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

In the title compound, C(16)H(14)NS(+)·C(6)H(4)BrO(3)S(-), the cation exists in an E configuration and is essentially planar, the dihedral angle between the quinolinium and thio-phene rings being 3.45 (9)°. The anion is inclined to the cation with dihedral angles of 75.43 (8) and 72.03 (11)°, respectively between the benzene ring and the quinolinium and thio-phene rings. In the crystal, the cations and anions are arranged individually into separate chains along the c axis. The cation chains are stacked in an anti-parallel manner along the a axis by π⋯π inter-actions with centroid-centroid distances of 3.7257 (13) and 3.7262 (14) Å. Weak C-H⋯O and C-H⋯π inter-actions link the cations and anions into a three-dimensional network. Short Br⋯S [3.7224 (5) Å] and Br⋯O [3.4267 (16) Å] contacts are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Chantrapromma et al. (2009a ▶,b ▶), Fun et al. (2009 ▶); Raimundo et al. (2002 ▶). For related structures, see: Chantrapromma et al. (2006 ▶); Ruanwas et al. (2008 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C16H14NS+·C6H4BrO3S−

M = 488.41

Monoclinic,

a = 7.9026 (1) Å

b = 18.8211 (2) Å

c = 13.4816 (1) Å

β = 93.292 (1)°

V = 2001.89 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.29 mm−1

T = 100 K

0.34 × 0.32 × 0.24 mm

Data collection

Bruker APEXII CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.511, T max = 0.612

51446 measured reflections

5827 independent reflections

5163 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.089

S = 1.12

5827 reflections

263 parameters

H-atom parameters constrained

Δρmax = 1.18 e Å−3

Δρmin = −0.46 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/S1600536810007488/sj2736sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007488/sj2736Isup2.hkl

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

C16H14NS+·C6H4BrO3S−	F(000) = 992
Mr = 488.41	Dx = 1.620 Mg m−3
Monoclinic, P21/c	Melting point = 538–539 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9026 (1) Å	Cell parameters from 5827 reflections
b = 18.8211 (2) Å	θ = 2.2–30.0°
c = 13.4816 (1) Å	µ = 2.29 mm−1
β = 93.292 (1)°	T = 100 K
V = 2001.89 (4) Å3	Block, brown
Z = 4	0.34 × 0.32 × 0.24 mm

