Bis(2-amino-1,3-benzothia­zol-3-ium) tetra­chloridozincate(II)

Riadh Kefi; Erwann Jeanneau; Frédéric Lefebvre; Cherif Ben Nasr

doi:10.1107/S1600536811015753

. 2011 May 7;67(Pt 6):m654–m655. doi: 10.1107/S1600536811015753

Bis(2-amino-1,3-benzothiazol-3-ium) tetrachloridozincate(II)

Riadh Kefi ^a, Erwann Jeanneau ^b, Frédéric Lefebvre ^c, Cherif Ben Nasr ^a,^*

PMCID: PMC3120423 PMID: 21754568

Abstract

The asymmetric unit of the title compound, (C₇H₇N₂S)₂[ZnCl₄], contains a network of 2-aminobenzothiazolium cations and tetrahedral [ZnCl₄]²⁻ anions. The crystal packing is influenced by cation-to-anion N—H⋯Cl and C—H⋯Cl hydrogen bonds. The [ZnCl₄]²⁻ anions have a distorded tetrahedral geometry. Intermolecular π–π stacking interactions are present between neighboring benzene rings, thiazole and benzene rings and neighboring thiazole 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 _r = 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
Δρ_max = 1.03 e Å⁻³
Δρ_min = −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.

Supplementary Material

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

e-67-0m654-sup1.cif^{(16.7KB, cif)}

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

e-67-0m654-Isup2.hkl^{(234KB, hkl)}

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

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⋯Cl5^iv	0.94	2.78	3.701 (5)	167
C11—H111⋯Cl4^v	0.93	2.73	3.592 (6)	154

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

Acknowledgments

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

supplementary crystallographic information

Comment

Inorganic-organic hybrid compounds provide a class of materials displaying interesting technological importance (Bringley & Rajeswaran, 2006; Pierpont & Jung, 1994; Dai et al., 2002). We report the crystal structure of one such compound, (C₇H₇N₂S)₂[ZnCl₄] (I), formed from the reaction of 2-aminobenzothiazole with zinc chloride. As shown in Fig.1, only the nitrogen atom of the thiazole ring of the title compound is protonated, but not that of the amine group. Thus, to ensure charge equilibrium, the structure associates each tetrachlorizincate anion with two (2-aminobenzothiazolium) cations. Fig.2 shows that the atomic arrangement of the title hybrid material can be described as inorganic ZnCl₄^2- units isolated from each other by the organic cations. The different entities are held together by coulombic attraction and multiple hydrogen bonds to form a three dimensional network. The tetraclorozincate anion geometrical features show that the Zn—Cl bond lengths vary between 2.245 (1) and 2.282 (1) Å and the Cl—Zn—Cl angles range from 103.35 (5) to 112.21 (5) °. These values, which are in good agreement with those reported previously, clearly indicate that the [ZnCl₄]^2- anion has a slightly distorted tetrahedral stereochemistry (Harrison, 2005). Intermolecular π-π stacking interactions are present between neighboring phenyl rings (centroid-centroid distance = 3.711 (2) Å), thiazole-phenyl rings (centroid-centroid distance = 3.554 (1) Å) and thiazole-thiazole rings (centroid-centroid distances = 3.536 (2) and 3.572 (1) Å) (Fig. 3).

Experimental

A mixture of an aqueous solution of 2-aminobenzothiazole (3 mmol, 0.450 g), zinc chloride (1.5 mmol, 0.297 g) and HCl (10 ml, 0.3 M) in a Petri dish was slowly evaporated at room temperature. Colorless single crystals of the title compound were isolated after several days (yield 58%).