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

In the title compound, C(16)H(15)N(2) (+)·C(6)H(4)ClO(3)S(-), the cation exists in an E configuration with respect to the central C=C bond and is approximately planar, with a dihedral angle of 2.95 (5)° between the pyridinium and indole rings. The mean plane of the π-conjugated system of the cation and the benzene ring of the anion are inclined to each other at a dihedral angle of 69.65 (4)°. In the crystal packing, the cations are stacked in an anti-parallel manner along the a axis, resulting in a π-π inter-action with a centroid-centroid distance of 3.5889 (7) Å. The anions are linked into a chain along the a axis by weak C-H⋯O inter-actions. The cations are linked with the anions into a three-dimensional network by N-H⋯O hydrogen bonds and weak C-H⋯O inter-actions. There are also short O⋯Cl [3.1272 (10) Å] and C⋯O [3.1432 (14)-3.3753 (14) Å] contacts. The crystal structure is further stabilized by C-H⋯π inter-actions.

Related literature

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

Experimental

Crystal data

C16H15N2 +·C6H4ClO3S−

M = 426.91

Monoclinic,

a = 7.4891 (1) Å

b = 13.1650 (1) Å

c = 20.3428 (2) Å

β = 98.801 (1)°

V = 1982.06 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 100 K

0.34 × 0.28 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.899, T max = 0.942

39049 measured reflections

8706 independent reflections

7032 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.110

S = 1.05

8706 reflections

267 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.88 e Å−3

Δρmin = −0.41 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/S1600536809029547/is2441sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029547/is2441Isup2.hkl

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

C16H15N2+·C6H4ClO3S−	F(000) = 888
Mr = 426.91	Dx = 1.431 Mg m−3
Monoclinic, P21/c	Melting point = 457–459 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4891 (1) Å	Cell parameters from 8706 reflections
b = 13.1650 (1) Å	θ = 1.8–35.0°
c = 20.3428 (2) Å	µ = 0.33 mm−1
β = 98.801 (1)°	T = 100 K
V = 1982.06 (4) Å3	Block, yellow
Z = 4	0.34 × 0.28 × 0.19 mm

Bruker APEXII CCD area-detector diffractometer	8706 independent reflections
Radiation source: sealed tube	7032 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 35.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
Tmin = 0.899, Tmax = 0.942	k = −21→16
39049 measured reflections	l = −32→32