Bruker APEXII CCD area detector diffractometer	5827 independent reflections
Radiation source: sealed tube	5163 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.511, Tmax = 0.612	k = −26→26
51446 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0325P)2 + 3.2344P] where P = (Fo2 + 2Fc2)/3
5827 reflections	(Δ/σ)max = 0.001
263 parameters	Δρmax = 1.18 e Å−3
0 restraints	Δρmin = −0.46 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	0.00270 (7)	0.06224 (3)	0.28565 (4)	0.02261 (11)
N1	0.3667 (2)	0.04462 (9)	0.63104 (13)	0.0179 (3)
C1	0.4567 (3)	0.03115 (11)	0.72171 (15)	0.0178 (4)
C2	0.4926 (3)	0.08556 (12)	0.79170 (16)	0.0219 (4)
H2A	0.4584	0.1320	0.7780	0.026*
C3	0.5783 (3)	0.06935 (13)	0.87999 (17)	0.0246 (4)
H3A	0.6020	0.1053	0.9260	0.030*
C4	0.6314 (3)	−0.00053 (14)	0.90275 (17)	0.0257 (5)
H4A	0.6896	−0.0104	0.9631	0.031*
C5	0.5967 (3)	−0.05415 (12)	0.83528 (16)	0.0220 (4)
H5A	0.6308	−0.1004	0.8501	0.026*
C6	0.5094 (3)	−0.03885 (11)	0.74348 (15)	0.0185 (4)
C7	0.4708 (3)	−0.09311 (11)	0.67292 (16)	0.0198 (4)
H7A	0.5081	−0.1393	0.6856	0.024*
C8	0.3799 (3)	−0.07819 (11)	0.58700 (16)	0.0204 (4)
H8A	0.3542	−0.1143	0.5415	0.025*
C9	0.3237 (3)	−0.00778 (11)	0.56601 (15)	0.0179 (4)
C10	0.2217 (3)	0.00785 (12)	0.47635 (16)	0.0217 (4)
H10A	0.1787	0.0537	0.4692	0.026*
C11	0.1837 (3)	−0.03853 (11)	0.40215 (16)	0.0197 (4)
H11A	0.2259	−0.0845	0.4089	0.024*
C12	0.0821 (3)	−0.02164 (11)	0.31320 (16)	0.0197 (4)
C13	0.0397 (3)	−0.06890 (11)	0.23773 (17)	0.0210 (4)
H13A	0.0709	−0.1166	0.2387	0.025*
C14	−0.0574 (3)	−0.03622 (13)	0.15811 (18)	0.0261 (5)
H14A	−0.0965	−0.0603	0.1010	0.031*
C15	−0.0870 (3)	0.03424 (13)	0.17442 (18)	0.0258 (5)
H15A	−0.1489	0.0635	0.1301	0.031*
C16	0.3192 (3)	0.11898 (12)	0.60670 (18)	0.0254 (5)
H16A	0.3170	0.1256	0.5360	0.038*
H16B	0.4009	0.1507	0.6383	0.038*
H16C	0.2091	0.1288	0.6300	0.038*
Br1	1.28408 (3)	0.278131 (13)	0.464999 (17)	0.02491 (7)
S2	0.66919 (6)	0.23502 (2)	0.13641 (3)	0.01276 (9)
O1	0.51250 (19)	0.23380 (8)	0.18823 (12)	0.0197 (3)
O2	0.6865 (2)	0.29873 (8)	0.07625 (11)	0.0202 (3)
O3	0.7004 (2)	0.16993 (8)	0.08184 (11)	0.0211 (3)
C17	0.8027 (3)	0.25412 (11)	0.32873 (15)	0.0177 (4)
H17A	0.6913	0.2560	0.3474	0.021*
C18	0.9364 (3)	0.26436 (12)	0.39958 (15)	0.0203 (4)
H18A	0.9153	0.2731	0.4656	0.024*
C19	1.1011 (3)	0.26130 (11)	0.36972 (15)	0.0174 (4)
C20	1.1376 (3)	0.24670 (11)	0.27242 (16)	0.0173 (4)
H20A	1.2492	0.2436	0.2544	0.021*
C21	1.0033 (3)	0.23684 (10)	0.20250 (15)	0.0161 (4)
H21A	1.0251	0.2274	0.1367	0.019*
C22	0.8362 (2)	0.24106 (10)	0.23020 (14)	0.0141 (3)

