2-(4-Methyl-sulfanylphen-yl)-1H-benzimidazol-3-ium bromide.

In the cation of the title compound, C(14)H(13)N(2)S(+)·Br(-), the essentially planar benzimidazole system (r.m.s. deviation = 0.0082 Å) is substituted with a 4-methyl-sulfanylphenyl ring. The dihedral angle between the benzimidazole system and the 4-methyl-sulfanylphenyl ring is 2.133 (2)°. The crystal structure is characterized by strong and highly directional inter-molecular N-H⋯Br hydrogen bonds involving the bromide ion. Moreover, C-H⋯S inter-actions result in chains of mol-ecules along the c axis. The supra-molecular assembly is further stabilized by π-π stacking inter-actions between the benzimidazole system and 4-methyl-sulfanylphenyl rings [centroid-centroid distance = 3.477 (4) Å].

Related literature

For general background to benzimidazoles and their derivatives, see: Huang & Scarborough (1999 ▶); Preston (1974 ▶); Zarrinmayeh et al. (1998 ▶); Zhu et al. (2000 ▶). For related structures, see: Goker et al. (1995 ▶); Ozbey et al. (1998 ▶); Vasudevan et al. (1994 ▶). For hydrogen bonding, see: Bernstein et al. (1995 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C14H13N2S+·Br−

M = 321.23

Monoclinic,

a = 5.3289 (2) Å

b = 24.0195 (12) Å

c = 10.9544 (5) Å

β = 100.113 (2)°

V = 1380.35 (11) Å3

Z = 4

Mo Kα radiation

μ = 3.11 mm−1

T = 296 K

0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.575, T max = 0.636

23823 measured reflections

3009 independent reflections

2273 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.069

S = 1.03

3009 reflections

215 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1996) ▶; software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000146/pb2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000146/pb2053Isup2.hkl

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

C14H13N2S+·Br−	F(000) = 648
Mr = 321.23	Dx = 1.546 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3009 reflections
a = 5.3289 (2) Å	θ = 1.7–27.0°
b = 24.0195 (12) Å	µ = 3.11 mm−1
c = 10.9544 (5) Å	T = 296 K
β = 100.113 (2)°	Block, yellow
V = 1380.35 (11) Å3	0.20 × 0.18 × 0.16 mm
Z = 4

Bruker SMART APEX CCD detector diffractometer	3009 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2273 reflections with I > 2σ(I)
graphite	Rint = 0.039
ω scans	θmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan Bruker Kappa APEX	h = −6→6
Tmin = 0.575, Tmax = 0.636	k = −30→30
23823 measured reflections	l = −13→13

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0338P)2 + 0.3109P] where P = (Fo2 + 2Fc2)/3
3009 reflections	(Δ/σ)max = 0.001
215 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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	0.27225 (4)	0.295277 (10)	0.33608 (2)	0.04982 (10)
S1	0.57379 (16)	−0.00128 (3)	0.21720 (8)	0.0710 (2)
N1	0.6485 (4)	0.28057 (8)	0.13508 (19)	0.0421 (5)
N2	0.9186 (4)	0.25577 (8)	0.01982 (17)	0.0408 (4)
C1	0.9109 (4)	0.31328 (10)	0.0161 (2)	0.0415 (5)
C2	1.0437 (5)	0.35189 (11)	−0.0424 (2)	0.0555 (6)
C3	0.9910 (6)	0.40696 (12)	−0.0233 (3)	0.0644 (7)
C4	0.8149 (6)	0.42307 (12)	0.0504 (3)	0.0659 (8)
C5	0.6847 (5)	0.38481 (11)	0.1084 (3)	0.0555 (6)
C6	0.7381 (4)	0.32913 (10)	0.0906 (2)	0.0430 (5)
C7	0.7610 (4)	0.23676 (9)	0.09243 (19)	0.0387 (5)
C8	0.7198 (4)	0.17861 (9)	0.1213 (2)	0.0391 (5)
C9	0.5449 (5)	0.16389 (11)	0.1960 (2)	0.0516 (6)
C10	0.5058 (5)	0.10930 (11)	0.2220 (2)	0.0558 (6)
C11	0.6392 (5)	0.06710 (10)	0.1762 (2)	0.0453 (5)
C12	0.8139 (6)	0.08164 (11)	0.1013 (3)	0.0586 (7)
C13	0.8530 (5)	0.13648 (11)	0.0746 (3)	0.0548 (7)
C14	0.7734 (8)	−0.04379 (14)	0.1398 (4)	0.0721 (9)
H1N	0.562 (5)	0.2802 (10)	0.181 (2)	0.042 (7)*
H9	0.464 (5)	0.1907 (12)	0.233 (2)	0.062 (8)*
H2N	0.991 (5)	0.2357 (11)	−0.017 (2)	0.049 (8)*
H12	0.909 (5)	0.0539 (11)	0.070 (2)	0.065 (8)*
H14C	0.736 (6)	−0.0776 (16)	0.159 (3)	0.086 (11)*
H14B	0.947 (7)	−0.0359 (13)	0.169 (3)	0.090 (11)*
H5	0.567 (5)	0.3946 (12)	0.163 (2)	0.075 (9)*
H4	0.781 (6)	0.4619 (13)	0.063 (3)	0.085 (10)*
H2	1.159 (5)	0.3398 (11)	−0.092 (2)	0.058 (7)*
H13	0.975 (5)	0.1462 (12)	0.022 (3)	0.079 (9)*
H10	0.389 (5)	0.0996 (11)	0.276 (2)	0.064 (7)*
H3	1.080 (5)	0.4350 (12)	−0.060 (2)	0.070 (8)*
H14A	0.736 (6)	−0.0374 (14)	0.054 (3)	0.097 (12)*