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.614P] where P = (Fo2 + 2Fc2)/3
8706 reflections	(Δ/σ)max = 0.001
267 parameters	Δρmax = 0.88 e Å−3
0 restraints	Δρmin = −0.41 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
Cl1	0.55212 (4)	0.54773 (2)	0.181673 (15)	0.02519 (7)
S1	−0.02841 (3)	0.876545 (19)	0.222068 (12)	0.01458 (6)
O1	−0.17202 (11)	0.82466 (7)	0.24875 (5)	0.02482 (17)
O2	−0.08774 (12)	0.92193 (7)	0.15750 (4)	0.02477 (17)
O3	0.07291 (12)	0.94718 (7)	0.26916 (5)	0.02529 (18)
N1	0.23969 (12)	0.71072 (7)	0.41746 (4)	0.01633 (15)
N2	0.22567 (13)	0.29591 (8)	0.64537 (5)	0.02030 (17)
H1N2	0.208 (2)	0.2594 (15)	0.6807 (9)	0.037 (5)*
C1	0.21569 (15)	0.80936 (9)	0.39837 (5)	0.02025 (19)
H1A	0.2359	0.8283	0.3561	0.024*
C2	0.16256 (16)	0.88143 (9)	0.43974 (6)	0.0221 (2)
H2A	0.1455	0.9485	0.4259	0.026*
C3	0.13459 (16)	0.85187 (9)	0.50329 (6)	0.0224 (2)
H3A	0.1008	0.8997	0.5327	0.027*
C4	0.15718 (15)	0.75206 (9)	0.52220 (5)	0.02003 (19)
H4A	0.1374	0.7328	0.5645	0.024*
C5	0.20982 (14)	0.67805 (8)	0.47878 (5)	0.01632 (17)
C6	0.23338 (15)	0.57173 (8)	0.49536 (5)	0.01806 (18)
H6A	0.2706	0.5282	0.4641	0.022*
C7	0.20377 (14)	0.53228 (8)	0.55435 (5)	0.01702 (17)
H7A	0.1680	0.5777	0.5848	0.020*
C8	0.22168 (14)	0.42820 (8)	0.57473 (5)	0.01636 (17)
C9	0.19715 (15)	0.39707 (9)	0.63827 (5)	0.01877 (18)
H9A	0.1657	0.4398	0.6711	0.023*
C10	0.26815 (14)	0.25655 (8)	0.58670 (5)	0.01868 (18)
C11	0.30803 (16)	0.15650 (9)	0.57189 (6)	0.0239 (2)
H11A	0.3097	0.1050	0.6033	0.029*
C12	0.34503 (17)	0.13712 (10)	0.50843 (7)	0.0270 (2)
H12A	0.3731	0.0713	0.4969	0.032*
C13	0.34089 (17)	0.21514 (10)	0.46122 (6)	0.0267 (2)
H13A	0.3646	0.1996	0.4188	0.032*
C14	0.30232 (16)	0.31472 (9)	0.47616 (5)	0.0216 (2)
H14A	0.3001	0.3656	0.4443	0.026*
C15	0.26664 (14)	0.33719 (8)	0.54046 (5)	0.01706 (17)
C16	0.29792 (15)	0.63874 (9)	0.36910 (5)	0.01985 (19)
H16A	0.4080	0.6061	0.3886	0.030*
H16B	0.3178	0.6749	0.3299	0.030*
H16C	0.2058	0.5884	0.3574	0.030*
C17	0.13112 (13)	0.78168 (8)	0.20886 (5)	0.01531 (17)
C18	0.31082 (14)	0.81082 (8)	0.20881 (5)	0.01712 (17)
H18A	0.3442	0.8785	0.2155	0.021*
C19	0.43933 (14)	0.73877 (8)	0.19873 (5)	0.01824 (18)
H19A	0.5587	0.7577	0.1981	0.022*
C20	0.38669 (15)	0.63786 (8)	0.18961 (5)	0.01780 (18)
C21	0.20887 (15)	0.60731 (8)	0.18910 (5)	0.01905 (19)
H21A	0.1764	0.5395	0.1826	0.023*
C22	0.07961 (14)	0.68040 (8)	0.19856 (5)	0.01777 (18)
H22A	−0.0403	0.6615	0.1980	0.021*

