2-[(E)-2-(1H-Indol-3-yl)ethen-yl]-1-methyl-pyridinium 4-bromo-benzene-sulfonate.

In the title compound, C(16)H(15)N(2) (+)·C(6)H(4)BrO(3)S(-), the cation exists in the E configuration and is essentially planar with a dihedral angle of 3.10 (5)° between the pyridinium ring and the indole ring system. The π-conjugated planes of the cation and the anion are inclined to each other at a dihedral angle of 64.32 (4)°. In the crystal structure, the cations are stacked in an anti-parallel manner along the a axis. The anions are linked into a chain along the a axis. The cations and the anions are linked into a three-dimensional network by N-H⋯O and weak C-H⋯O hydrogen bonds. The crystal structure is further stabilized by C-H⋯π inter-actions. A π-π inter-action between the five-membered heterocyclic ring of the indole system and the pyridinium ring is also observed with a centroid-centroid distance of 3.5855 (7) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to non-linear optical materials research, see: Coe et al. (2003 ▶); Dittrich et al. (2003 ▶); Ogawa et al. (2008 ▶); Otero et al. (2002 ▶); Weir et al. (2003 ▶); Yang et al. (2007 ▶). For related structures, see, for example: Chanawanno et al. (2008 ▶); Chantrapromma et al. (2006 ▶, 2007 ▶, 2008 ▶, 2009 ▶); Jindawong et al. (2005 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H15N2 +·C6H4BrO3S−

M = 471.36

Monoclinic,

a = 7.5188 (1) Å

b = 13.3659 (2) Å

c = 20.2670 (3) Å

β = 98.850 (1)°

V = 2012.49 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.17 mm−1

T = 100 K

0.31 × 0.27 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.548, T max = 0.706

67716 measured reflections

10581 independent reflections

8073 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.085

S = 1.03

10581 reflections

267 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.02 e Å−3

Δρmin = −0.66 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/S1600536809011386/is2401sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011386/is2401Isup2.hkl

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

C16H15N2+·C6H4BrO3S−	F(000) = 960
Mr = 471.36	Dx = 1.556 Mg m−3
Monoclinic, P21/c	Melting point = 508–510 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.5188 (1) Å	Cell parameters from 10581 reflections
b = 13.3659 (2) Å	θ = 2.0–37.5°
c = 20.2670 (3) Å	µ = 2.17 mm−1
β = 98.850 (1)°	T = 100 K
V = 2012.49 (5) Å3	Block, yellow
Z = 4	0.31 × 0.27 × 0.16 mm

Bruker APEXII CCD area-detector diffractometer	10581 independent reflections
Radiation source: sealed tube	8073 reflections with I > 2σ(I)
graphite	Rint = 0.033
φ and ω scans	θmax = 37.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→12
Tmin = 0.548, Tmax = 0.706	k = −22→22
67716 measured reflections	l = −34→34

