(E)-4-[4-(Dimethyl-amino)styr-yl]-1-methyl-pyridinium 4-bromo-benzene-sulfonate.

In the title compound, C(16)H(19)N(2) (+)·C(6)H(4)BrO(3)S(-), the cation is nearly planar, with a dihedral angle of 3.19 (15)° between the pyridinium and the dimethylaminophenyl rings, and exists in the trans configuration. In the crystal packing, the cations and anions are linked into chains parallel to the c axis. These chains are stacked along the b axis. The crystal is stabilized by weak C-H⋯O and C-H⋯π inter-actions, and a π-π inter-action is also observed with a Cg⋯Cg distance of 3.5675 (19) Å.

Related literature

For background to NLO materials research, see: Chia et al. (1995 ▶); Sato et al. (1999 ▶); Nogi et al. (2000 ▶); Otero et al. (2002 ▶); Dittrich et al. (2003 ▶). For related structures, see, for example: Adachi et al. (1999 ▶); Chantrapromma et al. (2006 ▶; 2008 ▶); Jagannathan et al. (2007 ▶); Ogawa et al. (2008 ▶); Rahman et al. (2003 ▶); Yang et al. (2007 ▶). For comparison bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C16H19N2 +·C6H4BrO3S−

M = 475.39

Monoclinic,

a = 10.3712 (4) Å

b = 10.9937 (5) Å

c = 17.9027 (8) Å

β = 92.442 (3)°

V = 2039.37 (15) Å3

Z = 4

Mo Kα radiation

μ = 2.15 mm−1

T = 100.0 (1) K

0.49 × 0.31 × 0.11 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.414, T max = 0.787

13146 measured reflections

6479 independent reflections

4811 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.097

S = 1.02

6479 reflections

265 parameters

2 restraints

H-atom parameters constrained

Δρmax = 1.01 e Å−3

Δρmin = −1.38 e Å−3

Absolute structure: Flack (1983 ▶), 1997 Friedel pairs

Flack parameter: 0.024 (7)

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, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043547/pk2136sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043547/pk2136Isup2.hkl

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

C16H19N2+·C6H4BrO3S−	F(000) = 976
Mr = 475.39	Dx = 1.548 Mg m−3
Monoclinic, Cc	Melting point = 536–537 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 10.3712 (4) Å	Cell parameters from 6479 reflections
b = 10.9937 (5) Å	θ = 2.7–35.0°
c = 17.9027 (8) Å	µ = 2.15 mm−1
β = 92.442 (3)°	T = 100 K
V = 2039.37 (15) Å3	Plate, red
Z = 4	0.49 × 0.31 × 0.11 mm

Bruker SMART APEX2 CCD area-detector diffractometer	6479 independent reflections
Radiation source: fine-focus sealed tube	4811 reflections with I > 2σ(I)
graphite	Rint = 0.043
Detector resolution: 8.33 pixels mm-1	θmax = 35.0°, θmin = 2.7°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→14
Tmin = 0.414, Tmax = 0.787	l = −28→19
13146 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.022P)2 + 0.6614P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
6479 reflections	Δρmax = 1.01 e Å−3
265 parameters	Δρmin = −1.38 e Å−3
2 restraints	Absolute structure: Flack (1983), 1997 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.024 (7)

