1-Methyl-4-[(E)-2-(2-thien-yl)ethen-yl]pyridinium 4-chloro-benzene-sulfonate.

In the title compound, C(12)H(12)NS(+)·C(6)H(4)ClO(3)S(-), the cation is almost planar and exists in the E configuration. The cations and anions form alternate layers parallel to the ab plane. Within each layer, both cations and anions form chains directed along the b axis. The mol-ecules are inter-connected by weak C-H⋯O inter-actions into a three-dimensional network. The crystal structure is further stabilized by C-H⋯π inter-actions involving the thio-phene ring. The sulfonate and thio-phene groups are involved in weak intra-molecular C-H⋯O and C-H⋯S inter-actions, respectively. The latter intra-molecular hydrogen bonds produce S(5) ring motifs.

Related literature

For bond lengths and angles, see Allen (2002 ▶); Allen et al. (1987 ▶). For related literature on hydrogen-bond motifs, see Bernstein et al. (1995 ▶). For related structures, see for example Chantrapromma et al. (2005 ▶, 2006a ▶,b ▶, 2007a ▶,b ▶,c ▶,d ▶); Drost et al. (1995 ▶); Jindawong et al. (2005 ▶); Subramaniyan et al. (2003 ▶).

Experimental

Crystal data

C12H12NS+·C6H4ClO3S−

M = 393.91

Monoclinic,

a = 7.3532 (1) Å

b = 14.0250 (2) Å

c = 18.3755 (2) Å

β = 111.232 (1)°

V = 1766.41 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.47 mm−1

T = 100.0 (1) K

0.49 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.883, T max = 0.919

23692 measured reflections

4688 independent reflections

3913 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.094

S = 1.06

4688 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.42 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808003929/fb2086sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003929/fb2086Isup2.hkl

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

C12H12NS+·C6H4ClO3S–	F000 = 816
Mr = 393.91	Dx = 1.481 Mg m−3
Monoclinic, P21/c	Melting point = 503–505 K
Hall symbol: -P 2ybc	Mo Kα radiation λ = 0.71073 Å
a = 7.3532 (1) Å	Cell parameters from 4688 reflections
b = 14.0250 (2) Å	θ = 1.9–29.0º
c = 18.3755 (2) Å	µ = 0.47 mm−1
β = 111.232 (1)º	T = 100.0 (1) K
V = 1766.41 (4) Å3	Block, brown
Z = 4	0.49 × 0.22 × 0.18 mm

