3-(3-Meth-oxy-phen-yl)benzo[d]thia-zolo[3,2-a]imidazol-9-ium hydrogen sulfate.

In the title mol-ecular salt, C(16)H(13)N(2)OS(+)·HSO(4) (-), the thia-zolo[3,2-a]benzimidazolium ring system is roughly planar [maximum deviation = 0.046 (3) Å] and makes a dihedral angle of 58.22 (11)° with the benzene ring. The meth-oxy group is almost coplanar with its attached benzene ring [C(meth-yl)-O-C-C = -1.6 (5)°]. In the crystal, the cation is linked to the anion by a bifurcated N-H⋯(O,O) hydrogen bond, generating an R(1) (2)(4) ring motif. The ion pairs are then connected by a C-H⋯O hydrogen bond into inversion dimers and these dimers are further linked by O-H⋯O hydrogen bonds into an infinite tape along [100]. A π-π stacking inter-action [centroid-to-centroid distance = 3.5738 (18) Å] and a short inter-molecular contact [S⋯O = 2.830 (3) Å] are also observed.

Related literature

For the biological activities of thia­zolo[3,2-a]benzimidazoles, see: Chimirri et al. (1988 ▶); Al-Rashood & Abdel-Aziz (2010 ▶); Hamdy et al. (2007 ▶); Abdel-Aziz et al. (2007 ▶, 2008 ▶); Farag et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H13N2OS+·HSO4 −

M = 378.41

Monoclinic,

a = 4.5428 (8) Å

b = 20.096 (4) Å

c = 17.788 (3) Å

β = 93.003 (4)°

V = 1621.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.36 mm−1

T = 100 K

0.31 × 0.15 × 0.12 mm

Data collection

Bruker APEX DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.898, T max = 0.959

12491 measured reflections

3699 independent reflections

2904 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.170

S = 1.04

3699 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.99 e Å−3

Δρmin = −0.68 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536812030541/hb6885sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030541/hb6885Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812030541/hb6885Isup3.cml

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

C16H13N2OS+·HSO4−	F(000) = 784
Mr = 378.41	Dx = 1.550 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4717 reflections
a = 4.5428 (8) Å	θ = 2.3–29.3°
b = 20.096 (4) Å	µ = 0.36 mm−1
c = 17.788 (3) Å	T = 100 K
β = 93.003 (4)°	Block, colourless
V = 1621.6 (5) Å3	0.31 × 0.15 × 0.12 mm
Z = 4

Bruker APEX DUO CCD diffractometer	3699 independent reflections
Radiation source: fine-focus sealed tube	2904 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
Tmin = 0.898, Tmax = 0.959	k = −26→24
12491 measured reflections	l = −19→23