	U11	U22	U33	U12	U13	U23
Br1	0.05371 (15)	0.05390 (17)	0.04775 (15)	0.00057 (11)	0.02515 (10)	0.00017 (11)
S1	0.0965 (6)	0.0390 (4)	0.0891 (5)	−0.0055 (3)	0.0480 (4)	0.0060 (3)
N1	0.0446 (11)	0.0397 (11)	0.0476 (11)	−0.0021 (8)	0.0233 (9)	−0.0012 (9)
N2	0.0441 (10)	0.0396 (11)	0.0436 (11)	−0.0006 (9)	0.0212 (9)	−0.0029 (9)
C1	0.0442 (12)	0.0399 (12)	0.0414 (12)	−0.0043 (10)	0.0105 (10)	−0.0003 (10)
C2	0.0593 (16)	0.0521 (16)	0.0598 (15)	−0.0093 (12)	0.0233 (13)	0.0045 (13)
C3	0.0741 (19)	0.0474 (16)	0.0755 (18)	−0.0129 (14)	0.0231 (15)	0.0080 (14)
C4	0.077 (2)	0.0386 (16)	0.082 (2)	−0.0056 (13)	0.0140 (16)	−0.0001 (14)
C5	0.0626 (16)	0.0411 (15)	0.0655 (16)	0.0024 (12)	0.0185 (13)	−0.0077 (13)
C6	0.0433 (12)	0.0414 (13)	0.0450 (12)	−0.0031 (10)	0.0099 (9)	−0.0011 (10)
C7	0.0380 (11)	0.0407 (13)	0.0392 (11)	−0.0013 (10)	0.0121 (9)	0.0001 (10)
C8	0.0400 (12)	0.0394 (13)	0.0392 (11)	−0.0015 (10)	0.0109 (9)	0.0009 (10)
C9	0.0621 (16)	0.0380 (13)	0.0626 (15)	0.0046 (11)	0.0331 (13)	0.0005 (12)
C10	0.0620 (16)	0.0484 (15)	0.0665 (16)	−0.0018 (12)	0.0377 (13)	0.0054 (13)
C11	0.0512 (13)	0.0386 (13)	0.0483 (13)	−0.0036 (10)	0.0147 (10)	0.0016 (10)
C12	0.0705 (18)	0.0389 (15)	0.0762 (18)	0.0019 (12)	0.0400 (15)	−0.0019 (13)
C13	0.0615 (16)	0.0436 (15)	0.0689 (16)	0.0011 (12)	0.0377 (14)	−0.0004 (12)
C14	0.091 (3)	0.0407 (18)	0.089 (3)	0.0024 (16)	0.028 (2)	−0.0003 (16)