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0369P)2 + 0.9196P] where P = (Fo2 + 2Fc2)/3
10581 reflections	(Δ/σ)max = 0.003
267 parameters	Δρmax = 1.02 e Å−3
0 restraints	Δρmin = −0.66 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat [Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.] 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	0.437510 (18)	0.545613 (9)	0.317640 (6)	0.02094 (4)
S1	1.03248 (4)	0.87587 (2)	0.276111 (13)	0.01297 (5)
O1	1.08595 (14)	0.92518 (8)	0.33975 (5)	0.02417 (19)
O2	1.17976 (12)	0.82343 (7)	0.25255 (5)	0.02343 (19)
O3	0.93322 (13)	0.94158 (8)	0.22583 (5)	0.0253 (2)
C17	0.87426 (15)	0.78270 (8)	0.29047 (5)	0.01413 (18)
C18	0.92454 (16)	0.68277 (9)	0.30078 (6)	0.01618 (19)
H18A	1.0438	0.6639	0.3012	0.019*
C19	0.79634 (16)	0.61112 (9)	0.31052 (6)	0.0171 (2)
H19A	0.8285	0.5442	0.3170	0.021*
C20	0.61934 (16)	0.64165 (8)	0.31029 (6)	0.01558 (19)
C21	0.56765 (15)	0.74130 (9)	0.30144 (6)	0.01596 (19)
H21A	0.4491	0.7603	0.3023	0.019*
C22	0.69622 (15)	0.81182 (8)	0.29127 (6)	0.01531 (18)
H22A	0.6637	0.8787	0.2850	0.018*
N1	0.75652 (13)	0.79242 (8)	0.58104 (5)	0.01574 (17)
N2	0.77966 (15)	1.20325 (8)	0.35483 (5)	0.01918 (19)
C1	0.77944 (17)	0.69502 (9)	0.59983 (6)	0.0196 (2)
H1A	0.7581	0.6761	0.6421	0.024*
C2	0.83291 (18)	0.62419 (9)	0.55835 (7)	0.0218 (2)
H2A	0.8490	0.5580	0.5721	0.026*
C3	0.86283 (18)	0.65363 (9)	0.49483 (6)	0.0210 (2)
H3A	0.8972	0.6067	0.4653	0.025*
C4	0.84120 (17)	0.75234 (9)	0.47621 (6)	0.0191 (2)
H4A	0.8621	0.7717	0.4340	0.023*
C5	0.78805 (15)	0.82472 (9)	0.51967 (5)	0.01522 (18)
C6	0.76564 (17)	0.92976 (9)	0.50349 (6)	0.01701 (19)
H6A	0.7261	0.9722	0.5346	0.020*
C7	0.79955 (16)	0.96932 (9)	0.44504 (6)	0.01598 (19)
H7A	0.8379	0.9250	0.4148	0.019*
C8	0.78260 (15)	1.07202 (9)	0.42496 (5)	0.01529 (18)
C9	0.80825 (16)	1.10341 (9)	0.36157 (6)	0.0178 (2)
H9A	0.8404	1.0618	0.3286	0.021*
C10	0.73615 (16)	1.24110 (9)	0.41377 (6)	0.0181 (2)
C11	0.69668 (18)	1.33969 (10)	0.42910 (7)	0.0234 (2)
H11A	0.6958	1.3909	0.3980	0.028*
C12	0.65886 (19)	1.35765 (10)	0.49284 (8)	0.0270 (3)
H12A	0.6305	1.4223	0.5047	0.032*
C13	0.66243 (19)	1.28055 (11)	0.53972 (7)	0.0263 (3)
H13A	0.6384	1.2953	0.5823	0.032*
C14	0.70096 (18)	1.18259 (10)	0.52424 (6)	0.0210 (2)
H14A	0.7027	1.1321	0.5559	0.025*
C15	0.73730 (16)	1.16115 (9)	0.45962 (6)	0.01610 (19)
C16	0.69856 (17)	0.86295 (10)	0.62973 (6)	0.0191 (2)
H16A	0.6809	0.8272	0.6693	0.029*
H16B	0.5877	0.8943	0.6105	0.029*
H16C	0.7894	0.9132	0.6410	0.029*
H1N2	0.796 (2)	1.2377 (15)	0.3209 (10)	0.028 (5)*