	U11	U22	U33	U12	U13	U23
Cl1	0.02721 (14)	0.01858 (13)	0.03119 (14)	0.00623 (10)	0.00897 (10)	0.00183 (10)
S1	0.01485 (10)	0.01459 (11)	0.01460 (10)	0.00137 (8)	0.00322 (7)	0.00272 (8)
O1	0.0196 (4)	0.0241 (4)	0.0330 (4)	−0.0001 (3)	0.0107 (3)	0.0088 (3)
O2	0.0280 (4)	0.0255 (4)	0.0211 (4)	0.0071 (3)	0.0046 (3)	0.0085 (3)
O3	0.0208 (4)	0.0233 (4)	0.0310 (4)	0.0017 (3)	0.0015 (3)	−0.0100 (3)
N1	0.0178 (4)	0.0155 (4)	0.0150 (3)	−0.0022 (3)	0.0004 (3)	0.0002 (3)
N2	0.0231 (4)	0.0187 (4)	0.0190 (4)	−0.0001 (3)	0.0028 (3)	0.0044 (3)
C1	0.0227 (5)	0.0176 (5)	0.0196 (4)	−0.0029 (4)	0.0003 (4)	0.0032 (4)
C2	0.0240 (5)	0.0156 (5)	0.0254 (5)	0.0000 (4)	0.0000 (4)	0.0021 (4)
C3	0.0244 (5)	0.0175 (5)	0.0247 (5)	0.0024 (4)	0.0019 (4)	−0.0031 (4)
C4	0.0238 (5)	0.0181 (5)	0.0182 (4)	0.0022 (4)	0.0034 (4)	−0.0008 (4)
C5	0.0177 (4)	0.0162 (4)	0.0147 (4)	−0.0002 (3)	0.0015 (3)	0.0006 (3)
C6	0.0227 (5)	0.0150 (4)	0.0169 (4)	0.0016 (4)	0.0045 (3)	0.0001 (3)
C7	0.0190 (4)	0.0159 (4)	0.0159 (4)	0.0005 (3)	0.0022 (3)	0.0000 (3)
C8	0.0179 (4)	0.0157 (4)	0.0153 (4)	0.0004 (3)	0.0019 (3)	0.0012 (3)
C9	0.0201 (4)	0.0190 (5)	0.0172 (4)	0.0010 (4)	0.0029 (3)	0.0014 (3)
C10	0.0171 (4)	0.0167 (5)	0.0217 (4)	0.0002 (3)	0.0010 (3)	0.0016 (4)
C11	0.0210 (5)	0.0156 (5)	0.0338 (6)	0.0004 (4)	0.0006 (4)	0.0016 (4)
C12	0.0237 (5)	0.0184 (5)	0.0384 (6)	0.0017 (4)	0.0032 (5)	−0.0064 (5)
C13	0.0275 (6)	0.0241 (6)	0.0290 (5)	−0.0001 (4)	0.0063 (4)	−0.0089 (4)
C14	0.0248 (5)	0.0203 (5)	0.0200 (4)	−0.0011 (4)	0.0043 (4)	−0.0030 (4)
C15	0.0168 (4)	0.0162 (5)	0.0178 (4)	0.0005 (3)	0.0015 (3)	−0.0002 (3)
C16	0.0238 (5)	0.0205 (5)	0.0155 (4)	−0.0021 (4)	0.0036 (3)	−0.0015 (3)
C17	0.0163 (4)	0.0144 (4)	0.0151 (4)	−0.0010 (3)	0.0019 (3)	0.0016 (3)
C18	0.0177 (4)	0.0146 (4)	0.0190 (4)	−0.0014 (3)	0.0027 (3)	−0.0003 (3)
C19	0.0167 (4)	0.0172 (5)	0.0208 (4)	−0.0007 (3)	0.0028 (3)	−0.0002 (3)
C20	0.0209 (4)	0.0155 (4)	0.0174 (4)	0.0029 (4)	0.0041 (3)	0.0007 (3)
C21	0.0240 (5)	0.0133 (4)	0.0205 (4)	−0.0016 (4)	0.0053 (4)	−0.0005 (3)
C22	0.0191 (4)	0.0154 (4)	0.0189 (4)	−0.0038 (3)	0.0032 (3)	0.0002 (3)

