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

In the title salt, C(14)H(13)ClN(+)·C(6)H(4)ClO(3)S(-), the cation exists in an E configuration with respect to the ethynyl bond and is approximately planar, with a dihedral angle of 3.4 (2)° between the pyridinium and benzene rings. The anion is approximately perpendicular to the cation plane, the benzene ring of the anion making dihedral angles of 89.4 (2) and 89.9 (2)°, respectively, with the pyridinium and benzene rings of the cation. In the crystal structure, the cations are linked into a chain along the c axis by C-H⋯Cl inter-actions. The anions are linked to the adjacent cation chains by C-H⋯O and C-H⋯Cl inter-actions, forming a two-dimensional network parallel to the bc plane. The crystal structure is further stabilized by C-H⋯π inter-actions. A π-π inter-action is also observed between the pyridinium ring and the benzene ring of the cation with a centroid-centroid distance of 3.668 (3) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Koshima & Matsuura (1998 ▶); Prasad & Williams (1991 ▶); Wenseleers et al. (1998 ▶). For related structures, see: Chanawanno et al. (2008 ▶); Chantrapromma et al. (2007 ▶, 2008 ▶); Chantrapromma, Chanawanno & Fun (2009 ▶); Chantrapromma, Jansrisewangwong et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C14H13ClN+·C6H4ClO3S−

M = 422.32

Monoclinic,

a = 7.9018 (7) Å

b = 18.5102 (17) Å

c = 12.6818 (12) Å

β = 93.942 (7)°

V = 1850.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.49 mm−1

T = 100 K

0.19 × 0.17 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.913, T max = 0.959

19968 measured reflections

4249 independent reflections

2426 reflections with I > 2σ(I)

R int = 0.123

Refinement

R[F 2 > 2σ(F 2)] = 0.085

wR(F 2) = 0.215

S = 1.05

4249 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.82 e Å−3

Δρmin = −0.58 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 nd PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021667/is2430sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021667/is2430Isup2.hkl

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

C14H13ClN+·C6H4ClO3S−	F(000) = 872
Mr = 422.32	Dx = 1.516 Mg m−3
Monoclinic, P21/c	Melting point = 485–487 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9018 (7) Å	Cell parameters from 4249 reflections
b = 18.5102 (17) Å	θ = 2.0–27.5°
c = 12.6818 (12) Å	µ = 0.49 mm−1
β = 93.942 (7)°	T = 100 K
V = 1850.5 (3) Å3	Needle, orange
Z = 4	0.19 × 0.17 × 0.09 mm

Bruker APEXII CCD area-detector diffractometer	4249 independent reflections
Radiation source: sealed tube	2426 reflections with I > 2σ(I)
graphite	Rint = 0.123
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.913, Tmax = 0.959	k = −24→23
19968 measured reflections	l = −15→16

