16	74.23 (12)
N1—C5—C6—C7	177.40 (14)	C20—C15—C16—C17	0.5 (2)
C4—C5—C6—C7	−4.1 (2)	S1—C15—C16—C17	178.87 (11)
C5—C6—C7—C8	178.74 (14)	C15—C16—C17—C18	−0.7 (2)
C6—C7—C8—C13	5.2 (2)	C16—C17—C18—C19	0.1 (2)
C6—C7—C8—C9	−174.16 (15)	C16—C17—C18—Br1	177.48 (10)
C13—C8—C9—C10	−0.4 (2)	C17—C18—C19—C20	0.59 (19)
C7—C8—C9—C10	178.93 (14)	Br1—C18—C19—C20	−176.75 (9)
C8—C9—C10—C11	1.6 (2)	C16—C15—C20—C19	0.17 (19)
C9—C10—C11—C12	−1.7 (2)	S1—C15—C20—C19	−178.11 (10)
C9—C10—C11—Cl1	178.16 (12)	C18—C19—C20—C15	−0.72 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Br1i	0.93	2.89	3.6585 (14)	141
C3—H3A···O3ii	0.93	2.53	3.4285 (17)	163
C6—H6A···O2iii	0.93	2.55	3.4702 (17)	172
C7—H7A···O1iv	0.93	2.51	3.4057 (17)	161
C13—H13A···O2iii	0.93	2.49	3.4205 (17)	180
C14—H14A···O1	0.96	2.49	3.3383 (17)	148
C14—H14C···O2iii	0.96	2.48	2.9917 (18)	113
C17—H17A···O1v	0.93	2.28	3.2110 (17)	175
C20—H20A···O1	0.93	2.55	2.9157 (17)	104
C10—H10A···Cg3vi	0.93	2.77	3.6831 (16)	169
C12—H12A···Cg3iii	0.93	2.79	3.6402 (16)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Br1i	0.93	2.89	3.6585 (14)	141
C3—H3A⋯O3ii	0.93	2.53	3.4285 (17)	163
C6—H6A⋯O2iii	0.93	2.55	3.4702 (17)	172
C7—H7A⋯O1iv	0.93	2.51	3.4057 (17)	161
C13—H13A⋯O2iii	0.93	2.49	3.4205 (17)	180
C14—H14A⋯O1	0.96	2.49	3.3383 (17)	148
C14—H14C⋯O2iii	0.96	2.48	2.9917 (18)	113
C17—H17A⋯O1v	0.93	2.28	3.2110 (17)	175
C20—H20A⋯O1	0.93	2.55	2.9157 (17)	104
C10—H10A⋯Cg3vi	0.93	2.77	3.6831 (16)	169
C12—H12A⋯Cg3iii	0.93	2.79	3.6402 (16)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg3 is the centroid of the C15–C20 ring.