4-(4-Bromo-styr-yl)-1-methylpyridinium tosyl-ate.

In the cation of the title compound, C14H13BrN(+)·C7H7O3S(-), the dihedral angle between the benzene and pyridine rings is 8.34 (11)°. The Br atom is disordered over two positions with site occupancies of 0.74 (2) and 0.26 (2). The mol-ecular structure is stabilized by a weak intra-molecular C-H⋯O inter-actions. The crystal structure exhibits weak C-H⋯O and π-π [centroid-centroid distance = 3.7466 (17) Å] inter-actions, forming a three dimensional network.

Related literature

For mol­ecular compounds with non-linear optical properties, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶). For similar structures, see: Krishnakumar et al. (2012 ▶); Okada et al. (1990 ▶); Sivakumar et al. (2012 ▶).

Experimental

Crystal data

C14H13BrN+·C7H7O3S−

M = 446.35

Monoclinic,

a = 9.0502 (2) Å

b = 6.4201 (1) Å

c = 33.9280 (7) Å

β = 94.469 (1)°

V = 1965.33 (7) Å3

Z = 4

Mo Kα radiation

μ = 2.22 mm−1

T = 295 K

0.28 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.575, T max = 0.665

22764 measured reflections

5596 independent reflections

3012 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.130

S = 1.01

5596 reflections

256 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009227/bt6900sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009227/bt6900Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009227/bt6900Isup3.cml

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

C14H13BrN+·C7H7O3S−	F(000) = 912
Mr = 446.35	Dx = 1.509 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4367 reflections
a = 9.0502 (2) Å	θ = 2.4–24.1°
b = 6.4201 (1) Å	µ = 2.22 mm−1
c = 33.9280 (7) Å	T = 295 K
β = 94.469 (1)°	Block, orange
V = 1965.33 (7) Å3	0.28 × 0.22 × 0.20 mm
Z = 4

Bruker APEXII CCD diffractometer	5596 independent reflections
Radiation source: fine-focus sealed tube	3012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω and φ scan	θmax = 29.8°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.575, Tmax = 0.665	k = −8→8
22764 measured reflections	l = −47→47

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0525P)2 + 0.7449P] where P = (Fo2 + 2Fc2)/3
5596 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.34 e Å−3
1 restraint	Δρmin = −0.30 e Å−3

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	Occ. (<1)
Br1	0.6169 (3)	0.7372 (4)	0.03376 (7)	0.0820 (5)	0.74 (2)
Br1A	0.661 (3)	0.7520 (14)	0.0342 (2)	0.114 (3)	0.26 (2)
S1	1.20686 (7)	0.07504 (10)	0.18347 (2)	0.04224 (18)
O1	1.07764 (19)	−0.0120 (3)	0.19985 (6)	0.0565 (5)
O2	1.34369 (19)	−0.0096 (3)	0.20147 (6)	0.0577 (5)
O3	1.2060 (3)	0.3000 (3)	0.18168 (7)	0.0682 (6)
N1	0.7301 (2)	−0.7025 (3)	0.21855 (6)	0.0415 (5)
C1	0.6600 (4)	0.5062 (5)	0.06660 (8)	0.0565 (8)
C2	0.7976 (4)	0.4692 (5)	0.08326 (10)	0.0673 (9)
H2	0.8749	0.5597	0.0788	0.081*
C3	0.8230 (3)	0.2970 (5)	0.10686 (10)	0.0627 (8)
H3	0.9181	0.2728	0.1183	0.075*
C4	0.7112 (3)	0.1586 (4)	0.11408 (8)	0.0473 (6)
C5	0.5724 (3)	0.2032 (5)	0.09664 (11)	0.0670 (9)
H5	0.4941	0.1143	0.1009	0.080*
C6	0.5463 (4)	0.3750 (5)	0.07309 (11)	0.0714 (9)
H6	0.4514	0.4017	0.0616	0.086*
C7	0.7449 (3)	−0.0240 (4)	0.13914 (8)	0.0504 (7)
H7	0.8441	−0.0491	0.1469	0.061*
C8	0.6481 (3)	−0.1545 (5)	0.15144 (9)	0.0521 (7)
H8	0.5487	−0.1269	0.1443	0.063*
C9	0.6818 (3)	−0.3409 (4)	0.17554 (8)	0.0455 (6)
C10	0.8234 (3)	−0.4050 (4)	0.18908 (8)	0.0493 (7)
H10	0.9046	−0.3240	0.1837	0.059*
C11	0.8453 (3)	−0.5847 (4)	0.21009 (8)	0.0470 (6)
H11	0.9411	−0.6258	0.2186	0.056*
C12	0.5923 (3)	−0.6440 (5)	0.20655 (9)	0.0512 (7)
H12	0.5127	−0.7259	0.2128	0.061*
C13	0.5670 (3)	−0.4672 (4)	0.18542 (9)	0.0530 (7)
H13	0.4700	−0.4300	0.1774	0.064*
C14	0.7558 (3)	−0.8921 (4)	0.24243 (9)	0.0569 (7)
H14A	0.7714	−0.8550	0.2698	0.085*
H14B	0.8416	−0.9633	0.2343	0.085*
H14C	0.6709	−0.9818	0.2387	0.085*
C15	1.1957 (2)	−0.0120 (4)	0.13392 (7)	0.0364 (5)
C16	1.1865 (3)	−0.2225 (4)	0.12499 (9)	0.0510 (7)
H16	1.1866	−0.3207	0.1451	0.061*
C17	1.1773 (4)	−0.2852 (4)	0.08614 (10)	0.0608 (8)
H17	1.1720	−0.4269	0.0805	0.073*
C18	1.1756 (3)	−0.1453 (5)	0.05514 (9)	0.0552 (7)
C19	1.1841 (3)	0.0620 (4)	0.06475 (9)	0.0581 (8)
H19	1.1825	0.1602	0.0446	0.070*
C20	1.1949 (3)	0.1286 (4)	0.10329 (9)	0.0506 (7)
H20	1.2017	0.2703	0.1088	0.061*
C21	1.1620 (5)	−0.2217 (6)	0.01292 (11)	0.0876 (12)
H21A	1.2117	−0.1265	−0.0034	0.131*
H21B	1.0592	−0.2301	0.0037	0.131*
H21C	1.2065	−0.3571	0.0117	0.131*