Experimental. The low-temperature 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
Br1	0.36598 (3)	0.77042 (3)	0.68824 (2)	0.02730 (9)
S1	0.98401 (6)	0.80532 (7)	0.66253 (5)	0.01869 (16)
O1	1.0332 (2)	0.6820 (2)	0.65917 (15)	0.0260 (5)
O2	1.0299 (2)	0.8717 (2)	0.72875 (14)	0.0264 (5)
O3	0.9990 (2)	0.8740 (2)	0.59428 (14)	0.0275 (5)
N1	0.1505 (2)	0.3126 (2)	0.93738 (17)	0.0235 (6)
N2	1.1241 (3)	0.6429 (3)	0.91479 (17)	0.0288 (6)
C1	0.3252 (3)	0.3957 (3)	1.0096 (2)	0.0267 (7)
H1A	0.3595	0.4215	1.0557	0.032*
C2	0.2023 (3)	0.3507 (3)	1.0041 (2)	0.0248 (7)
H2A	0.1538	0.3462	1.0466	0.030*
C3	0.2213 (3)	0.3179 (3)	0.8760 (2)	0.0230 (7)
H3A	0.1854	0.2908	0.8305	0.028*
C4	0.3442 (3)	0.3621 (3)	0.8789 (2)	0.0238 (7)
H4A	0.3909	0.3646	0.8357	0.029*
C5	0.4003 (3)	0.4034 (3)	0.9463 (2)	0.0231 (7)
C6	0.5317 (3)	0.4507 (3)	0.9554 (2)	0.0265 (8)
H6A	0.5609	0.4749	1.0029	0.032*
C7	0.6126 (3)	0.4612 (3)	0.8992 (2)	0.0231 (7)
H7A	0.5821	0.4373	0.8519	0.028*
C8	0.7443 (3)	0.5069 (3)	0.9063 (2)	0.0238 (7)
C9	0.8152 (3)	0.5165 (3)	0.84225 (19)	0.0224 (7)
H9A	0.7775	0.4917	0.7967	0.027*
C10	0.9406 (3)	0.5618 (3)	0.8439 (2)	0.0229 (7)
H10A	0.9842	0.5690	0.7998	0.027*
C11	1.0015 (3)	0.5969 (3)	0.9124 (2)	0.0225 (7)
C12	0.9307 (3)	0.5851 (3)	0.9777 (2)	0.0260 (7)
H12A	0.9690	0.6066	1.0237	0.031*
C13	0.8055 (3)	0.5421 (3)	0.9742 (2)	0.0250 (7)
H13A	0.7608	0.5363	1.0179	0.030*
C14	0.0170 (3)	0.2686 (3)	0.9326 (2)	0.0298 (8)
H14A	0.0039	0.2197	0.8885	0.045*
H14B	−0.0409	0.3367	0.9302	0.045*
H14C	0.0007	0.2206	0.9760	0.045*
C15	1.1928 (3)	0.6611 (3)	0.8465 (2)	0.0295 (8)
H15A	1.1404	0.7084	0.8119	0.044*
H15B	1.2110	0.5835	0.8246	0.044*
H15C	1.2722	0.7032	0.8579	0.044*
C16	1.1872 (3)	0.6788 (3)	0.9852 (2)	0.0304 (8)
H16A	1.1782	0.6151	1.0213	0.046*
H16B	1.1480	0.7518	1.0030	0.046*
H16C	1.2771	0.6932	0.9781	0.046*
C17	0.8138 (3)	0.7927 (3)	0.6710 (2)	0.0176 (6)
C18	0.7402 (3)	0.8978 (3)	0.6780 (2)	0.0192 (7)
H18A	0.7809	0.9732	0.6797	0.023*
C19	0.6080 (3)	0.8917 (3)	0.6823 (2)	0.0209 (7)
H19A	0.5594	0.9624	0.6858	0.025*
C20	0.5489 (3)	0.7790 (3)	0.6814 (2)	0.0207 (6)
C21	0.6187 (3)	0.6722 (3)	0.6750 (2)	0.0220 (7)
H21A	0.5774	0.5970	0.6743	0.026*
C22	0.7524 (3)	0.6800 (3)	0.6696 (2)	0.0191 (7)
H22A	0.8008	0.6094	0.6649	0.023*