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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.215	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0922P)2 + 0.5785P] where P = (Fo2 + 2Fc2)/3
4249 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.82 e Å−3
0 restraints	Δρmin = −0.58 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
S1	0.14744 (15)	0.73096 (6)	0.57427 (10)	0.0223 (3)
Cl1	0.60079 (17)	0.44645 (8)	0.83430 (11)	0.0374 (4)
Cl2	0.76914 (16)	0.68816 (7)	0.90585 (10)	0.0315 (4)
N1	−0.0338 (5)	0.5768 (2)	0.2267 (3)	0.0242 (9)
O1	0.1460 (4)	0.80779 (17)	0.5473 (3)	0.0273 (8)
O2	−0.0022 (4)	0.70865 (18)	0.6258 (3)	0.0273 (8)
O3	0.1871 (4)	0.68462 (18)	0.4870 (3)	0.0300 (9)
C1	−0.1248 (6)	0.5785 (3)	0.1326 (4)	0.0295 (12)
H1A	−0.1595	0.6228	0.1040	0.035*
C2	−0.1670 (6)	0.5162 (3)	0.0788 (4)	0.0306 (12)
H2A	−0.2302	0.5180	0.0142	0.037*
C3	−0.1146 (6)	0.4514 (3)	0.1215 (4)	0.0306 (13)
H3A	−0.1406	0.4087	0.0852	0.037*
C4	−0.0239 (6)	0.4492 (3)	0.2176 (4)	0.0312 (13)
H4A	0.0093	0.4048	0.2464	0.037*
C5	0.0196 (6)	0.5129 (3)	0.2734 (4)	0.0283 (12)
C6	0.1196 (6)	0.5163 (3)	0.3718 (4)	0.0296 (12)
H6A	0.1531	0.5615	0.3979	0.035*
C7	0.1672 (6)	0.4577 (3)	0.4281 (4)	0.0309 (13)
H7A	0.1299	0.4131	0.4018	0.037*
C8	0.2740 (6)	0.4578 (3)	0.5282 (4)	0.0256 (12)
C9	0.3296 (6)	0.3914 (3)	0.5712 (4)	0.0292 (12)
H9A	0.2971	0.3487	0.5368	0.035*
C10	0.4323 (6)	0.3886 (3)	0.6639 (4)	0.0314 (13)
H10A	0.4709	0.3444	0.6909	0.038*
C11	0.4766 (6)	0.4515 (3)	0.7157 (4)	0.0246 (11)
C12	0.4242 (6)	0.5184 (3)	0.6760 (4)	0.0271 (12)
H12A	0.4562	0.5607	0.7116	0.032*
C13	0.3237 (6)	0.5208 (3)	0.5825 (4)	0.0268 (12)
H13A	0.2885	0.5654	0.5551	0.032*
C14	0.0109 (6)	0.6469 (3)	0.2776 (4)	0.0296 (12)
H14A	−0.0401	0.6855	0.2360	0.044*
H14B	0.1319	0.6527	0.2828	0.044*
H14C	−0.0301	0.6480	0.3471	0.044*
C15	0.3208 (6)	0.7181 (2)	0.6698 (4)	0.0217 (11)
C16	0.2956 (6)	0.7066 (2)	0.7776 (4)	0.0229 (11)
H16A	0.1862	0.7062	0.8004	0.027*
C17	0.4327 (6)	0.6958 (2)	0.8495 (4)	0.0248 (11)
H17A	0.4160	0.6872	0.9203	0.030*
C18	0.5940 (6)	0.6977 (2)	0.8154 (4)	0.0248 (11)
C19	0.6226 (6)	0.7092 (3)	0.7092 (4)	0.0242 (11)
H19A	0.7322	0.7099	0.6867	0.029*
C20	0.4844 (6)	0.7192 (2)	0.6385 (4)	0.0231 (11)
H20A	0.5020	0.7270	0.5676	0.028*

	U11	U22	U33	U12	U13	U23
S1	0.0271 (6)	0.0151 (7)	0.0242 (7)	0.0003 (5)	−0.0022 (5)	−0.0002 (5)
Cl1	0.0445 (8)	0.0359 (9)	0.0306 (8)	−0.0021 (6)	−0.0061 (6)	0.0026 (6)
Cl2	0.0339 (7)	0.0273 (7)	0.0317 (8)	0.0026 (5)	−0.0097 (6)	−0.0012 (6)
N1	0.029 (2)	0.021 (2)	0.023 (2)	−0.0022 (18)	0.0003 (19)	−0.0006 (18)
O1	0.0359 (19)	0.0165 (19)	0.028 (2)	0.0014 (15)	−0.0052 (16)	0.0039 (15)
O2	0.0245 (17)	0.023 (2)	0.033 (2)	−0.0006 (14)	−0.0059 (15)	0.0014 (16)
O3	0.041 (2)	0.023 (2)	0.025 (2)	0.0034 (16)	−0.0047 (16)	−0.0076 (15)
C1	0.033 (3)	0.033 (3)	0.022 (3)	0.000 (2)	0.003 (2)	0.003 (2)
C2	0.039 (3)	0.033 (3)	0.020 (3)	−0.006 (2)	0.004 (2)	−0.004 (2)
C3	0.039 (3)	0.029 (3)	0.025 (3)	−0.012 (2)	0.008 (2)	−0.003 (2)
C4	0.038 (3)	0.015 (3)	0.041 (3)	−0.003 (2)	0.006 (3)	0.000 (2)
C5	0.024 (3)	0.029 (3)	0.033 (3)	0.000 (2)	0.003 (2)	0.003 (2)
C6	0.037 (3)	0.017 (3)	0.034 (3)	−0.004 (2)	−0.001 (3)	−0.002 (2)
C7	0.035 (3)	0.021 (3)	0.036 (3)	0.000 (2)	0.002 (3)	−0.004 (2)
C8	0.025 (3)	0.024 (3)	0.028 (3)	−0.001 (2)	−0.003 (2)	0.001 (2)
C9	0.040 (3)	0.018 (3)	0.030 (3)	−0.001 (2)	0.002 (2)	−0.002 (2)
C10	0.038 (3)	0.020 (3)	0.036 (3)	0.002 (2)	−0.002 (3)	0.006 (2)
C11	0.031 (3)	0.023 (3)	0.020 (3)	0.001 (2)	0.000 (2)	0.001 (2)
C12	0.030 (3)	0.020 (3)	0.032 (3)	−0.005 (2)	0.003 (2)	−0.004 (2)
C13	0.031 (3)	0.016 (3)	0.033 (3)	0.000 (2)	−0.002 (2)	0.002 (2)
C14	0.043 (3)	0.017 (3)	0.029 (3)	−0.005 (2)	0.001 (2)	−0.001 (2)
C15	0.028 (3)	0.015 (3)	0.021 (3)	−0.001 (2)	0.000 (2)	−0.005 (2)
C16	0.030 (3)	0.010 (2)	0.029 (3)	0.0008 (19)	0.004 (2)	−0.002 (2)
C17	0.037 (3)	0.014 (3)	0.022 (3)	0.002 (2)	−0.007 (2)	−0.001 (2)
C18	0.030 (3)	0.011 (3)	0.032 (3)	0.001 (2)	−0.005 (2)	−0.002 (2)
C19	0.022 (2)	0.023 (3)	0.027 (3)	0.000 (2)	−0.001 (2)	−0.002 (2)
C20	0.029 (3)	0.019 (3)	0.021 (3)	−0.004 (2)	0.000 (2)	−0.002 (2)