	U11	U22	U33	U12	U13	U23
Br1	0.1112 (16)	0.0651 (6)	0.0679 (8)	−0.0001 (6)	−0.0054 (9)	0.0221 (5)
Br1A	0.221 (9)	0.0675 (15)	0.056 (2)	−0.014 (4)	0.035 (3)	0.0058 (14)
S1	0.0401 (3)	0.0448 (3)	0.0418 (4)	−0.0058 (3)	0.0029 (3)	0.0025 (3)
O1	0.0419 (10)	0.0793 (14)	0.0494 (12)	−0.0104 (9)	0.0113 (9)	0.0024 (10)
O2	0.0403 (10)	0.0760 (13)	0.0552 (13)	−0.0059 (9)	−0.0076 (9)	0.0081 (11)
O3	0.0979 (16)	0.0441 (11)	0.0628 (15)	−0.0029 (11)	0.0076 (12)	−0.0069 (10)
N1	0.0467 (13)	0.0424 (11)	0.0358 (12)	−0.0019 (9)	0.0053 (10)	−0.0073 (9)
C1	0.081 (2)	0.0525 (16)	0.0361 (16)	0.0023 (15)	0.0046 (15)	−0.0002 (13)
C2	0.064 (2)	0.070 (2)	0.069 (2)	−0.0132 (16)	0.0120 (17)	0.0067 (17)
C3	0.0457 (17)	0.076 (2)	0.066 (2)	0.0034 (15)	0.0024 (15)	0.0074 (17)
C4	0.0510 (16)	0.0518 (14)	0.0388 (15)	0.0038 (12)	0.0018 (12)	−0.0070 (11)
C5	0.0480 (17)	0.073 (2)	0.079 (2)	−0.0073 (15)	−0.0014 (16)	0.0167 (18)
C6	0.061 (2)	0.076 (2)	0.075 (2)	0.0052 (17)	−0.0104 (17)	0.0167 (19)
C7	0.0467 (15)	0.0560 (15)	0.0480 (17)	0.0027 (13)	−0.0005 (13)	−0.0029 (12)
C8	0.0437 (15)	0.0581 (16)	0.0536 (18)	0.0031 (13)	−0.0022 (13)	−0.0059 (14)
C9	0.0499 (16)	0.0482 (14)	0.0382 (15)	−0.0011 (12)	0.0026 (12)	−0.0095 (12)
C10	0.0436 (15)	0.0543 (15)	0.0497 (17)	−0.0118 (12)	0.0026 (12)	0.0000 (13)
C11	0.0361 (13)	0.0595 (16)	0.0449 (16)	−0.0010 (12)	−0.0010 (11)	−0.0060 (13)
C12	0.0409 (15)	0.0594 (17)	0.0534 (18)	−0.0091 (12)	0.0052 (13)	−0.0055 (14)
C13	0.0393 (15)	0.0634 (18)	0.0561 (19)	0.0012 (13)	0.0025 (13)	0.0013 (14)
C14	0.076 (2)	0.0468 (15)	0.0483 (18)	0.0000 (14)	0.0070 (15)	0.0009 (13)
C15	0.0309 (12)	0.0393 (12)	0.0389 (14)	0.0003 (9)	0.0024 (10)	0.0049 (10)
C16	0.0661 (18)	0.0366 (13)	0.0499 (18)	0.0002 (12)	0.0017 (14)	0.0081 (12)
C17	0.082 (2)	0.0402 (15)	0.060 (2)	−0.0009 (14)	0.0030 (17)	−0.0045 (14)
C18	0.0548 (17)	0.0639 (18)	0.0465 (18)	0.0039 (14)	0.0019 (14)	−0.0039 (15)
C19	0.077 (2)	0.0534 (16)	0.0438 (18)	−0.0008 (15)	0.0046 (15)	0.0125 (14)
C20	0.0622 (17)	0.0384 (13)	0.0515 (18)	−0.0031 (12)	0.0069 (14)	0.0067 (12)
C21	0.111 (3)	0.097 (3)	0.054 (2)	0.002 (2)	0.003 (2)	−0.016 (2)