	U11	U22	U33	U12	U13	U23
Br1	0.02422 (6)	0.01477 (5)	0.02501 (6)	−0.00464 (4)	0.00755 (4)	−0.00167 (4)
S1	0.01221 (11)	0.01335 (10)	0.01371 (10)	−0.00058 (8)	0.00315 (8)	−0.00260 (9)
O1	0.0282 (5)	0.0241 (4)	0.0212 (4)	−0.0076 (4)	0.0070 (3)	−0.0102 (4)
O2	0.0167 (4)	0.0236 (4)	0.0319 (5)	0.0008 (3)	0.0096 (3)	−0.0090 (4)
O3	0.0191 (4)	0.0244 (5)	0.0314 (5)	−0.0025 (3)	0.0008 (3)	0.0130 (4)
C17	0.0150 (5)	0.0134 (4)	0.0139 (4)	0.0011 (3)	0.0021 (3)	−0.0009 (3)
C18	0.0155 (5)	0.0147 (4)	0.0185 (4)	0.0037 (4)	0.0031 (3)	0.0000 (4)
C19	0.0210 (5)	0.0130 (4)	0.0177 (4)	0.0029 (4)	0.0044 (4)	0.0003 (4)
C20	0.0187 (5)	0.0128 (4)	0.0156 (4)	−0.0010 (4)	0.0035 (3)	−0.0006 (4)
C21	0.0150 (5)	0.0147 (4)	0.0183 (4)	0.0008 (4)	0.0030 (3)	0.0006 (4)
C22	0.0161 (5)	0.0118 (4)	0.0181 (4)	0.0018 (3)	0.0032 (3)	0.0004 (4)
N1	0.0177 (4)	0.0157 (4)	0.0134 (4)	−0.0026 (3)	0.0012 (3)	0.0000 (3)
N2	0.0209 (5)	0.0179 (4)	0.0184 (4)	−0.0003 (4)	0.0023 (3)	0.0052 (4)
C1	0.0216 (5)	0.0172 (5)	0.0191 (5)	−0.0032 (4)	0.0004 (4)	0.0039 (4)
C2	0.0241 (6)	0.0150 (5)	0.0253 (5)	−0.0007 (4)	0.0004 (4)	0.0023 (4)
C3	0.0229 (6)	0.0165 (5)	0.0230 (5)	0.0023 (4)	0.0020 (4)	−0.0021 (4)
C4	0.0234 (6)	0.0175 (5)	0.0164 (4)	0.0021 (4)	0.0032 (4)	−0.0001 (4)
C5	0.0159 (5)	0.0156 (4)	0.0138 (4)	−0.0009 (4)	0.0011 (3)	0.0007 (4)
C6	0.0207 (5)	0.0151 (4)	0.0157 (4)	0.0013 (4)	0.0044 (4)	0.0006 (4)
C7	0.0180 (5)	0.0153 (4)	0.0145 (4)	0.0004 (4)	0.0020 (3)	0.0002 (4)
C8	0.0157 (5)	0.0152 (4)	0.0148 (4)	0.0000 (4)	0.0017 (3)	0.0008 (4)
C9	0.0180 (5)	0.0186 (5)	0.0166 (4)	0.0000 (4)	0.0025 (4)	0.0017 (4)
C10	0.0161 (5)	0.0164 (5)	0.0210 (5)	−0.0002 (4)	0.0006 (4)	0.0012 (4)
C11	0.0200 (6)	0.0151 (5)	0.0338 (6)	0.0013 (4)	0.0004 (5)	0.0019 (5)
C12	0.0230 (6)	0.0178 (5)	0.0402 (7)	0.0017 (5)	0.0045 (5)	−0.0072 (5)
C13	0.0269 (7)	0.0238 (6)	0.0290 (6)	0.0002 (5)	0.0073 (5)	−0.0085 (5)
C14	0.0241 (6)	0.0197 (5)	0.0197 (5)	−0.0005 (4)	0.0054 (4)	−0.0030 (4)
C15	0.0154 (5)	0.0152 (4)	0.0173 (4)	−0.0001 (4)	0.0016 (3)	0.0002 (4)
C16	0.0233 (6)	0.0200 (5)	0.0143 (4)	−0.0028 (4)	0.0043 (4)	−0.0022 (4)