Cl1—C20	1.7407 (11)	C8—C15	1.4515 (15)
S1—O1	1.4480 (8)	C9—H9A	0.9300
S1—O2	1.4495 (8)	C10—C11	1.3937 (16)
S1—O3	1.4615 (9)	C10—C15	1.4172 (15)
S1—C17	1.7769 (11)	C11—C12	1.3848 (19)
N1—C1	1.3595 (14)	C11—H11A	0.9300
N1—C5	1.3699 (13)	C12—C13	1.4033 (19)
N1—C16	1.4790 (14)	C12—H12A	0.9300
N2—C9	1.3531 (15)	C13—C14	1.3862 (17)
N2—C10	1.3823 (15)	C13—H13A	0.9300
N2—H1N2	0.891 (18)	C14—C15	1.4060 (15)
C1—C2	1.3673 (17)	C14—H14A	0.9300
C1—H1A	0.9300	C16—H16A	0.9600
C2—C3	1.3961 (17)	C16—H16B	0.9600
C2—H2A	0.9300	C16—H16C	0.9600
C3—C4	1.3723 (16)	C17—C22	1.3949 (15)
C3—H3A	0.9300	C17—C18	1.3996 (14)
C4—C5	1.4111 (15)	C18—C19	1.3887 (15)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.4442 (15)	C19—C20	1.3901 (15)
C6—C7	1.3567 (14)	C19—H19A	0.9300
C6—H6A	0.9300	C20—C21	1.3896 (16)
C7—C8	1.4318 (15)	C21—C22	1.3990 (15)
C7—H7A	0.9300	C21—H21A	0.9300
C8—C9	1.3947 (14)	C22—H22A	0.9300
O1—S1—O2	113.07 (5)	C11—C10—C15	123.00 (10)
O1—S1—O3	113.29 (6)	C12—C11—C10	117.11 (11)
O2—S1—O3	112.84 (6)	C12—C11—H11A	121.4
O1—S1—C17	106.28 (5)	C10—C11—H11A	121.4
O2—S1—C17	105.82 (5)	C11—C12—C13	121.10 (11)
O3—S1—C17	104.64 (5)	C11—C12—H12A	119.5
C1—N1—C5	121.81 (9)	C13—C12—H12A	119.5
C1—N1—C16	117.49 (9)	C14—C13—C12	121.72 (11)
C5—N1—C16	120.70 (9)	C14—C13—H13A	119.1
C9—N2—C10	109.27 (9)	C12—C13—H13A	119.1
C9—N2—H1N2	125.2 (12)	C13—C14—C15	118.59 (11)
C10—N2—H1N2	125.2 (12)	C13—C14—H14A	120.7
N1—C1—C2	121.68 (10)	C15—C14—H14A	120.7
N1—C1—H1A	119.2	C14—C15—C10	118.46 (10)
C2—C1—H1A	119.2	C14—C15—C8	135.36 (10)
C1—C2—C3	118.40 (11)	C10—C15—C8	106.17 (9)
C1—C2—H2A	120.8	N1—C16—H16A	109.5
C3—C2—H2A	120.8	N1—C16—H16B	109.5
C4—C3—C2	119.79 (11)	H16A—C16—H16B	109.5
C4—C3—H3A	120.1	N1—C16—H16C	109.5
C2—C3—H3A	120.1	H16A—C16—H16C	109.5
C3—C4—C5	121.33 (10)	H16B—C16—H16C	109.5
C3—C4—H4A	119.3	C22—C17—C18	120.38 (10)
C5—C4—H4A	119.3	C22—C17—S1	121.17 (8)
N1—C5—C4	116.96 (10)	C18—C17—S1	118.44 (8)
N1—C5—C6	119.06 (9)	C19—C18—C17	120.07 (10)
C4—C5—C6	123.98 (9)	C19—C18—H18A	120.0
C7—C6—C5	123.15 (10)	C17—C18—H18A	120.0
C7—C6—H6A	118.4	C18—C19—C20	118.93 (10)
C5—C6—H6A	118.4	C18—C19—H19A	120.5
C6—C7—C8	126.99 (10)	C20—C19—H19A	120.5
C6—C7—H7A	116.5	C21—C20—C19	121.96 (10)
C8—C7—H7A	116.5	C21—C20—Cl1	119.80 (8)
C9—C8—C7	121.99 (10)	C19—C20—Cl1	118.19 (8)
C9—C8—C15	106.00 (9)	C20—C21—C22	118.85 (10)
C7—C8—C15	132.01 (9)	C20—C21—H21A	120.6
N2—C9—C8	110.32 (10)	C22—C21—H21A	120.6
N2—C9—H9A	124.8	C17—C22—C21	119.79 (10)
C8—C9—H9A	124.8	C17—C22—H22A	120.1