Br1—C1	1.878 (4)	C9—C10	1.390 (4)
Br1A—C1	1.924 (9)	C10—C11	1.362 (4)
S1—O2	1.4435 (19)	C10—H10	0.9300
S1—O3	1.445 (2)	C11—H11	0.9300
S1—O1	1.4458 (19)	C12—C13	1.352 (4)
S1—C15	1.767 (3)	C12—H12	0.9300
N1—C12	1.335 (3)	C13—H13	0.9300
N1—C11	1.337 (3)	C14—H14A	0.9600
N1—C14	1.471 (3)	C14—H14B	0.9600
C1—C2	1.348 (4)	C14—H14C	0.9600
C1—C6	1.361 (4)	C15—C20	1.376 (4)
C2—C3	1.374 (4)	C15—C16	1.387 (3)
C2—H2	0.9300	C16—C17	1.375 (4)
C3—C4	1.383 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.382 (4)
C4—C5	1.376 (4)	C17—H17	0.9300
C4—C7	1.466 (4)	C18—C19	1.371 (4)
C5—C6	1.372 (4)	C18—C21	1.510 (5)
C5—H5	0.9300	C19—C20	1.372 (4)
C6—H6	0.9300	C19—H19	0.9300
C7—C8	1.304 (4)	C20—H20	0.9300
C7—H7	0.9300	C21—H21A	0.9600
C8—C9	1.468 (4)	C21—H21B	0.9600
C8—H8	0.9300	C21—H21C	0.9600
C9—C13	1.380 (4)
O2—S1—O3	113.31 (13)	C9—C10—H10	119.5
O2—S1—O1	112.63 (12)	N1—C11—C10	120.5 (2)
O3—S1—O1	113.60 (13)	N1—C11—H11	119.8
O2—S1—C15	105.49 (12)	C10—C11—H11	119.8
O3—S1—C15	106.03 (12)	N1—C12—C13	120.9 (3)
O1—S1—C15	104.81 (11)	N1—C12—H12	119.6
C12—N1—C11	120.1 (2)	C13—C12—H12	119.6
C12—N1—C14	120.3 (2)	C12—C13—C9	121.5 (3)
C11—N1—C14	119.6 (2)	C12—C13—H13	119.2
C2—C1—C6	120.6 (3)	C9—C13—H13	119.2
C2—C1—Br1	122.0 (3)	N1—C14—H14A	109.5
C6—C1—Br1	117.4 (3)	N1—C14—H14B	109.5
C2—C1—Br1A	109.9 (10)	H14A—C14—H14B	109.5
C6—C1—Br1A	129.5 (10)	N1—C14—H14C	109.5
C1—C2—C3	119.5 (3)	H14A—C14—H14C	109.5
C1—C2—H2	120.2	H14B—C14—H14C	109.5
C3—C2—H2	120.2	C20—C15—C16	118.5 (3)
C2—C3—C4	122.0 (3)	C20—C15—S1	120.5 (2)
C2—C3—H3	119.0	C16—C15—S1	120.9 (2)
C4—C3—H3	119.0	C17—C16—C15	119.5 (3)
C5—C4—C3	116.5 (3)	C17—C16—H16	120.2
C5—C4—C7	123.9 (3)	C15—C16—H16	120.2
C3—C4—C7	119.6 (2)	C16—C17—C18	122.4 (3)
C6—C5—C4	121.9 (3)	C16—C17—H17	118.8
C6—C5—H5	119.1	C18—C17—H17	118.8
C4—C5—H5	119.1	C19—C18—C17	116.9 (3)
C1—C6—C5	119.6 (3)	C19—C18—C21	122.7 (3)