S1—O2	1.450 (3)	C8—C9	1.402 (7)
S1—O3	1.451 (3)	C9—C10	1.383 (7)
S1—O1	1.462 (3)	C9—H9A	0.9300
S1—C15	1.781 (5)	C10—C11	1.370 (7)
Cl1—C11	1.741 (5)	C10—H10A	0.9300
Cl2—C18	1.745 (5)	C11—C12	1.389 (7)
N1—C1	1.350 (6)	C12—C13	1.382 (7)
N1—C5	1.375 (6)	C12—H12A	0.9300
N1—C14	1.482 (6)	C13—H13A	0.9300
C1—C2	1.369 (7)	C14—H14A	0.9600
C1—H1A	0.9300	C14—H14B	0.9600
C2—C3	1.370 (7)	C14—H14C	0.9600
C2—H2A	0.9300	C15—C20	1.379 (6)
C3—C4	1.372 (7)	C15—C16	1.411 (6)
C3—H3A	0.9300	C16—C17	1.382 (7)
C4—C5	1.406 (7)	C16—H16A	0.9300
C4—H4A	0.9300	C17—C18	1.374 (7)
C5—C6	1.432 (7)	C17—H17A	0.9300
C6—C7	1.339 (7)	C18—C19	1.398 (7)
C6—H6A	0.9300	C19—C20	1.377 (6)
C7—C8	1.475 (7)	C19—H19A	0.9300
C7—H7A	0.9300	C20—H20A	0.9300
C8—C13	1.397 (7)
O2—S1—O3	113.6 (2)	C11—C10—C9	119.4 (5)
O2—S1—O1	112.9 (2)	C11—C10—H10A	120.3
O3—S1—O1	113.3 (2)	C9—C10—H10A	120.3
O2—S1—C15	105.5 (2)	C10—C11—C12	121.5 (5)
O3—S1—C15	104.1 (2)	C10—C11—Cl1	118.6 (4)
O1—S1—C15	106.4 (2)	C12—C11—Cl1	119.8 (4)
C1—N1—C5	122.0 (4)	C13—C12—C11	118.7 (5)
C1—N1—C14	117.4 (4)	C13—C12—H12A	120.7
C5—N1—C14	120.5 (4)	C11—C12—H12A	120.7
N1—C1—C2	121.1 (5)	C12—C13—C8	121.4 (5)
N1—C1—H1A	119.4	C12—C13—H13A	119.3
C2—C1—H1A	119.4	C8—C13—H13A	119.3
C1—C2—C3	119.0 (5)	N1—C14—H14A	109.5
C1—C2—H2A	120.5	N1—C14—H14B	109.5
C3—C2—H2A	120.5	H14A—C14—H14B	109.5
C2—C3—C4	120.2 (5)	N1—C14—H14C	109.5
C2—C3—H3A	119.9	H14A—C14—H14C	109.5
C4—C3—H3A	119.9	H14B—C14—H14C	109.5
C3—C4—C5	121.2 (5)	C20—C15—C16	118.6 (4)
C3—C4—H4A	119.4	C20—C15—S1	119.6 (4)
C5—C4—H4A	119.4	C16—C15—S1	121.8 (4)
N1—C5—C4	116.6 (5)	C17—C16—C15	120.3 (4)
N1—C5—C6	118.2 (4)	C17—C16—H16A	119.8
C4—C5—C6	125.2 (5)	C15—C16—H16A	119.8
C7—C6—C5	123.1 (5)	C18—C17—C16	119.4 (5)
C7—C6—H6A	118.4	C18—C17—H17A	120.3
C5—C6—H6A	118.4	C16—C17—H17A	120.3
C6—C7—C8	125.5 (5)	C17—C18—C19	121.5 (4)
C6—C7—H7A	117.2	C17—C18—Cl2	120.1 (4)
C8—C7—H7A	117.2	C19—C18—Cl2	118.4 (4)
C13—C8—C9	118.1 (5)	C20—C19—C18	118.3 (4)
C13—C8—C7	123.3 (5)	C20—C19—H19A	120.8
C9—C8—C7	118.6 (5)	C18—C19—H19A	120.8
C10—C9—C8	120.9 (5)	C19—C20—C15	121.9 (4)