N2—C10—C11	128.76 (11)	C21—C22—H22A	120.1
N2—C10—C15	108.23 (10)
C5—N1—C1—C2	0.81 (16)	C13—C14—C15—C10	−1.26 (16)
C16—N1—C1—C2	−179.81 (10)	C13—C14—C15—C8	−179.77 (12)
N1—C1—C2—C3	0.65 (17)	N2—C10—C15—C14	−178.58 (10)
C1—C2—C3—C4	−1.28 (17)	C11—C10—C15—C14	1.74 (16)
C2—C3—C4—C5	0.51 (18)	N2—C10—C15—C8	0.33 (12)
C1—N1—C5—C4	−1.56 (15)	C11—C10—C15—C8	−179.35 (10)
C16—N1—C5—C4	179.08 (9)	C9—C8—C15—C14	177.96 (12)
C1—N1—C5—C6	178.44 (10)	C7—C8—C15—C14	−2.8 (2)
C16—N1—C5—C6	−0.92 (14)	C9—C8—C15—C10	−0.68 (12)
C3—C4—C5—N1	0.90 (16)	C7—C8—C15—C10	178.61 (11)
C3—C4—C5—C6	−179.10 (11)	O1—S1—C17—C22	25.07 (10)
N1—C5—C6—C7	−178.80 (10)	O2—S1—C17—C22	−95.40 (9)
C4—C5—C6—C7	1.21 (17)	O3—S1—C17—C22	145.20 (9)
C5—C6—C7—C8	179.27 (10)	O1—S1—C17—C18	−155.09 (8)
C6—C7—C8—C9	176.40 (11)	O2—S1—C17—C18	84.44 (9)
C6—C7—C8—C15	−2.78 (19)	O3—S1—C17—C18	−34.96 (9)
C10—N2—C9—C8	−0.61 (13)	C22—C17—C18—C19	−0.23 (15)
C7—C8—C9—N2	−178.58 (10)	S1—C17—C18—C19	179.92 (8)
C15—C8—C9—N2	0.79 (12)	C17—C18—C19—C20	−0.80 (15)
C9—N2—C10—C11	179.81 (11)	C18—C19—C20—C21	1.17 (16)
C9—N2—C10—C15	0.15 (12)	C18—C19—C20—Cl1	−176.49 (8)
N2—C10—C11—C12	179.53 (11)	C19—C20—C21—C22	−0.48 (16)
C15—C10—C11—C12	−0.86 (17)	Cl1—C20—C21—C22	177.14 (8)
C10—C11—C12—C13	−0.48 (18)	C18—C17—C22—C21	0.93 (15)
C11—C12—C13—C14	0.92 (19)	S1—C17—C22—C21	−179.23 (8)
C12—C13—C14—C15	−0.01 (18)	C20—C21—C22—C17	−0.57 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1i	0.891 (18)	1.864 (19)	2.7541 (14)	176.2 (18)
C1—H1A···O3	0.93	2.53	3.2380 (14)	133
C7—H7A···O2ii	0.93	2.59	3.3067 (14)	134
C14—H14A···O2iii	0.93	2.52	3.2605 (14)	137
C16—H16C···O2iii	0.96	2.37	3.2645 (15)	156
C19—H19A···O1iv	0.93	2.30	3.1432 (14)	151
C21—H21A···O3iii	0.93	2.55	3.1885 (14)	127
C4—H4A···Cg3v	0.93	2.85	3.5956 (11)	138
C16—H16A···Cg1vi	0.96	2.72	3.4622 (12)	134
C16—H16B···Cg3	0.96	2.67	3.5533 (11)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1i	0.891 (18)	1.864 (19)	2.7541 (14)	176.2 (18)
C1—H1A⋯O3	0.93	2.53	3.2380 (14)	133
C7—H7A⋯O2ii	0.93	2.59	3.3067 (14)	134
C14—H14A⋯O2iii	0.93	2.52	3.2605 (14)	137
C16—H16C⋯O2iii	0.96	2.37	3.2645 (15)	156
C19—H19A⋯O1iv	0.93	2.30	3.1432 (14)	151
C21—H21A⋯O3iii	0.93	2.55	3.1885 (14)	127
C4—H4A⋯Cg3v	0.93	2.85	3.5956 (11)	138
C16—H16A⋯Cg1vi	0.96	2.72	3.4622 (12)	134
C16—H16B⋯Cg3	0.96	2.67	3.5533 (11)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1 and Cg3 are the centroids of the N2/C8–C9/C10/C15 and C10–C15 rings, respectively.