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0882P)2 + 3.0462P] where P = (Fo2 + 2Fc2)/3
3699 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.99 e Å−3
0 restraints	Δρmin = −0.68 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 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
S1	0.21267 (17)	0.46487 (4)	0.42583 (4)	0.0192 (2)
S2	0.24639 (17)	0.37855 (4)	0.66173 (4)	0.0214 (2)
O1	0.7757 (6)	0.47885 (11)	0.06026 (13)	0.0313 (6)
O2	0.0440 (5)	0.31645 (11)	0.67548 (13)	0.0281 (5)
H1O2	−0.1640	0.3283	0.6741	0.042*
O3	0.5152 (6)	0.34615 (13)	0.63785 (13)	0.0325 (6)
O4	0.1087 (6)	0.41582 (12)	0.59898 (14)	0.0315 (6)
O5	0.2805 (7)	0.41374 (13)	0.73091 (15)	0.0416 (7)
N1	0.5806 (6)	0.36239 (12)	0.48611 (14)	0.0176 (5)
N2	0.5187 (5)	0.37532 (11)	0.36286 (13)	0.0154 (5)
C1	0.7199 (6)	0.32219 (14)	0.37436 (16)	0.0162 (6)
C2	0.8648 (7)	0.28056 (14)	0.32574 (16)	0.0185 (6)
H2A	0.8406	0.2849	0.2737	0.022*
C3	1.0472 (7)	0.23229 (15)	0.35886 (17)	0.0217 (6)
H3A	1.1477	0.2035	0.3282	0.026*
C4	1.0841 (7)	0.22567 (15)	0.43704 (17)	0.0209 (6)
H4A	1.2093	0.1927	0.4569	0.025*
C5	0.9397 (7)	0.26676 (14)	0.48591 (17)	0.0195 (6)
H5A	0.9654	0.2624	0.5379	0.023*
C6	0.7538 (6)	0.31496 (14)	0.45269 (16)	0.0173 (6)
C7	0.4426 (6)	0.39749 (14)	0.43096 (16)	0.0168 (6)
C8	0.2254 (7)	0.46239 (14)	0.32772 (16)	0.0198 (6)
H8A	0.1249	0.4926	0.2961	0.024*
C9	0.3934 (6)	0.41295 (14)	0.30187 (15)	0.0167 (6)
C10	0.4589 (6)	0.39786 (14)	0.22327 (16)	0.0171 (6)
C11	0.5788 (7)	0.44837 (14)	0.18026 (16)	0.0186 (6)
H11A	0.6104	0.4906	0.2006	0.022*
C12	0.6502 (7)	0.43475 (15)	0.10674 (16)	0.0212 (6)
C13	0.6007 (7)	0.37120 (15)	0.07654 (17)	0.0226 (6)
H13A	0.6500	0.3621	0.0275	0.027*
C14	0.4790 (7)	0.32211 (15)	0.11920 (17)	0.0212 (6)
H14A	0.4460	0.2801	0.0986	0.025*
C15	0.4049 (6)	0.33474 (14)	0.19277 (16)	0.0188 (6)
H15A	0.3207	0.3016	0.2212	0.023*
C16	0.8306 (10)	0.54428 (17)	0.0891 (2)	0.0367 (9)
H16A	0.9177	0.5709	0.0513	0.055*
H16B	0.9628	0.5418	0.1329	0.055*