	U11	U22	U33	U12	U13	U23
Br1	0.01676 (11)	0.03575 (17)	0.02948 (18)	−0.00106 (18)	0.00199 (10)	−0.0056 (2)
S1	0.0163 (3)	0.0187 (4)	0.0211 (4)	0.0010 (2)	0.0013 (3)	0.0020 (3)
O1	0.0167 (9)	0.0242 (12)	0.0375 (16)	−0.0007 (8)	0.0055 (10)	0.0016 (11)
O2	0.0198 (10)	0.0342 (13)	0.0251 (14)	−0.0022 (9)	−0.0010 (9)	−0.0054 (11)
O3	0.0247 (10)	0.0308 (13)	0.0270 (14)	−0.0007 (9)	0.0021 (9)	0.0068 (10)
N1	0.0221 (12)	0.0201 (13)	0.0287 (18)	0.0065 (10)	0.0035 (12)	0.0037 (12)
N2	0.0305 (13)	0.0347 (16)	0.0212 (16)	−0.0087 (12)	0.0001 (12)	−0.0013 (14)
C1	0.0304 (15)	0.0215 (16)	0.028 (2)	0.0070 (12)	−0.0003 (14)	−0.0023 (14)
C2	0.0302 (15)	0.0235 (16)	0.0210 (19)	0.0080 (12)	0.0049 (14)	0.0013 (14)
C3	0.0269 (14)	0.0220 (16)	0.0197 (19)	0.0052 (12)	−0.0011 (13)	0.0028 (13)
C4	0.0249 (14)	0.0245 (16)	0.0223 (19)	0.0063 (12)	0.0044 (12)	0.0034 (14)
C5	0.0235 (13)	0.0176 (14)	0.0285 (19)	0.0062 (11)	0.0033 (13)	0.0004 (14)
C6	0.0229 (14)	0.0271 (17)	0.030 (2)	0.0064 (12)	0.0001 (14)	−0.0039 (15)
C7	0.0247 (14)	0.0203 (15)	0.0240 (19)	0.0036 (11)	−0.0007 (13)	−0.0008 (13)
C8	0.0245 (14)	0.0215 (15)	0.025 (2)	0.0047 (11)	0.0022 (13)	−0.0003 (14)
C9	0.0281 (14)	0.0203 (15)	0.0185 (18)	0.0035 (11)	−0.0031 (13)	−0.0020 (13)
C10	0.0265 (14)	0.0208 (15)	0.0214 (19)	0.0036 (11)	0.0017 (13)	−0.0004 (13)
C11	0.0284 (14)	0.0164 (14)	0.0228 (19)	0.0018 (11)	0.0008 (13)	0.0023 (13)
C12	0.0308 (15)	0.0245 (17)	0.0224 (19)	0.0005 (12)	−0.0014 (14)	−0.0009 (14)
C13	0.0277 (15)	0.0258 (16)	0.0217 (19)	0.0003 (12)	0.0023 (13)	−0.0035 (14)
C14	0.0250 (14)	0.0274 (16)	0.037 (2)	0.0018 (13)	0.0038 (14)	0.0079 (16)
C15	0.0299 (15)	0.0315 (18)	0.027 (2)	−0.0053 (13)	−0.0018 (14)	0.0038 (16)
C16	0.0354 (17)	0.0309 (18)	0.024 (2)	−0.0066 (14)	−0.0055 (15)	−0.0007 (16)
C17	0.0174 (12)	0.0168 (14)	0.0186 (18)	0.0008 (10)	0.0004 (12)	−0.0001 (12)
C18	0.0182 (12)	0.0177 (16)	0.0215 (19)	−0.0021 (11)	0.0002 (12)	−0.0015 (13)
C19	0.0229 (14)	0.0202 (16)	0.0197 (18)	0.0029 (11)	0.0012 (12)	−0.0028 (13)
C20	0.0167 (12)	0.0293 (16)	0.0160 (17)	0.0013 (12)	0.0003 (11)	−0.0020 (14)
C21	0.0230 (14)	0.0181 (16)	0.025 (2)	−0.0009 (11)	−0.0009 (13)	−0.0004 (14)
C22	0.0226 (14)	0.0150 (15)	0.0197 (19)	0.0036 (11)	−0.0001 (13)	0.0039 (13)