Bruker SMART APEX2 CCD area-detector diffractometer	4688 independent reflections
Radiation source: fine-focus sealed tube	3913 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.037
Detector resolution: 8.33 pixels mm-1	θmax = 29.0º
T = 100.0(1) K	θmin = 1.9º
ω scans	h = −10→10
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −19→19
Tmin = 0.883, Tmax = 0.919	l = −21→25
23692 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0415P)2 + 1.1208P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
4688 reflections	Δρmax = 0.57 e Å−3
227 parameters	Δρmin = −0.42 e Å−3
63 constraints	Extinction correction: none
Primary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
S1	0.57131 (7)	0.72654 (3)	0.43805 (3)	0.02450 (11)
S2	1.05267 (5)	0.60506 (3)	0.27447 (2)	0.01477 (10)
Cl1	0.37650 (6)	0.31936 (3)	0.25045 (2)	0.02092 (10)
O1	1.09007 (17)	0.58763 (9)	0.20315 (7)	0.0219 (3)
O2	1.21870 (16)	0.58102 (9)	0.34443 (7)	0.0196 (3)
O3	0.97435 (17)	0.69943 (8)	0.27824 (7)	0.0210 (3)
N1	0.8323 (2)	1.24164 (11)	0.49389 (9)	0.0214 (3)
C1	0.6981 (3)	1.10669 (14)	0.41625 (11)	0.0273 (4)
H1A	0.6342	1.0808	0.3669	0.033*
C2	0.7408 (3)	1.20156 (14)	0.42351 (11)	0.0265 (4)
H2A	0.7060	1.2394	0.3790	0.032*
C3	0.8863 (3)	1.18711 (14)	0.55895 (11)	0.0259 (4)
H3A	0.9501	1.2150	0.6075	0.031*
C4	0.8481 (3)	1.09132 (14)	0.55424 (11)	0.0267 (4)
H4A	0.8881	1.0547	0.5995	0.032*
C5	0.7490 (2)	1.04783 (13)	0.48184 (11)	0.0216 (3)
C6	0.6999 (3)	0.94698 (14)	0.47236 (11)	0.0239 (4)
H6A	0.6262	0.9252	0.4226	0.029*
C7	0.7537 (3)	0.88364 (13)	0.53044 (11)	0.0227 (4)
H7A	0.8268	0.9066	0.5799	0.027*
C8	0.7098 (2)	0.78300 (13)	0.52426 (10)	0.0213 (3)
C9	0.7700 (2)	0.72058 (12)	0.58541 (10)	0.0190 (3)
H9A	0.8451	0.7379	0.6363	0.023*
C10	0.7037 (3)	0.62467 (13)	0.56186 (11)	0.0234 (4)
H10A	0.7313	0.5730	0.5958	0.028*
C11	0.5956 (3)	0.61854 (13)	0.48386 (11)	0.0234 (4)
H11A	0.5415	0.5622	0.4586	0.028*
C12	0.8779 (3)	1.34470 (13)	0.50102 (12)	0.0287 (4)
H12A	0.8119	1.3754	0.4518	0.043*
H12B	1.0161	1.3535	0.5159	0.043*
H12C	0.8353	1.3722	0.5400	0.043*
C13	0.8648 (2)	0.52345 (12)	0.27171 (9)	0.0151 (3)
C14	0.8824 (2)	0.42781 (12)	0.25482 (9)	0.0165 (3)
