Bis(2-amino-1,3-benzothia-zol-3-ium) tetra-chloridozincate(II).

The asymmetric unit of the title compound, (C(7)H(7)N(2)S)(2)[ZnCl(4)], contains a network of 2-amino-benzothia-zolium cations and tetra-hedral [ZnCl(4)](2-) anions. The crystal packing is influenced by cation-to-anion N-H⋯Cl and C-H⋯Cl hydrogen bonds. The [ZnCl(4)](2-) anions have a distorded tetra-hedral geometry. Inter-molecular π-π stacking inter-actions are present between neighboring benzene rings, thia-zole and benzene rings and neighboring thia-zole rings [centroid-centroid distances = 3.711 (2), 3.554 (1), 3.536 (2) and 3.572 (1) Å].

Related literature

For common applications of organic–inorganic hybrid mat­erials, see: Bringley & Rajeswaran (2006 ▶); Pierpont & Jung (1994 ▶); Dai et al. (2002 ▶). For the geometry around the zinc atom, see: Harrison (2005 ▶). For the weighting scheme used, see: Prince (1982 ▶); Watkin (1994 ▶) and for the extinction correction, see: Larson (1970 ▶).

Experimental

Crystal data

(C7H7N2S)2[ZnCl4]

M = 509.61

Triclinic,

a = 7.543 (1) Å

b = 7.828 (1) Å

c = 17.109 (2) Å

α = 94.250 (1)°

β = 100.930 (1)°

γ = 92.465 (1)°

V = 987.5 (2) Å3

Z = 2

Mo Kα radiation

μ = 2.00 mm−1

T = 110 K

0.49 × 0.23 × 0.14 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer

Absorption correction: analytical [using a multifaceted crystal model based on expressions derived by Clark & Reid (1995 ▶), implemented in CrysAlis PRO (Agilent, 2010 ▶)] T min = 0.498, T max = 0.771

10196 measured reflections

4685 independent reflections

3630 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.111

S = 0.94

4685 reflections

227 parameters

H-atom parameters constrained

Δρmax = 1.03 e Å−3

Δρmin = −1.23 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015753/vn2006sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015753/vn2006Isup2.hkl

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

(C7H7N2S)2[ZnCl4]	Z = 2
Mr = 509.61	F(000) = 512
Triclinic, P1	Dx = 1.714 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 7.543 (1) Å	Cell parameters from 3221 reflections
b = 7.828 (1) Å	θ = 3.4–29.4°
c = 17.109 (2) Å	µ = 2.00 mm−1
α = 94.250 (1)°	T = 110 K
β = 100.930 (1)°	Plate, colorless
γ = 92.465 (1)°	0.49 × 0.23 × 0.14 mm
V = 987.5 (2) Å3

Agilent Xcalibur Atlas Gemini ultra diffractometer	4685 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3630 reflections with I > 2σ(I)
graphite	Rint = 0.045
Detector resolution: 10.4685 pixels mm-1	θmax = 29.5°, θmin = 3.4°
ω scans	h = −9→9
Absorption correction: analytical [using a multifaceted crystal model based on expressions derived by Clark & Reid (1995), implemented in CrysAlis PRO (Agilent, 2010)]	k = −10→10
Tmin = 0.498, Tmax = 0.771	l = −22→23
10196 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.230E + 04 0.321E + 04 0.179E + 04 528.
wR(F2) = 0.111	(Δ/σ)max = 0.001
S = 0.94	Δρmax = 1.03 e Å−3
4685 reflections	Δρmin = −1.23 e Å−3
227 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 20 (3)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
Zn1	0.49814 (8)	0.31162 (7)	0.75071 (4)	0.0243
Cl2	0.29039 (16)	0.43801 (16)	0.81360 (8)	0.0274
Cl3	0.50293 (17)	0.47084 (17)	0.64494 (8)	0.0312
Cl4	0.43482 (19)	0.03141 (16)	0.71252 (8)	0.0327
Cl5	0.76785 (17)	0.33826 (17)	0.83422 (9)	0.0348
S6	0.80197 (17)	0.66813 (17)	0.54732 (8)	0.0271
C7	0.9702 (6)	0.6161 (6)	0.6239 (3)	0.0238
N8	1.1348 (6)	0.6629 (5)	0.6125 (3)	0.0270
C9	1.1369 (7)	0.7391 (6)	0.5413 (3)	0.0259
C10	0.9660 (7)	0.7508 (6)	0.4981 (3)	0.0274
C11	0.9378 (8)	0.8213 (7)	0.4244 (3)	0.0334
C12	1.0891 (9)	0.8761 (7)	0.3964 (4)	0.0399
C13	1.2610 (8)	0.8636 (7)	0.4407 (4)	0.0371
C14	1.2880 (7)	0.7940 (7)	0.5137 (4)	0.0332
N15	0.9376 (6)	0.5413 (6)	0.6864 (3)	0.0301
N16	0.4666 (6)	0.2078 (6)	1.1438 (3)	0.0318
C17	0.3739 (7)	0.1401 (6)	1.0765 (3)	0.0267
S18	0.33424 (17)	0.24680 (16)	0.98962 (8)	0.0267
C19	0.2084 (7)	0.0651 (7)	0.9370 (3)	0.0272
C20	0.1203 (7)	0.0453 (7)	0.8583 (3)	0.0289
C21	0.0273 (7)	−0.1091 (7)	0.8316 (3)	0.0305
C22	0.0266 (7)	−0.2424 (6)	0.8813 (3)	0.0298
C23	0.1155 (7)	−0.2224 (6)	0.9596 (3)	0.0279
C24	0.2056 (7)	−0.0673 (6)	0.9873 (3)	0.0258
N25	0.2989 (6)	−0.0203 (5)	1.0642 (3)	0.0256
H111	0.8216	0.8312	0.3963	0.0401*
H121	1.0765	0.9226	0.3472	0.0479*
H131	1.3614	0.9009	0.4205	0.0452*
H141	1.4023	0.7848	0.5425	0.0398*
H201	0.1216	0.1333	0.8250	0.0348*
H211	−0.0354	−0.1254	0.7796	0.0368*
H221	−0.0350	−0.3478	0.8606	0.0360*
H231	0.1136	−0.3105	0.9923	0.0341*
H152	1.0268	0.5160	0.7218	0.0362*
H162	0.5251	0.3062	1.1464	0.0382*
H161	0.4973	0.1448	1.1825	0.0382*
H151	0.8275	0.5082	0.6881	0.0364*
H81	1.2342	0.6334	0.6426	0.0335*
H251	0.3111	−0.0904	1.1014	0.0316*