H16C	0.6481	0.5641	0.1023	0.055*
H1N1	0.540 (8)	0.3670 (18)	0.537 (2)	0.022 (9)*

	U11	U22	U33	U12	U13	U23
S1	0.0257 (4)	0.0124 (4)	0.0195 (4)	0.0041 (3)	0.0020 (3)	−0.0003 (3)
S2	0.0273 (4)	0.0140 (4)	0.0233 (4)	0.0020 (3)	0.0053 (3)	−0.0002 (3)
O1	0.0577 (17)	0.0144 (11)	0.0228 (11)	−0.0097 (10)	0.0120 (11)	0.0003 (9)
O2	0.0312 (13)	0.0176 (11)	0.0352 (13)	−0.0015 (9)	−0.0016 (10)	0.0050 (9)
O3	0.0345 (14)	0.0369 (15)	0.0262 (12)	0.0089 (10)	0.0037 (10)	0.0035 (10)
O4	0.0381 (14)	0.0203 (12)	0.0365 (13)	0.0082 (10)	0.0046 (10)	0.0096 (10)
O5	0.067 (2)	0.0288 (14)	0.0294 (13)	−0.0083 (12)	0.0063 (12)	−0.0110 (11)
N1	0.0243 (13)	0.0119 (12)	0.0165 (12)	0.0029 (9)	0.0011 (9)	−0.0007 (9)
N2	0.0198 (12)	0.0094 (11)	0.0169 (11)	0.0001 (8)	−0.0001 (9)	0.0004 (9)
C1	0.0178 (14)	0.0089 (13)	0.0219 (14)	−0.0009 (10)	0.0012 (10)	0.0031 (10)
C2	0.0228 (15)	0.0137 (14)	0.0190 (13)	−0.0015 (11)	0.0013 (11)	−0.0008 (11)
C3	0.0260 (16)	0.0132 (14)	0.0262 (15)	0.0016 (11)	0.0047 (12)	−0.0031 (12)
C4	0.0249 (16)	0.0125 (14)	0.0252 (15)	0.0027 (11)	−0.0014 (11)	0.0020 (11)
C5	0.0242 (16)	0.0138 (14)	0.0203 (14)	0.0003 (11)	0.0001 (11)	0.0020 (11)
C6	0.0224 (15)	0.0123 (13)	0.0172 (13)	−0.0009 (10)	0.0024 (10)	0.0005 (11)
C7	0.0190 (14)	0.0119 (13)	0.0196 (14)	−0.0017 (10)	0.0011 (10)	−0.0004 (10)
C8	0.0269 (16)	0.0105 (14)	0.0218 (14)	0.0022 (11)	0.0005 (11)	0.0022 (11)
C9	0.0217 (15)	0.0102 (13)	0.0179 (14)	−0.0007 (10)	−0.0015 (10)	0.0029 (10)
C10	0.0204 (15)	0.0114 (13)	0.0192 (13)	0.0005 (10)	−0.0011 (10)	0.0012 (11)
C11	0.0254 (16)	0.0093 (13)	0.0209 (14)	−0.0018 (10)	−0.0005 (11)	0.0000 (11)
C12	0.0312 (17)	0.0132 (14)	0.0194 (14)	−0.0026 (11)	0.0024 (11)	0.0028 (11)
C13	0.0334 (18)	0.0165 (15)	0.0181 (14)	−0.0027 (12)	0.0027 (12)	−0.0036 (11)
C14	0.0261 (16)	0.0116 (14)	0.0256 (15)	−0.0029 (11)	−0.0021 (12)	−0.0018 (11)
C15	0.0236 (15)	0.0114 (13)	0.0214 (14)	−0.0038 (10)	0.0001 (11)	0.0000 (11)
C16	0.066 (3)	0.0121 (16)	0.0334 (19)	−0.0074 (15)	0.0170 (17)	0.0012 (13)