H14A	0.9944	0.4067	0.2475	0.020*
C15	0.7332 (2)	0.36386 (12)	0.24892 (10)	0.0174 (3)
H15A	0.7434	0.3000	0.2372	0.021*
C16	0.5682 (2)	0.39778 (12)	0.26093 (9)	0.0165 (3)
C17	0.5512 (2)	0.49151 (12)	0.28055 (10)	0.0186 (3)
H17A	0.4417	0.5120	0.2902	0.022*
C18	0.7013 (2)	0.55480 (12)	0.28563 (10)	0.0181 (3)
H18A	0.6920	0.6183	0.2984	0.022*

	U11	U22	U33	U12	U13	U23
S1	0.0255 (2)	0.0248 (2)	0.0196 (2)	−0.00284 (17)	0.00382 (17)	0.00120 (17)
S2	0.01233 (18)	0.01553 (19)	0.01604 (19)	0.00021 (14)	0.00465 (14)	0.00095 (14)
Cl1	0.01861 (19)	0.0189 (2)	0.0272 (2)	−0.00466 (14)	0.01069 (16)	−0.00201 (16)
O1	0.0200 (6)	0.0292 (7)	0.0181 (6)	−0.0020 (5)	0.0090 (5)	0.0007 (5)
O2	0.0144 (5)	0.0239 (6)	0.0174 (6)	0.0000 (4)	0.0022 (5)	0.0013 (5)
O3	0.0181 (6)	0.0143 (6)	0.0314 (7)	−0.0003 (4)	0.0099 (5)	0.0002 (5)
N1	0.0225 (7)	0.0214 (7)	0.0240 (8)	−0.0001 (6)	0.0127 (6)	0.0011 (6)
C1	0.0289 (9)	0.0304 (10)	0.0204 (9)	−0.0058 (8)	0.0063 (7)	−0.0019 (7)
C2	0.0298 (10)	0.0285 (10)	0.0192 (8)	−0.0031 (8)	0.0066 (7)	0.0034 (7)
C3	0.0309 (9)	0.0293 (10)	0.0174 (8)	−0.0016 (8)	0.0085 (7)	−0.0019 (7)
C4	0.0329 (10)	0.0273 (10)	0.0208 (9)	0.0009 (8)	0.0108 (8)	0.0035 (7)
C5	0.0192 (8)	0.0227 (9)	0.0256 (9)	−0.0001 (6)	0.0114 (7)	−0.0001 (7)
C6	0.0219 (8)	0.0285 (9)	0.0209 (8)	−0.0034 (7)	0.0073 (7)	−0.0016 (7)
C7	0.0192 (8)	0.0274 (9)	0.0224 (9)	0.0001 (7)	0.0086 (7)	−0.0019 (7)
C8	0.0181 (8)	0.0239 (9)	0.0227 (8)	−0.0015 (6)	0.0085 (7)	−0.0015 (7)
C9	0.0176 (8)	0.0251 (9)	0.0133 (7)	−0.0012 (6)	0.0045 (6)	0.0008 (6)
C10	0.0219 (8)	0.0249 (9)	0.0220 (9)	−0.0019 (7)	0.0061 (7)	0.0044 (7)
C11	0.0225 (8)	0.0211 (9)	0.0242 (9)	−0.0038 (7)	0.0058 (7)	0.0004 (7)
C12	0.0318 (10)	0.0219 (9)	0.0376 (11)	−0.0020 (8)	0.0186 (9)	−0.0005 (8)
C13	0.0139 (7)	0.0171 (8)	0.0142 (7)	−0.0002 (6)	0.0048 (6)	−0.0002 (6)
C14	0.0145 (7)	0.0190 (8)	0.0170 (8)	0.0024 (6)	0.0068 (6)	−0.0008 (6)
C15	0.0186 (7)	0.0148 (7)	0.0192 (8)	0.0016 (6)	0.0075 (6)	−0.0010 (6)
C16	0.0148 (7)	0.0176 (8)	0.0166 (7)	−0.0027 (6)	0.0051 (6)	0.0008 (6)
C17	0.0148 (7)	0.0180 (8)	0.0249 (9)	0.0018 (6)	0.0094 (7)	0.0001 (6)
C18	0.0182 (8)	0.0148 (8)	0.0217 (8)	0.0011 (6)	0.0078 (6)	−0.0014 (6)