C1—C6—H6	120.2	C17—C18—C21	120.4 (3)
C5—C6—H6	120.2	C18—C19—C20	121.8 (3)
C8—C7—C4	125.7 (3)	C18—C19—H19	119.1
C8—C7—H7	117.1	C20—C19—H19	119.1
C4—C7—H7	117.1	C19—C20—C15	120.8 (3)
C7—C8—C9	125.9 (3)	C19—C20—H20	119.6
C7—C8—H8	117.1	C15—C20—H20	119.6
C9—C8—H8	117.1	C18—C21—H21A	109.5
C13—C9—C10	116.0 (3)	C18—C21—H21B	109.5
C13—C9—C8	119.2 (2)	H21A—C21—H21B	109.5
C10—C9—C8	124.9 (2)	C18—C21—H21C	109.5
C11—C10—C9	121.1 (2)	H21A—C21—H21C	109.5
C11—C10—H10	119.5	H21B—C21—H21C	109.5
C6—C1—C2—C3	0.2 (5)	C11—N1—C12—C13	0.7 (4)
Br1—C1—C2—C3	−179.6 (3)	C14—N1—C12—C13	178.3 (3)
Br1A—C1—C2—C3	−178.3 (3)	N1—C12—C13—C9	−0.1 (5)
C1—C2—C3—C4	0.2 (5)	C10—C9—C13—C12	−0.9 (4)
C2—C3—C4—C5	−0.5 (5)	C8—C9—C13—C12	178.0 (3)
C2—C3—C4—C7	179.3 (3)	O2—S1—C15—C20	−117.6 (2)
C3—C4—C5—C6	0.4 (5)	O3—S1—C15—C20	2.8 (2)
C7—C4—C5—C6	−179.4 (3)	O1—S1—C15—C20	123.3 (2)
C2—C1—C6—C5	−0.3 (5)	O2—S1—C15—C16	62.9 (2)
Br1—C1—C6—C5	179.5 (3)	O3—S1—C15—C16	−176.7 (2)
Br1A—C1—C6—C5	177.8 (4)	O1—S1—C15—C16	−56.2 (2)
C4—C5—C6—C1	0.0 (6)	C20—C15—C16—C17	0.2 (4)
C5—C4—C7—C8	−7.5 (5)	S1—C15—C16—C17	179.7 (2)
C3—C4—C7—C8	172.8 (3)	C15—C16—C17—C18	−0.5 (5)
C4—C7—C8—C9	178.1 (3)	C16—C17—C18—C19	0.2 (5)
C7—C8—C9—C13	−178.3 (3)	C16—C17—C18—C21	−178.7 (3)
C7—C8—C9—C10	0.5 (5)	C17—C18—C19—C20	0.5 (5)
C13—C9—C10—C11	1.3 (4)	C21—C18—C19—C20	179.3 (3)
C8—C9—C10—C11	−177.5 (3)	C18—C19—C20—C15	−0.8 (5)
C12—N1—C11—C10	−0.3 (4)	C16—C15—C20—C19	0.5 (4)
C14—N1—C11—C10	−177.9 (3)	S1—C15—C20—C19	−179.1 (2)
C9—C10—C11—N1	−0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.57	3.415 (3)	151
C20—H20···O3	0.93	2.48	2.873 (4)	106
C12—H12···O2i	0.93	2.39	3.247 (3)	153
C14—H14B···O1ii	0.96	2.53	3.438 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1	0.93	2.57	3.415 (3)	151
C12—H12⋯O2i	0.93	2.39	3.247 (3)	153
C14—H14B⋯O1ii	0.96	2.53	3.438 (4)	157

Symmetry codes: (i) ; (ii) .