Br1—C20	1.8978 (12)	C3—C4	1.3750 (18)
S1—O1	1.4492 (9)	C3—H3A	0.9300
S1—O2	1.4519 (9)	C4—C5	1.4070 (16)
S1—O3	1.4604 (10)	C4—H4A	0.9300
S1—C17	1.7768 (12)	C5—C6	1.4458 (16)
C17—C18	1.3952 (16)	C6—C7	1.3568 (16)
C17—C22	1.3966 (16)	C6—H6A	0.9300
C18—C19	1.3942 (17)	C7—C8	1.4318 (16)
C18—H18A	0.9300	C7—H7A	0.9300
C19—C20	1.3913 (17)	C8—C9	1.3929 (16)
C19—H19A	0.9300	C8—C15	1.4498 (16)
C20—C21	1.3913 (16)	C9—H9A	0.9300
C21—C22	1.3881 (16)	C10—C11	1.3961 (18)
C21—H21A	0.9300	C10—C15	1.4153 (16)
C22—H22A	0.9300	C11—C12	1.386 (2)
N1—C1	1.3599 (16)	C11—H11A	0.9300
N1—C5	1.3712 (15)	C12—C13	1.399 (2)
N1—C16	1.4782 (16)	C12—H12A	0.9300
N2—C9	1.3552 (16)	C13—C14	1.3874 (19)
N2—C10	1.3821 (16)	C13—H13A	0.9300
N2—H1N2	0.850 (19)	C14—C15	1.4079 (17)
C1—C2	1.3669 (19)	C14—H14A	0.9300
C1—H1A	0.9300	C16—H16A	0.9600
C2—C3	1.3971 (19)	C16—H16B	0.9600
C2—H2A	0.9300	C16—H16C	0.9600
O1—S1—O2	113.02 (6)	C5—C4—H4A	119.3
O1—S1—O3	112.93 (6)	N1—C5—C4	117.17 (10)
O2—S1—O3	113.24 (6)	N1—C5—C6	118.76 (10)
O1—S1—C17	105.91 (6)	C4—C5—C6	124.07 (10)
O2—S1—C17	106.22 (6)	C7—C6—C5	123.06 (11)
O3—S1—C17	104.63 (5)	C7—C6—H6A	118.5
C18—C17—C22	120.21 (11)	C5—C6—H6A	118.5
C18—C17—S1	121.51 (9)	C6—C7—C8	126.96 (11)
C22—C17—S1	118.27 (8)	C6—C7—H7A	116.5
C19—C18—C17	120.10 (11)	C8—C7—H7A	116.5
C19—C18—H18A	120.0	C9—C8—C7	122.14 (11)
C17—C18—H18A	119.9	C9—C8—C15	105.99 (10)
C20—C19—C18	118.68 (10)	C7—C8—C15	131.86 (10)
C20—C19—H19A	120.7	N2—C9—C8	110.32 (11)
C18—C19—H19A	120.7	N2—C9—H9A	124.8
C21—C20—C19	121.96 (11)	C8—C9—H9A	124.8
C21—C20—Br1	117.86 (9)	N2—C10—C11	128.65 (12)
C19—C20—Br1	120.10 (9)	N2—C10—C15	108.22 (10)
C22—C21—C20	118.82 (11)	C11—C10—C15	123.14 (12)
C22—C21—H21A	120.6	C12—C11—C10	116.88 (12)
C20—C21—H21A	120.6	C12—C11—H11A	121.6
C21—C22—C17	120.21 (10)	C10—C11—H11A	121.6
C21—C22—H22A	119.9	C11—C12—C13	121.35 (12)
C17—C22—H22A	119.9	C11—C12—H12A	119.3
C1—N1—C5	121.55 (10)	C13—C12—H12A	119.3
C1—N1—C16	117.47 (10)	C14—C13—C12	121.62 (13)
C5—N1—C16	120.98 (10)	C14—C13—H13A	119.2
C9—N2—C10	109.17 (10)	C12—C13—H13A	119.2
C9—N2—H1N2	125.1 (13)	C13—C14—C15	118.67 (12)
C10—N2—H1N2	125.5 (13)	C13—C14—H14A	120.7
N1—C1—C2	121.83 (11)	C15—C14—H14A	120.7
N1—C1—H1A	119.1	C14—C15—C10	118.33 (11)
C2—C1—H1A	119.1	C14—C15—C8	135.36 (11)
C1—C2—C3	118.42 (12)	C10—C15—C8	106.29 (10)
C1—C2—H2A	120.8	N1—C16—H16A	109.5
C3—C2—H2A	120.8	N1—C16—H16B	109.5
C4—C3—C2	119.61 (12)	H16A—C16—H16B	109.5
C4—C3—H3A	120.2	N1—C16—H16C	109.5
C2—C3—H3A	120.2	H16A—C16—H16C	109.5