S1—C7	1.710 (3)	C4—C5	1.388 (4)
S1—C8	1.750 (3)	C4—H4A	0.9300
S2—O5	1.421 (3)	C5—C6	1.396 (4)
S2—O4	1.458 (2)	C5—H5A	0.9300
S2—O3	1.466 (3)	C8—C9	1.348 (4)
S2—O2	1.577 (2)	C8—H8A	0.9300
O1—C12	1.358 (4)	C9—C10	1.476 (4)
O1—C16	1.428 (4)	C10—C15	1.396 (4)
O2—H1O2	0.9734	C10—C11	1.399 (4)
N1—C7	1.337 (4)	C11—C12	1.391 (4)
N1—C6	1.389 (4)	C11—H11A	0.9300
N1—H1N1	0.93 (4)	C12—C13	1.399 (4)
N2—C7	1.353 (4)	C13—C14	1.378 (4)
N2—C1	1.413 (4)	C13—H13A	0.9300
N2—C9	1.417 (3)	C14—C15	1.392 (4)
C1—C2	1.393 (4)	C14—H14A	0.9300
C1—C6	1.401 (4)	C15—H15A	0.9300
C2—C3	1.387 (4)	C16—H16A	0.9600
C2—H2A	0.9300	C16—H16B	0.9600
C3—C4	1.398 (4)	C16—H16C	0.9600
C3—H3A	0.9300
C7—S1—C8	88.78 (14)	N1—C7—N2	110.6 (2)
O5—S2—O4	115.49 (16)	N1—C7—S1	135.9 (2)
O5—S2—O3	114.67 (17)	N2—C7—S1	113.4 (2)
O4—S2—O3	109.68 (14)	C9—C8—S1	114.2 (2)
O5—S2—O2	107.32 (15)	C9—C8—H8A	122.9
O4—S2—O2	107.17 (14)	S1—C8—H8A	122.9
O3—S2—O2	101.22 (15)	C8—C9—N2	110.1 (2)
C12—O1—C16	117.0 (2)	C8—C9—C10	128.3 (3)
S2—O2—H1O2	112.1	N2—C9—C10	121.5 (2)
C7—N1—C6	107.6 (2)	C15—C10—C11	120.8 (3)
C7—N1—H1N1	123 (2)	C15—C10—C9	121.0 (3)
C6—N1—H1N1	129 (2)	C11—C10—C9	118.2 (3)
C7—N2—C1	108.2 (2)	C12—C11—C10	119.2 (3)
C7—N2—C9	113.5 (2)	C12—C11—H11A	120.4
C1—N2—C9	138.1 (2)	C10—C11—H11A	120.4
C2—C1—C6	121.6 (3)	O1—C12—C11	124.8 (3)
C2—C1—N2	133.4 (3)	O1—C12—C13	115.2 (3)
C6—C1—N2	105.0 (2)	C11—C12—C13	120.0 (3)
C3—C2—C1	116.6 (3)	C14—C13—C12	120.2 (3)
C3—C2—H2A	121.7	C14—C13—H13A	119.9
C1—C2—H2A	121.7	C12—C13—H13A	119.9
C2—C3—C4	121.8 (3)	C13—C14—C15	120.7 (3)
C2—C3—H3A	119.1	C13—C14—H14A	119.6
C4—C3—H3A	119.1	C15—C14—H14A	119.6
C5—C4—C3	122.0 (3)	C14—C15—C10	119.0 (3)
C5—C4—H4A	119.0	C14—C15—H15A	120.5
C3—C4—H4A	119.0	C10—C15—H15A	120.5
C4—C5—C6	116.3 (3)	O1—C16—H16A	109.5
C4—C5—H5A	121.9	O1—C16—H16B	109.5
C6—C5—H5A	121.9	H16A—C16—H16B	109.5
N1—C6—C5	129.7 (3)	O1—C16—H16C	109.5
N1—C6—C1	108.6 (2)	H16A—C16—H16C	109.5
C5—C6—C1	121.7 (3)	H16B—C16—H16C	109.5
C7—N2—C1—C2	178.7 (3)	C8—S1—C7—N2	−0.4 (2)
C9—N2—C1—C2	−6.0 (6)	C7—S1—C8—C9	0.3 (2)
C7—N2—C1—C6	0.2 (3)	S1—C8—C9—N2	−0.1 (3)
C9—N2—C1—C6	175.4 (3)	S1—C8—C9—C10	−178.0 (2)
C6—C1—C2—C3	−0.8 (4)	C7—N2—C9—C8	−0.2 (3)
N2—C1—C2—C3	−179.2 (3)	C1—N2—C9—C8	−175.2 (3)
C1—C2—C3—C4	0.0 (4)	C7—N2—C9—C10	177.9 (3)
C2—C3—C4—C5	0.3 (5)	C1—N2—C9—C10	2.8 (5)
C3—C4—C5—C6	0.3 (4)	C8—C9—C10—C15	−125.6 (3)
C7—N1—C6—C5	179.7 (3)	N2—C9—C10—C15	56.7 (4)
C7—N1—C6—C1	0.4 (3)	C8—C9—C10—C11	54.9 (4)
C4—C5—C6—N1	179.6 (3)	N2—C9—C10—C11	−122.8 (3)
C4—C5—C6—C1	−1.2 (4)	C15—C10—C11—C12	−1.3 (4)
C2—C1—C6—N1	−179.1 (3)	C9—C10—C11—C12	178.2 (3)
N2—C1—C6—N1	−0.4 (3)	C16—O1—C12—C11	−1.6 (5)
C2—C1—C6—C5	1.5 (4)	C16—O1—C12—C13	−179.9 (3)
N2—C1—C6—C5	−179.8 (3)	C10—C11—C12—O1	−177.9 (3)
C6—N1—C7—N2	−0.3 (3)	C10—C11—C12—C13	0.3 (5)
C6—N1—C7—S1	−176.2 (3)	O1—C12—C13—C14	178.9 (3)
C1—N2—C7—N1	0.0 (3)	C11—C12—C13—C14	0.5 (5)
C9—N2—C7—N1	−176.5 (2)	C12—C13—C14—C15	−0.3 (5)
C1—N2—C7—S1	176.94 (19)	C13—C14—C15—C10	−0.8 (5)
C9—N2—C7—S1	0.4 (3)	C11—C10—C15—C14	1.6 (4)
C8—S1—C7—N1	175.4 (3)	C9—C10—C15—C14	−177.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	0.94 (4)	1.85 (4)	2.750 (3)	160 (3)
N1—H1N1···O4	0.94 (4)	2.50 (4)	3.199 (4)	132 (3)
O2—H1O2···O3i	0.97	1.60	2.531 (4)	158
C11—H11A···O5ii	0.93	2.32	3.237 (4)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	0.94 (4)	1.85 (4)	2.750 (3)	160 (3)
N1—H1N1⋯O4	0.94 (4)	2.50 (4)	3.199 (4)	132 (3)
O2—H1O2⋯O3i	0.97	1.60	2.531 (4)	158
C11—H11A⋯O5ii	0.93	2.32	3.237 (4)	170

Symmetry codes: (i) ; (ii) .