	U11	U22	U33	U12	U13	U23
S1	0.0243 (3)	0.0173 (2)	0.0262 (3)	0.00428 (19)	0.0006 (2)	0.00228 (19)
N1	0.0176 (8)	0.0160 (8)	0.0201 (8)	−0.0014 (6)	0.0019 (6)	−0.0001 (6)
C1	0.0151 (9)	0.0204 (9)	0.0182 (9)	−0.0018 (7)	0.0033 (7)	−0.0004 (7)
C2	0.0207 (10)	0.0209 (10)	0.0243 (10)	−0.0012 (8)	0.0026 (8)	−0.0038 (8)
C3	0.0239 (11)	0.0281 (11)	0.0220 (10)	−0.0047 (9)	0.0020 (8)	−0.0083 (8)
C4	0.0229 (11)	0.0358 (12)	0.0183 (10)	−0.0039 (9)	0.0000 (8)	0.0013 (9)
C5	0.0206 (10)	0.0230 (10)	0.0226 (10)	−0.0011 (8)	0.0026 (8)	0.0053 (8)
C6	0.0170 (9)	0.0211 (10)	0.0177 (9)	−0.0025 (7)	0.0035 (7)	0.0001 (7)
C7	0.0218 (10)	0.0154 (9)	0.0222 (10)	−0.0007 (7)	0.0026 (8)	0.0016 (7)
C8	0.0235 (10)	0.0160 (9)	0.0217 (10)	−0.0026 (8)	0.0013 (8)	−0.0030 (7)
C9	0.0176 (9)	0.0173 (9)	0.0189 (9)	−0.0023 (7)	0.0027 (7)	0.0001 (7)
C10	0.0237 (10)	0.0192 (9)	0.0221 (10)	0.0007 (8)	0.0007 (8)	0.0001 (8)
C11	0.0191 (10)	0.0179 (9)	0.0222 (10)	0.0000 (7)	0.0021 (8)	0.0020 (7)
C12	0.0178 (9)	0.0180 (9)	0.0232 (10)	0.0002 (7)	0.0002 (8)	0.0040 (8)
C13	0.0195 (10)	0.0158 (9)	0.0279 (11)	−0.0001 (7)	0.0024 (8)	0.0010 (8)
C14	0.0260 (11)	0.0250 (11)	0.0266 (11)	−0.0017 (9)	−0.0039 (9)	0.0001 (9)
C15	0.0219 (10)	0.0273 (11)	0.0274 (11)	0.0046 (9)	−0.0056 (8)	0.0065 (9)
C16	0.0293 (11)	0.0152 (9)	0.0310 (11)	−0.0001 (8)	−0.0046 (9)	−0.0004 (8)
Br1	0.02009 (11)	0.03105 (12)	0.02239 (11)	−0.00586 (8)	−0.00934 (8)	0.00605 (8)
S2	0.0121 (2)	0.0129 (2)	0.01296 (19)	−0.00040 (15)	−0.00194 (15)	0.00143 (15)
O1	0.0130 (7)	0.0228 (7)	0.0230 (7)	−0.0007 (5)	−0.0006 (5)	0.0033 (6)
O2	0.0221 (7)	0.0189 (7)	0.0193 (7)	−0.0012 (6)	−0.0031 (6)	0.0072 (6)
O3	0.0228 (7)	0.0187 (7)	0.0211 (7)	0.0018 (6)	−0.0048 (6)	−0.0048 (6)
C17	0.0147 (9)	0.0231 (10)	0.0156 (9)	−0.0020 (7)	0.0022 (7)	0.0008 (7)
C18	0.0206 (10)	0.0269 (10)	0.0132 (8)	−0.0032 (8)	−0.0004 (7)	0.0011 (7)
C19	0.0141 (9)	0.0196 (9)	0.0178 (9)	−0.0032 (7)	−0.0058 (7)	0.0041 (7)
C20	0.0118 (8)	0.0178 (9)	0.0221 (9)	0.0002 (7)	−0.0001 (7)	0.0030 (7)
C21	0.0153 (9)	0.0168 (9)	0.0164 (8)	−0.0001 (7)	0.0016 (7)	0.0003 (7)
C22	0.0138 (8)	0.0123 (8)	0.0160 (8)	−0.0005 (6)	−0.0014 (7)	0.0008 (6)