S1—C11	1.754 (2)	C5—C6	1.388 (3)
S1—C14	1.791 (4)	C5—H5	0.97 (3)
N1—C7	1.335 (3)	C7—C8	1.457 (3)
N1—C6	1.381 (3)	C8—C13	1.384 (3)
N1—H1N	0.74 (3)	C8—C9	1.390 (3)
N2—C7	1.334 (3)	C9—C10	1.365 (4)
N2—C1	1.382 (3)	C9—H9	0.91 (3)
N2—H2N	0.77 (3)	C10—C11	1.382 (3)
C1—C6	1.386 (3)	C10—H10	0.96 (3)
C1—C2	1.390 (3)	C11—C12	1.389 (3)
C2—C3	1.376 (4)	C12—C13	1.373 (4)
C2—H2	0.93 (3)	C12—H12	0.94 (3)
C3—C4	1.395 (4)	C13—H13	0.97 (3)
C3—H3	0.95 (3)	C14—H14C	0.87 (4)
C4—C5	1.373 (4)	C14—H14B	0.94 (3)
C4—H4	0.96 (3)	C14—H14A	0.94 (3)
C11—S1—C14	104.57 (15)	N2—C7—C8	126.29 (19)
C7—N1—C6	109.73 (19)	N1—C7—C8	125.82 (18)
C7—N1—H1N	127.0 (19)	C13—C8—C9	118.2 (2)
C6—N1—H1N	123.0 (19)	C13—C8—C7	120.93 (19)
C7—N2—C1	109.94 (18)	C9—C8—C7	120.9 (2)
C7—N2—H2N	121.6 (19)	C10—C9—C8	120.6 (2)
C1—N2—H2N	128.3 (19)	C10—C9—H9	118.9 (17)
N2—C1—C6	106.04 (19)	C8—C9—H9	120.3 (17)
N2—C1—C2	131.7 (2)	C9—C10—C11	121.5 (2)
C6—C1—C2	122.2 (2)	C9—C10—H10	120.0 (16)
C3—C2—C1	115.9 (3)	C11—C10—H10	118.4 (16)
C3—C2—H2	124.1 (16)	C10—C11—C12	118.1 (2)
C1—C2—H2	120.0 (16)	C10—C11—S1	117.15 (18)
C2—C3—C4	122.1 (3)	C12—C11—S1	124.79 (19)
C2—C3—H3	119.2 (17)	C13—C12—C11	120.6 (2)
C4—C3—H3	118.7 (17)	C13—C12—H12	119.2 (17)
C5—C4—C3	121.9 (3)	C11—C12—H12	120.2 (17)
C5—C4—H4	117.2 (19)	C12—C13—C8	121.1 (2)
C3—C4—H4	121.0 (19)	C12—C13—H13	120.1 (17)
C4—C5—C6	116.5 (3)	C8—C13—H13	118.9 (18)
C4—C5—H5	123.9 (18)	S1—C14—H14C	104 (2)
C6—C5—H5	119.5 (18)	S1—C14—H14B	111 (2)
N1—C6—C1	106.4 (2)	H14C—C14—H14B	111 (3)
N1—C6—C5	132.2 (2)	S1—C14—H14A	110 (2)
C1—C6—C5	121.4 (2)	H14C—C14—H14A	112 (3)
N2—C7—N1	107.9 (2)	H14B—C14—H14A	109 (3)
C7—N2—C1—C6	−0.2 (3)	C6—N1—C7—C8	178.60 (19)
C7—N2—C1—C2	177.8 (3)	N2—C7—C8—C13	1.4 (3)
N2—C1—C2—C3	−178.5 (2)	N1—C7—C8—C13	−178.0 (2)
C6—C1—C2—C3	−0.8 (4)	N2—C7—C8—C9	−178.3 (2)
C1—C2—C3—C4	0.0 (4)	N1—C7—C8—C9	2.2 (3)
C2—C3—C4—C5	0.3 (5)	C13—C8—C9—C10	−0.2 (4)
C3—C4—C5—C6	0.3 (4)	C7—C8—C9—C10	179.5 (2)
C7—N1—C6—C1	0.8 (3)	C8—C9—C10—C11	0.6 (4)
C7—N1—C6—C5	−179.2 (3)	C9—C10—C11—C12	−0.7 (4)
N2—C1—C6—N1	−0.4 (2)	C9—C10—C11—S1	179.5 (2)
C2—C1—C6—N1	−178.6 (2)	C14—S1—C11—C10	178.8 (2)
N2—C1—C6—C5	179.6 (2)	C14—S1—C11—C12	−1.0 (3)
C2—C1—C6—C5	1.4 (4)	C10—C11—C12—C13	0.4 (4)
C4—C5—C6—N1	178.9 (3)	S1—C11—C12—C13	−179.8 (2)
C4—C5—C6—C1	−1.1 (4)	C11—C12—C13—C8	−0.1 (5)
C1—N2—C7—N1	0.7 (3)	C9—C8—C13—C12	−0.1 (4)
C1—N2—C7—C8	−178.83 (19)	C7—C8—C13—C12	−179.8 (2)
C6—N1—C7—N2	−0.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Br1	0.74 (2)	2.51 (2)	3.247 (2)	171 (2)
N2—H2N···Br1i	0.77 (3)	2.50 (2)	3.231 (2)	159
C5—H5···S1ii	0.97 (3)	2.98 (3)	3.736 (3)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Br1	0.74 (2)	2.51 (2)	3.247 (2)	171 (2)
N2—H2N⋯Br1i	0.77 (3)	2.50 (2)	3.231 (2)	159
C5—H5⋯S1ii	0.97 (3)	2.98 (3)	3.736 (3)	135

Symmetry codes: (i) ; (ii) .