C3—C4—C5	121.40 (11)	H16B—C16—H16C	109.5
C3—C4—H4A	119.3
O1—S1—C17—C18	−98.92 (10)	C3—C4—C5—C6	179.02 (12)
O2—S1—C17—C18	21.50 (11)	N1—C5—C6—C7	177.69 (11)
O3—S1—C17—C18	141.54 (10)	C4—C5—C6—C7	−2.13 (19)
O1—S1—C17—C22	81.05 (10)	C5—C6—C7—C8	−179.49 (11)
O2—S1—C17—C22	−158.53 (9)	C6—C7—C8—C9	−175.13 (12)
O3—S1—C17—C22	−38.49 (10)	C6—C7—C8—C15	3.9 (2)
C22—C17—C18—C19	1.37 (17)	C10—N2—C9—C8	0.64 (14)
S1—C17—C18—C19	−178.65 (9)	C7—C8—C9—N2	178.35 (11)
C17—C18—C19—C20	−0.57 (17)	C15—C8—C9—N2	−0.92 (14)
C18—C19—C20—C21	−0.76 (17)	C9—N2—C10—C11	179.84 (13)
C18—C19—C20—Br1	175.97 (9)	C9—N2—C10—C15	−0.08 (14)
C19—C20—C21—C22	1.26 (17)	N2—C10—C11—C12	−179.37 (13)
Br1—C20—C21—C22	−175.54 (8)	C15—C10—C11—C12	0.53 (19)
C20—C21—C22—C17	−0.44 (17)	C10—C11—C12—C13	0.8 (2)
C18—C17—C22—C21	−0.86 (17)	C11—C12—C13—C14	−1.1 (2)
S1—C17—C22—C21	179.16 (9)	C12—C13—C14—C15	0.1 (2)
C5—N1—C1—C2	−0.78 (18)	C13—C14—C15—C10	1.18 (18)
C16—N1—C1—C2	−179.93 (11)	C13—C14—C15—C8	179.66 (13)
N1—C1—C2—C3	−0.56 (19)	N2—C10—C15—C14	178.40 (11)
C1—C2—C3—C4	1.17 (19)	C11—C10—C15—C14	−1.52 (18)
C2—C3—C4—C5	−0.48 (19)	N2—C10—C15—C8	−0.48 (13)
C1—N1—C5—C4	1.44 (16)	C11—C10—C15—C8	179.60 (12)
C16—N1—C5—C4	−179.43 (11)	C9—C8—C15—C14	−177.76 (14)
C1—N1—C5—C6	−178.40 (11)	C7—C8—C15—C14	3.1 (2)
C16—N1—C5—C6	0.73 (16)	C9—C8—C15—C10	0.84 (13)
C3—C4—C5—N1	−0.81 (18)	C7—C8—C15—C10	−178.33 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2i	0.85 (2)	1.91 (2)	2.7593 (14)	175.2 (17)
C1—H1A···O3ii	0.93	2.53	3.2067 (16)	130
C7—H7A···O1	0.93	2.58	3.3095 (16)	136
C9—H9A···O1	0.93	2.58	3.2426 (16)	128
C14—H14A···O1iii	0.93	2.56	3.2987 (16)	137
C16—H16C···O1iii	0.96	2.36	3.2739 (17)	158
C19—H19A···O3iv	0.93	2.51	3.2052 (16)	131
C21—H21A···O2v	0.93	2.28	3.1310 (15)	152
C4—H4A···Cg3	0.93	2.82	3.5579 (13)	137
C16—H16A···Cg3vi	0.96	2.69	3.5731 (13)	154
C16—H16B···Cg1vii	0.96	2.74	3.4836 (14)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2i	0.85 (2)	1.91 (2)	2.7593 (14)	175.2 (17)
C1—H1A⋯O3ii	0.93	2.53	3.2067 (16)	130
C7—H7A⋯O1	0.93	2.58	3.3095 (16)	136
C9—H9A⋯O1	0.93	2.58	3.2426 (16)	128
C14—H14A⋯O1iii	0.93	2.56	3.2987 (16)	137
C16—H16C⋯O1iii	0.96	2.36	3.2739 (17)	158
C19—H19A⋯O3iv	0.93	2.51	3.2052 (16)	131
C21—H21A⋯O2v	0.93	2.28	3.1310 (15)	152
C4—H4A⋯Cg3	0.93	2.82	3.5579 (13)	137
C16—H16A⋯Cg3vi	0.96	2.69	3.5731 (13)	154
C16—H16B⋯Cg1vii	0.96	2.74	3.4836 (14)	135

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) . Cg1 and Cg3 are the centroids of the N2/C8–C10/C15 and C10–C15 rings, respectively.