S1—C15	1.705 (2)	C12—C13	1.378 (3)
S1—C12	1.731 (2)	C13—C14	1.423 (3)
N1—C9	1.350 (3)	C13—H13A	0.9300
N1—C1	1.402 (3)	C14—C15	1.367 (3)
N1—C16	1.481 (3)	C14—H14A	0.9300
C1—C6	1.407 (3)	C15—H15A	0.9300
C1—C2	1.410 (3)	C16—H16A	0.9600
C2—C3	1.370 (3)	C16—H16B	0.9600
C2—H2A	0.9300	C16—H16C	0.9600
C3—C4	1.409 (4)	Br1—C19	1.9050 (19)
C3—H3A	0.9300	S2—O1	1.4565 (16)
C4—C5	1.376 (3)	S2—O3	1.4572 (15)
C4—H4A	0.9300	S2—O2	1.4585 (15)
C5—C6	1.412 (3)	S2—C22	1.778 (2)
C5—H5A	0.9300	C17—C22	1.391 (3)
C6—C7	1.417 (3)	C17—C18	1.396 (3)
C7—C8	1.357 (3)	C17—H17A	0.9300
C7—H7A	0.9300	C18—C19	1.385 (3)
C8—C9	1.421 (3)	C18—H18A	0.9300
C8—H8A	0.9300	C19—C20	1.387 (3)
C9—C10	1.444 (3)	C20—C21	1.391 (3)
C10—C11	1.348 (3)	C20—H20A	0.9300
C10—H10A	0.9300	C21—C22	1.395 (3)
C11—C12	1.440 (3)	C21—H21A	0.9300
C11—H11A	0.9300
C15—S1—C12	91.95 (11)	C12—C13—C14	112.1 (2)
C9—N1—C1	122.04 (18)	C12—C13—H13A	124.0
C9—N1—C16	119.69 (18)	C14—C13—H13A	124.0
C1—N1—C16	118.27 (18)	C15—C14—C13	112.8 (2)
N1—C1—C6	118.71 (18)	C15—C14—H14A	123.6
N1—C1—C2	121.65 (19)	C13—C14—H14A	123.6
C6—C1—C2	119.6 (2)	C14—C15—S1	112.02 (17)
C3—C2—C1	119.4 (2)	C14—C15—H15A	124.0
C3—C2—H2A	120.3	S1—C15—H15A	124.0
C1—C2—H2A	120.3	N1—C16—H16A	109.5
C2—C3—C4	121.6 (2)	N1—C16—H16B	109.5
C2—C3—H3A	119.2	H16A—C16—H16B	109.5
C4—C3—H3A	119.2	N1—C16—H16C	109.5
C5—C4—C3	119.7 (2)	H16A—C16—H16C	109.5
C5—C4—H4A	120.2	H16B—C16—H16C	109.5
C3—C4—H4A	120.2	O1—S2—O3	113.71 (9)
C4—C5—C6	119.9 (2)	O1—S2—O2	112.89 (9)
C4—C5—H5A	120.0	O3—S2—O2	112.74 (9)
C6—C5—H5A	120.0	O1—S2—C22	106.05 (9)
C1—C6—C5	119.8 (2)	O3—S2—C22	105.82 (9)
C1—C6—C7	119.02 (19)	O2—S2—C22	104.69 (9)
C5—C6—C7	121.1 (2)	C22—C17—C18	119.99 (19)
C8—C7—C6	120.5 (2)	C22—C17—H17A	120.0
C8—C7—H7A	119.8	C18—C17—H17A	120.0
C6—C7—H7A	119.8	C19—C18—C17	118.81 (19)
C7—C8—C9	120.48 (19)	C19—C18—H18A	120.6
C7—C8—H8A	119.8	C17—C18—H18A	120.6
C9—C8—H8A	119.8	C18—C19—C20	122.23 (18)
N1—C9—C8	119.19 (19)	C18—C19—Br1	119.13 (16)
N1—C9—C10	120.16 (19)	C20—C19—Br1	118.64 (15)
C8—C9—C10	120.65 (19)	C19—C20—C21	118.37 (18)
C11—C10—C9	125.4 (2)	C19—C20—H20A	120.8
C11—C10—H10A	117.3	C21—C20—H20A	120.8
C9—C10—H10A	117.3	C20—C21—C22	120.55 (18)
C10—C11—C12	124.4 (2)	C20—C21—H21A	119.7
C10—C11—H11A	117.8	C22—C21—H21A	119.7
C12—C11—H11A	117.8	C17—C22—C21	120.02 (18)
C13—C12—C11	124.9 (2)	C17—C22—S2	121.09 (15)
C13—C12—S1	111.13 (16)	C21—C22—S2	118.77 (15)
C11—C12—S1	123.91 (17)
C9—N1—C1—C6	2.6 (3)	C9—C10—C11—C12	−179.8 (2)
C16—N1—C1—C6	−177.04 (19)	C10—C11—C12—C13	−178.7 (2)
C9—N1—C1—C2	−176.27 (19)	C10—C11—C12—S1	3.4 (3)
C16—N1—C1—C2	4.1 (3)	C15—S1—C12—C13	0.22 (18)
N1—C1—C2—C3	178.8 (2)	C15—S1—C12—C11	178.3 (2)
C6—C1—C2—C3	0.0 (3)	C11—C12—C13—C14	−178.2 (2)
C1—C2—C3—C4	−0.1 (3)	S1—C12—C13—C14	−0.1 (2)
C2—C3—C4—C5	−0.1 (4)	C12—C13—C14—C15	−0.2 (3)
C3—C4—C5—C6	0.5 (3)	C13—C14—C15—S1	0.3 (3)
N1—C1—C6—C5	−178.50 (18)	C12—S1—C15—C14	−0.3 (2)
C2—C1—C6—C5	0.4 (3)	C22—C17—C18—C19	0.1 (3)
N1—C1—C6—C7	0.4 (3)	C17—C18—C19—C20	−1.6 (3)
C2—C1—C6—C7	179.31 (19)	C17—C18—C19—Br1	178.06 (16)
C4—C5—C6—C1	−0.6 (3)	C18—C19—C20—C21	1.8 (3)
C4—C5—C6—C7	−179.5 (2)	Br1—C19—C20—C21	−177.86 (15)
C1—C6—C7—C8	−2.0 (3)	C19—C20—C21—C22	−0.5 (3)
C5—C6—C7—C8	176.9 (2)	C18—C17—C22—C21	1.2 (3)
C6—C7—C8—C9	0.7 (3)	C18—C17—C22—S2	−174.80 (16)
C1—N1—C9—C8	−3.9 (3)	C20—C21—C22—C17	−1.0 (3)
C16—N1—C9—C8	175.7 (2)	C20—C21—C22—S2	175.11 (15)
C1—N1—C9—C10	176.08 (19)	O1—S2—C22—C17	−9.57 (19)
C16—N1—C9—C10	−4.3 (3)	O3—S2—C22—C17	−130.66 (17)
C7—C8—C9—N1	2.2 (3)	O2—S2—C22—C17	110.03 (17)
C7—C8—C9—C10	−177.8 (2)	O1—S2—C22—C21	174.37 (15)
N1—C9—C10—C11	173.8 (2)	O3—S2—C22—C21	53.28 (18)
C8—C9—C10—C11	−6.2 (3)	O2—S2—C22—C21	−66.04 (17)