C10—C9—H9A	119.6	C19—C20—H20A	119.1
C8—C9—H9A	119.6	C15—C20—H20A	119.1
C5—N1—C1—C2	−0.6 (7)	C10—C11—C12—C13	0.6 (7)
C14—N1—C1—C2	178.0 (4)	Cl1—C11—C12—C13	−179.1 (4)
N1—C1—C2—C3	−0.3 (7)	C11—C12—C13—C8	0.3 (7)
C1—C2—C3—C4	1.1 (7)	C9—C8—C13—C12	−0.3 (7)
C2—C3—C4—C5	−1.1 (7)	C7—C8—C13—C12	−179.8 (4)
C1—N1—C5—C4	0.6 (6)	O2—S1—C15—C20	165.8 (4)
C14—N1—C5—C4	−177.9 (4)	O3—S1—C15—C20	45.9 (4)
C1—N1—C5—C6	178.3 (4)	O1—S1—C15—C20	−74.1 (4)
C14—N1—C5—C6	−0.3 (6)	O2—S1—C15—C16	−14.1 (4)
C3—C4—C5—N1	0.2 (7)	O3—S1—C15—C16	−134.0 (4)
C3—C4—C5—C6	−177.3 (5)	O1—S1—C15—C16	106.0 (4)
N1—C5—C6—C7	174.7 (5)	C20—C15—C16—C17	−0.8 (7)
C4—C5—C6—C7	−7.9 (8)	S1—C15—C16—C17	179.1 (4)
C5—C6—C7—C8	178.2 (4)	C15—C16—C17—C18	1.2 (7)
C6—C7—C8—C13	7.1 (8)	C16—C17—C18—C19	−1.1 (7)
C6—C7—C8—C9	−172.5 (5)	C16—C17—C18—Cl2	177.2 (4)
C13—C8—C9—C10	−0.7 (7)	C17—C18—C19—C20	0.6 (7)
C7—C8—C9—C10	178.9 (4)	Cl2—C18—C19—C20	−177.7 (4)
C8—C9—C10—C11	1.6 (7)	C18—C19—C20—C15	−0.2 (7)
C9—C10—C11—C12	−1.6 (7)	C16—C15—C20—C19	0.3 (7)
C9—C10—C11—Cl1	178.2 (4)	S1—C15—C20—C19	−179.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl2i	0.93	2.81	3.572 (5)	140
C3—H3A···O1ii	0.93	2.51	3.411 (6)	163
C6—H6A···O3	0.93	2.55	3.467 (6)	168
C7—H7A···O2iii	0.93	2.48	3.395 (6)	166
C13—H13A···O3	0.93	2.48	3.413 (6)	178
C14—H14A···O2iv	0.96	2.44	3.292 (6)	148
C14—H14C···O3	0.96	2.48	2.995 (6)	114
C16—H16A···O2	0.93	2.58	2.936 (6)	103
C19—H19A···O2v	0.93	2.29	3.216 (6)	178
C10—H10A···Cg3vi	0.93	2.71	3.632 (6)	172
C12—H12A···Cg3	0.93	2.75	3.614 (6)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl2i	0.93	2.81	3.572 (5)	140
C3—H3A⋯O1ii	0.93	2.51	3.411 (6)	163
C6—H6A⋯O3	0.93	2.55	3.467 (6)	168
C7—H7A⋯O2iii	0.93	2.48	3.395 (6)	166
C13—H13A⋯O3	0.93	2.48	3.413 (6)	178
C14—H14A⋯O2iv	0.96	2.44	3.292 (6)	148
C14—H14C⋯O3	0.96	2.48	2.995 (6)	114
C16—H16A⋯O2	0.93	2.58	2.936 (6)	103
C19—H19A⋯O2v	0.93	2.29	3.216 (6)	178
C10—H10A⋯Cg3vi	0.93	2.71	3.632 (6)	172
C12—H12A⋯Cg3	0.93	2.75	3.614 (6)	154

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