S1—C11	1.7105 (19)	C7—C8	1.443 (3)
S1—C8	1.7335 (18)	C7—H7A	0.9300
S2—O1	1.4541 (12)	C8—C9	1.366 (2)
S2—O3	1.4550 (12)	C9—C10	1.443 (2)
S2—O2	1.4560 (12)	C9—H9A	0.9300
S2—C13	1.7806 (16)	C10—C11	1.367 (3)
Cl1—C16	1.7428 (16)	C10—H10A	0.9300
N1—C2	1.346 (2)	C11—H11A	0.9300
N1—C3	1.352 (2)	C12—H12A	0.9600
N1—C12	1.479 (2)	C12—H12B	0.9600
C1—C2	1.363 (3)	C12—H12C	0.9600
C1—C5	1.395 (3)	C13—C18	1.388 (2)
C1—H1A	0.9300	C13—C14	1.393 (2)
C2—H2A	0.9300	C14—C15	1.390 (2)
C3—C4	1.369 (3)	C14—H14A	0.9300
C3—H3A	0.9300	C15—C16	1.393 (2)
C4—C5	1.404 (3)	C15—H15A	0.9300
C4—H4A	0.9300	C16—C17	1.381 (2)
C5—C6	1.455 (3)	C17—C18	1.393 (2)
C6—C7	1.334 (3)	C17—H17A	0.9300
C6—H6A	0.9300	C18—H18A	0.9300
C11—S1—C8	91.87 (9)	C8—C9—C10	112.16 (15)
O1—S2—O3	113.77 (7)	C8—C9—H9A	123.9
O1—S2—O2	112.64 (7)	C10—C9—H9A	123.9
O3—S2—O2	112.86 (7)	C11—C10—C9	112.22 (16)
O1—S2—C13	105.32 (7)	C11—C10—H10A	123.9
O3—S2—C13	105.65 (7)	C9—C10—H10A	123.9
O2—S2—C13	105.68 (7)	C10—C11—S1	112.19 (14)
C2—N1—C3	119.87 (16)	C10—C11—H11A	123.9
C2—N1—C12	120.78 (16)	S1—C11—H11A	123.9
C3—N1—C12	119.34 (16)	N1—C12—H12A	109.5
C2—C1—C5	120.86 (18)	N1—C12—H12B	109.5
C2—C1—H1A	119.6	H12A—C12—H12B	109.5
C5—C1—H1A	119.6	N1—C12—H12C	109.5
N1—C2—C1	121.28 (17)	H12A—C12—H12C	109.5
N1—C2—H2A	119.4	H12B—C12—H12C	109.5
C1—C2—H2A	119.4	C18—C13—C14	120.17 (15)
N1—C3—C4	120.76 (17)	C18—C13—S2	120.39 (13)
N1—C3—H3A	119.6	C14—C13—S2	119.44 (12)
C4—C3—H3A	119.6	C15—C14—C13	120.28 (15)
C3—C4—C5	120.70 (17)	C15—C14—H14A	119.9
C3—C4—H4A	119.6	C13—C14—H14A	119.9
C5—C4—H4A	119.6	C14—C15—C16	118.36 (15)
C1—C5—C4	116.51 (17)	C14—C15—H15A	120.8
C1—C5—C6	119.63 (17)	C16—C15—H15A	120.8
C4—C5—C6	123.86 (17)	C17—C16—C15	122.20 (15)
C7—C6—C5	124.26 (17)	C17—C16—Cl1	118.91 (12)
C7—C6—H6A	117.9	C15—C16—Cl1	118.89 (13)
C5—C6—H6A	117.9	C16—C17—C18	118.65 (15)
C6—C7—C8	126.54 (17)	C16—C17—H17A	120.7
C6—C7—H7A	116.7	C18—C17—H17A	120.7
C8—C7—H7A	116.7	C13—C18—C17	120.27 (15)
C9—C8—C7	124.44 (16)	C13—C18—H18A	119.9
C9—C8—S1	111.55 (13)	C17—C18—H18A	119.9
C7—C8—S1	124.01 (14)
C3—N1—C2—C1	1.0 (3)	C8—C9—C10—C11	−0.1 (2)
C12—N1—C2—C1	179.98 (18)	C9—C10—C11—S1	−0.2 (2)
C5—C1—C2—N1	−0.3 (3)	C8—S1—C11—C10	0.36 (15)
C2—N1—C3—C4	−0.4 (3)	O1—S2—C13—C18	−130.91 (14)
C12—N1—C3—C4	−179.30 (17)	O3—S2—C13—C18	−10.19 (16)
N1—C3—C4—C5	−1.1 (3)	O2—S2—C13—C18	109.65 (14)
C2—C1—C5—C4	−1.0 (3)	O1—S2—C13—C14	48.59 (15)
C2—C1—C5—C6	179.41 (18)	O3—S2—C13—C14	169.30 (13)
C3—C4—C5—C1	1.7 (3)	O2—S2—C13—C14	−70.85 (14)
C3—C4—C5—C6	−178.76 (17)	C18—C13—C14—C15	2.4 (2)
C1—C5—C6—C7	175.16 (18)	S2—C13—C14—C15	−177.09 (12)
C4—C5—C6—C7	−4.4 (3)	C13—C14—C15—C16	−0.5 (2)
C5—C6—C7—C8	−179.72 (17)	C14—C15—C16—C17	−1.9 (3)
C6—C7—C8—C9	179.23 (18)	C14—C15—C16—Cl1	177.84 (12)
C6—C7—C8—S1	−1.5 (3)	C15—C16—C17—C18	2.4 (3)
C11—S1—C8—C9	−0.44 (14)	Cl1—C16—C17—C18	−177.33 (13)
C11—S1—C8—C7	−179.82 (15)	C14—C13—C18—C17	−1.9 (2)
C7—C8—C9—C10	179.78 (16)	S2—C13—C18—C17	177.59 (13)
S1—C8—C9—C10	0.40 (19)	C16—C17—C18—C13	−0.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O3i	0.93	2.31	3.211 (2)	164
C6—H6A···S1	0.93	2.84	3.228 (2)	106
C7—H7A···O1ii	0.93	2.39	3.266 (2)	157
C9—H9A···O3ii	0.93	2.59	3.495 (2)	166
C10—H10A···O2iii	0.93	2.39	3.302 (2)	167
C11—H11A···O2iv	0.93	2.55	3.063 (2)	115
C12—H12C···O2i	0.96	2.39	3.334 (2)	168
C17—H17A···O2iv	0.93	2.41	3.318 (2)	166
C18—H18A···O3	0.93	2.51	2.892 (2)	105
C12—H12B···Cg1i	0.96	2.69	3.515 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1/C8–C11 thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O3i	0.93	2.31	3.211 (2)	164
C6—H6A⋯S1	0.93	2.84	3.228 (2)	106
C7—H7A⋯O1ii	0.93	2.39	3.266 (2)	157
C9—H9A⋯O3ii	0.93	2.58	3.495 (2)	166
C10—H10A⋯O2iii	0.93	2.39	3.302 (2)	167
C11—H11A⋯O2iv	0.93	2.55	3.063 (2)	115
C12—H12C⋯O2i	0.96	2.39	3.334 (2)	168
C17—H17A⋯O2iv	0.93	2.41	3.318 (2)	166
C18—H18A⋯O3	0.93	2.51	2.892 (2)	105
C12—H12B⋯Cg1i	0.96	2.69	3.515 (2)	144

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