Cg4 is the centroid of the C17–C22 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O3i	0.93	2.51	3.409 (3)	162
C7—H7A···O1ii	0.93	2.47	3.241 (3)	140
C8—H8A···O2iii	0.93	2.29	3.218 (3)	175
C10—H10A···S1	0.93	2.77	3.185 (2)	108
C11—H11A···O2iii	0.93	2.31	3.238 (3)	176
C15—H15A···O3iv	0.93	2.40	3.265 (3)	154
C16—H16B···O1v	0.96	2.43	3.321 (3)	155
C17—H17A···O1	0.93	2.54	2.915 (3)	105
C20—H20A···O1vi	0.93	2.32	3.242 (3)	172
C13—H13A···Cg4iii	0.93	2.57	3.434 (2)	155

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C17–C22 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O3i	0.93	2.51	3.409 (3)	162
C7—H7A⋯O1ii	0.93	2.47	3.241 (3)	140
C8—H8A⋯O2iii	0.93	2.29	3.218 (3)	175
C10—H10A⋯S1	0.93	2.77	3.185 (2)	108
C11—H11A⋯O2iii	0.93	2.31	3.238 (3)	176
C15—H15A⋯O3iv	0.93	2.40	3.265 (3)	154
C16—H16B⋯O1v	0.96	2.43	3.321 (3)	155
C17—H17A⋯O1	0.93	2.54	2.915 (3)	105
C20—H20A⋯O1vi	0.93	2.32	3.242 (3)	172
C13—H13A⋯Cg4iii	0.93	2.57	3.434 (2)	155

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