	U11	U22	U33	U12	U13	U23
Zn1	0.0209 (3)	0.0234 (3)	0.0286 (3)	0.0006 (2)	0.0037 (2)	0.0055 (2)
Cl2	0.0251 (6)	0.0269 (6)	0.0310 (6)	0.0003 (5)	0.0074 (5)	0.0040 (5)
Cl3	0.0238 (6)	0.0367 (7)	0.0359 (7)	0.0048 (5)	0.0079 (5)	0.0140 (5)
Cl4	0.0414 (7)	0.0246 (6)	0.0303 (6)	−0.0007 (5)	0.0031 (5)	0.0032 (5)
Cl5	0.0256 (6)	0.0321 (7)	0.0434 (8)	−0.0064 (5)	−0.0049 (5)	0.0156 (6)
S6	0.0210 (6)	0.0287 (6)	0.0299 (6)	0.0014 (5)	0.0004 (5)	0.0036 (5)
C7	0.018 (2)	0.024 (2)	0.031 (3)	0.0051 (18)	0.0061 (19)	0.004 (2)
N8	0.022 (2)	0.025 (2)	0.034 (2)	0.0004 (16)	0.0037 (17)	0.0024 (18)
C9	0.028 (3)	0.024 (2)	0.028 (2)	0.0062 (19)	0.009 (2)	0.002 (2)
C10	0.032 (3)	0.021 (2)	0.028 (3)	0.003 (2)	0.004 (2)	−0.003 (2)
C11	0.045 (3)	0.025 (3)	0.029 (3)	−0.001 (2)	0.004 (2)	−0.001 (2)
C12	0.061 (4)	0.026 (3)	0.032 (3)	−0.009 (3)	0.013 (3)	−0.003 (2)
C13	0.043 (3)	0.029 (3)	0.044 (3)	0.002 (2)	0.023 (3)	−0.004 (2)
C14	0.026 (3)	0.030 (3)	0.045 (3)	0.001 (2)	0.010 (2)	0.001 (2)
N15	0.026 (2)	0.035 (2)	0.029 (2)	−0.0015 (18)	0.0020 (18)	0.0060 (19)
N16	0.034 (2)	0.028 (2)	0.032 (2)	−0.0031 (19)	0.0012 (19)	0.0066 (19)
C17	0.023 (2)	0.026 (2)	0.032 (3)	−0.0024 (19)	0.007 (2)	0.006 (2)
S18	0.0268 (6)	0.0231 (6)	0.0308 (6)	−0.0029 (5)	0.0068 (5)	0.0054 (5)
C19	0.021 (2)	0.029 (3)	0.034 (3)	0.0000 (19)	0.010 (2)	0.006 (2)
C20	0.028 (3)	0.027 (3)	0.035 (3)	0.002 (2)	0.011 (2)	0.005 (2)
C21	0.029 (3)	0.031 (3)	0.030 (3)	−0.007 (2)	0.008 (2)	−0.002 (2)
C22	0.029 (3)	0.019 (2)	0.041 (3)	−0.0046 (19)	0.010 (2)	−0.004 (2)
C23	0.028 (3)	0.022 (2)	0.036 (3)	−0.0003 (19)	0.011 (2)	0.004 (2)
C24	0.022 (2)	0.025 (2)	0.032 (3)	0.0034 (19)	0.011 (2)	0.003 (2)
N25	0.028 (2)	0.0190 (19)	0.031 (2)	0.0027 (16)	0.0072 (18)	0.0060 (17)