Br1—C20	1.909 (3)	C9—H9A	0.9300
S1—O3	1.450 (3)	C10—C11	1.409 (5)
S1—O1	1.451 (2)	C10—H10A	0.9300
S1—O2	1.455 (2)	C11—C12	1.413 (5)
S1—C17	1.784 (3)	C12—C13	1.380 (4)
N1—C3	1.349 (4)	C12—H12A	0.9300
N1—C2	1.355 (4)	C13—H13A	0.9300
N1—C14	1.466 (4)	C14—H14A	0.9600
N2—C11	1.367 (4)	C14—H14B	0.9600
N2—C16	1.451 (4)	C14—H14C	0.9600
N2—C15	1.455 (5)	C15—H15A	0.9600
C1—C2	1.367 (5)	C15—H15B	0.9600
C1—C5	1.405 (5)	C15—H15C	0.9600
C1—H1A	0.9300	C16—H16A	0.9600
C2—H2A	0.9300	C16—H16B	0.9600
C3—C4	1.363 (4)	C16—H16C	0.9600
C3—H3A	0.9300	C17—C18	1.392 (4)
C4—C5	1.393 (5)	C17—C22	1.393 (4)
C4—H4A	0.9300	C18—C19	1.378 (4)
C5—C6	1.461 (4)	C18—H18A	0.9300
C6—C7	1.342 (5)	C19—C20	1.382 (5)
C6—H6A	0.9300	C19—H19A	0.9300
C7—C8	1.455 (4)	C20—C21	1.387 (5)
C7—H7A	0.9300	C21—C22	1.396 (4)
C8—C9	1.393 (5)	C21—H21A	0.9300
C8—C13	1.402 (5)	C22—H22A	0.9300
C9—C10	1.391 (4)
O3—S1—O1	113.63 (15)	C10—C11—C12	117.7 (3)
O3—S1—O2	112.50 (15)	C13—C12—C11	121.0 (3)
O1—S1—O2	113.53 (14)	C13—C12—H12A	119.5
O3—S1—C17	104.72 (14)	C11—C12—H12A	119.5
O1—S1—C17	106.37 (13)	C12—C13—C8	121.6 (3)
O2—S1—C17	105.09 (15)	C12—C13—H13A	119.2
C3—N1—C2	119.8 (3)	C8—C13—H13A	119.2
C3—N1—C14	120.8 (3)	N1—C14—H14A	109.5
C2—N1—C14	119.4 (3)	N1—C14—H14B	109.5
C11—N2—C16	120.8 (3)	H14A—C14—H14B	109.5
C11—N2—C15	120.8 (3)	N1—C14—H14C	109.5
C16—N2—C15	118.3 (3)	H14A—C14—H14C	109.5
C2—C1—C5	120.8 (3)	H14B—C14—H14C	109.5
C2—C1—H1A	119.6	N2—C15—H15A	109.5
C5—C1—H1A	119.6	N2—C15—H15B	109.5
N1—C2—C1	120.5 (3)	H15A—C15—H15B	109.5
N1—C2—H2A	119.7	N2—C15—H15C	109.5
C1—C2—H2A	119.7	H15A—C15—H15C	109.5
N1—C3—C4	121.6 (3)	H15B—C15—H15C	109.5
N1—C3—H3A	119.2	N2—C16—H16A	109.5
C4—C3—H3A	119.2	N2—C16—H16B	109.5
C3—C4—C5	120.3 (3)	H16A—C16—H16B	109.5
C3—C4—H4A	119.8	N2—C16—H16C	109.5
C5—C4—H4A	119.8	H16A—C16—H16C	109.5
C4—C5—C1	117.0 (3)	H16B—C16—H16C	109.5
C4—C5—C6	124.4 (3)	C18—C17—C22	119.2 (3)
C1—C5—C6	118.6 (3)	C18—C17—S1	119.4 (2)
C7—C6—C5	123.9 (3)	C22—C17—S1	121.4 (2)
C7—C6—H6A	118.1	C19—C18—C17	121.0 (3)
C5—C6—H6A	118.1	C19—C18—H18A	119.5
C6—C7—C8	125.4 (3)	C17—C18—H18A	119.5
C6—C7—H7A	117.3	C18—C19—C20	119.0 (3)
C8—C7—H7A	117.3	C18—C19—H19A	120.5
C9—C8—C13	117.2 (3)	C20—C19—H19A	120.5
C9—C8—C7	118.8 (3)	C19—C20—C21	121.8 (3)
C13—C8—C7	124.0 (3)	C19—C20—Br1	119.0 (2)
C10—C9—C8	122.4 (3)	C21—C20—Br1	119.1 (2)
C10—C9—H9A	118.8	C20—C21—C22	118.5 (3)
C8—C9—H9A	118.8	C20—C21—H21A	120.8
C9—C10—C11	120.0 (3)	C22—C21—H21A	120.8
C9—C10—H10A	120.0	C17—C22—C21	120.5 (3)
C11—C10—H10A	120.0	C17—C22—H22A	119.7
N2—C11—C10	120.7 (3)	C21—C22—H22A	119.7
N2—C11—C12	121.6 (3)
C3—N1—C2—C1	0.7 (5)	C9—C10—C11—C12	−0.5 (4)
C14—N1—C2—C1	−177.9 (3)	N2—C11—C12—C13	177.9 (3)
C5—C1—C2—N1	0.0 (5)	C10—C11—C12—C13	−0.8 (5)
C2—N1—C3—C4	−0.7 (5)	C11—C12—C13—C8	0.9 (5)
C14—N1—C3—C4	177.9 (3)	C9—C8—C13—C12	0.3 (5)
N1—C3—C4—C5	0.0 (5)	C7—C8—C13—C12	−179.9 (3)
C3—C4—C5—C1	0.7 (4)	O3—S1—C17—C18	−61.5 (3)
C3—C4—C5—C6	179.1 (3)	O1—S1—C17—C18	177.9 (3)
C2—C1—C5—C4	−0.7 (5)	O2—S1—C17—C18	57.2 (3)
C2—C1—C5—C6	−179.2 (3)	O3—S1—C17—C22	117.4 (3)
C4—C5—C6—C7	1.0 (5)	O1—S1—C17—C22	−3.2 (3)
C1—C5—C6—C7	179.4 (3)	O2—S1—C17—C22	−123.8 (3)
C5—C6—C7—C8	−179.5 (3)	C22—C17—C18—C19	−1.0 (5)
C6—C7—C8—C9	−177.8 (3)	S1—C17—C18—C19	178.0 (3)
C6—C7—C8—C13	2.4 (5)	C17—C18—C19—C20	1.5 (5)
C13—C8—C9—C10	−1.7 (5)	C18—C19—C20—C21	−1.1 (5)
C7—C8—C9—C10	178.5 (3)	C18—C19—C20—Br1	179.5 (3)
C8—C9—C10—C11	1.8 (5)	C19—C20—C21—C22	0.2 (5)
C16—N2—C11—C10	−179.9 (3)	Br1—C20—C21—C22	179.6 (3)
C15—N2—C11—C10	2.3 (5)	C18—C17—C22—C21	0.1 (5)
C16—N2—C11—C12	1.5 (5)	S1—C17—C22—C21	−178.9 (3)
C15—N2—C11—C12	−176.4 (3)	C20—C21—C22—C17	0.4 (5)
C9—C10—C11—N2	−179.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1i	0.93	2.44	3.366 (4)	175
C4—H4A···O2ii	0.93	2.45	3.375 (4)	175
C6—H6A···O3iii	0.93	2.44	3.175 (4)	136
C7—H7A···O2ii	0.93	2.36	3.285 (4)	173
C14—H14C···O3i	0.96	2.36	3.304 (4)	168
C15—H15A···O2	0.96	2.57	3.515 (4)	168
C19—H19A···O1iv	0.93	2.47	3.306 (4)	149
C3—H3A···Cg3ii	0.93	2.76	3.601 (4)	151
C14—H14B···Cg2v	0.96	2.55	3.468 (4)	161
C16—H16A···Cg3vi	0.93	2.98	3.446 (4)	111

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1i	0.93	2.44	3.366 (4)	175
C4—H4A⋯O2ii	0.93	2.45	3.375 (4)	175
C6—H6A⋯O3iii	0.93	2.44	3.175 (4)	136
C7—H7A⋯O2ii	0.93	2.36	3.285 (4)	173
C14—H14C⋯O3i	0.96	2.36	3.304 (4)	168
C15—H15A⋯O2	0.96	2.57	3.515 (4)	168
C19—H19A⋯O1iv	0.93	2.47	3.306 (4)	149
C3—H3A⋯Cg3ii	0.93	2.76	3.601 (4)	151
C14—H14B⋯Cg2v	0.96	2.55	3.468 (4)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) . Cg2 and Cg3 are the centroids of the C8–C13 and C17–C22 rings.