Zn1—Cl2	2.2820 (14)	N15—H152	0.856
Zn1—Cl3	2.2770 (14)	N15—H151	0.865
Zn1—Cl4	2.2462 (14)	N16—C17	1.292 (7)
Zn1—Cl5	2.2452 (14)	N16—H162	0.865
S6—C7	1.728 (5)	N16—H161	0.858
S6—C10	1.750 (5)	C17—S18	1.741 (5)
C7—N8	1.333 (6)	C17—N25	1.340 (6)
C7—N15	1.315 (6)	S18—C19	1.762 (5)
N8—C9	1.397 (6)	C19—C20	1.379 (7)
N8—H81	0.876	C19—C24	1.398 (7)
C9—C10	1.369 (7)	C20—C21	1.372 (7)
C9—C14	1.378 (7)	C20—H201	0.926
C10—C11	1.398 (7)	C21—C22	1.394 (7)
C11—C12	1.383 (8)	C21—H211	0.922
C11—H111	0.926	C22—C23	1.375 (8)
C12—C13	1.384 (9)	C22—H221	0.940
C12—H121	0.932	C23—C24	1.372 (7)
C13—C14	1.384 (8)	C23—H231	0.920
C13—H131	0.934	C24—N25	1.385 (7)
C14—H141	0.917	N25—H251	0.865
Cl2—Zn1—Cl3	103.35 (5)	C7—N15—H152	119.0
Cl2—Zn1—Cl4	114.50 (5)	C7—N15—H151	119.2
Cl3—Zn1—Cl4	112.21 (6)	H152—N15—H151	121.4
Cl2—Zn1—Cl5	108.54 (6)	C17—N16—H162	120.4
Cl3—Zn1—Cl5	110.34 (5)	C17—N16—H161	119.8
Cl4—Zn1—Cl5	107.81 (6)	H162—N16—H161	117.3
C7—S6—C10	90.0 (2)	N16—C17—S18	123.7 (4)
S6—C7—N8	112.2 (4)	N16—C17—N25	124.7 (5)
S6—C7—N15	123.3 (4)	S18—C17—N25	111.6 (4)
N8—C7—N15	124.5 (5)	C17—S18—C19	90.6 (2)
C7—N8—C9	114.5 (4)	S18—C19—C20	128.4 (4)
C7—N8—H81	123.0	S18—C19—C24	110.2 (4)
C9—N8—H81	121.8	C20—C19—C24	121.4 (5)
N8—C9—C10	111.9 (5)	C19—C20—C21	117.2 (5)
N8—C9—C14	126.5 (5)	C19—C20—H201	121.4
C10—C9—C14	121.6 (5)	C21—C20—H201	121.4
S6—C10—C9	111.4 (4)	C20—C21—C22	121.5 (5)
S6—C10—C11	127.5 (4)	C20—C21—H211	119.3
C9—C10—C11	121.1 (5)	C22—C21—H211	119.2
C10—C11—C12	117.4 (6)	C21—C22—C23	121.1 (5)
C10—C11—H111	120.4	C21—C22—H221	119.2
C12—C11—H111	122.1	C23—C22—H221	119.7
C11—C12—C13	120.8 (6)	C22—C23—C24	117.9 (5)
C11—C12—H121	120.2	C22—C23—H231	120.7
C13—C12—H121	118.9	C24—C23—H231	121.4
C12—C13—C14	121.5 (5)	C19—C24—C23	120.9 (5)
C12—C13—H131	119.5	C19—C24—N25	112.3 (4)
C14—C13—H131	119.0	C23—C24—N25	126.8 (5)
C13—C14—C9	117.5 (5)	C24—N25—C17	115.3 (4)
C13—C14—H141	121.0	C24—N25—H251	122.4
C9—C14—H141	121.5	C17—N25—H251	122.2

D—H···A	D—H	H···A	D···A	D—H···A
N8—H81···Cl3i	0.88	2.43	3.190 (5)	145
N15—H151···Cl3	0.86	2.42	3.235 (5)	157
N15—H152···Cl2i	0.86	2.42	3.274 (5)	176
N25—H251···Cl5ii	0.86	2.41	3.215 (5)	155
N16—H161···Cl4ii	0.86	2.34	3.196 (5)	177
N16—H162···Cl2iii	0.86	2.37	3.215 (5)	166
C20—H201···Cl2	0.93	2.69	3.473 (6)	142
C22—H221···Cl5iv	0.94	2.78	3.701 (5)	167
C11—H111···Cl4v	0.93	2.73	3.592 (6)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H81⋯Cl3i	0.88	2.43	3.190 (5)	145
N15—H151⋯Cl3	0.86	2.42	3.235 (5)	157
N15—H152⋯Cl2i	0.86	2.42	3.274 (5)	176
N25—H251⋯Cl5ii	0.86	2.41	3.215 (5)	155
N16—H161⋯Cl4ii	0.86	2.34	3.196 (5)	177
N16—H162⋯Cl2iii	0.86	2.37	3.215 (5)	166
C20—H201⋯Cl2	0.93	2.69	3.473 (6)	142
C22—H221⋯Cl5iv	0.94	2.78	3.701 (5)	167
C11—H111⋯Cl4v	0.93	2.73	3.592 (6)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .