Bis(2,5-dimethyl­anilinium) tetra­chlorido­zincate(II)

Sofiane Souissi; Wajda Smirani; Mohamed Rzaigui

doi:10.1107/S1600536809009982

. 2009 Mar 25;65(Pt 4):m442. doi: 10.1107/S1600536809009982

Bis(2,5-dimethylanilinium) tetrachloridozincate(II)

Sofiane Souissi ^a, Wajda Smirani ^a,^*, Mohamed Rzaigui ^a

PMCID: PMC2968953 PMID: 21582379

Abstract

In the title compound, (C₈H₁₂N)₂[ZnCl₄], the Zn²⁺ ion adopts a distorted tetrahedral coordination geometry. In the crystal, the cations and anions are linked by N—H⋯Cl hydrogen bonds, leading to ribbons propagating parallel to the a axis.

Related literature

For related structures, see: Guo et al. (2007 ▶); Smirani & Rzaigui (2009 ▶). For background on hybrid materials, see: Tao et al. (2003 ▶); Bringley & Rajeswaran (2006 ▶).

Experimental

Crystal data

(C₈H₁₂N)₂[ZnCl₄]
M _r = 451.58
Monoclinic,
a = 7.425 (2) Å
b = 12.884 (2) Å
c = 22.809 (2) Å
β = 96.16 (2)°
V = 2169.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 293 K
0.20 × 0.13 × 0.10 mm

Data collection

Enraf–Nonius Turbo CAD-4 diffractometer
Absorption correction: none
6539 measured reflections
3947 independent reflections
2621 reflections with I > 2σ(I)
R _int = 0.033
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F ² > 2σ(F ²)] = 0.079
wR(F ²) = 0.229
S = 1.05
3947 reflections
214 parameters
H-atom parameters not refined
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009982/hb2930sup1.cif

e-65-0m442-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009982/hb2930Isup2.hkl

e-65-0m442-Isup2.hkl^{(189.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—Cl1	2.248 (2)
Zn1—Cl2	2.2502 (16)
Zn1—Cl3	2.274 (2)
Zn1—Cl4	2.2721 (18)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl4ⁱ	0.89	2.25	3.125 (6)	169
N1—H1B⋯Cl3ⁱⁱ	0.89	2.54	3.304 (6)	145
N1—H1C⋯Cl2ⁱⁱⁱ	0.89	2.31	3.172 (7)	162
N2—H2A⋯Cl1ⁱ	0.89	2.34	3.219 (6)	171
N2—H2B⋯Cl4^iv	0.89	2.70	3.505 (7)	151
N2—H2C⋯Cl3ⁱⁱ	0.89	2.39	3.262 (6)	168

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

supplementary crystallographic information

Comment

Inorganic-organic hybrid materials are of great interest in solid state chemistry due to their enormous variety of intriguing structural topologies and their fascinating properties as well as great potential applications in many fields (Tao et al., 2003; Bringley & Rajeswaran, 2006). Here we report the crystal structure of bis(2,5-xylidinium) tetrachlorozincate (I).

As shown in Fig. 1, the asymmetric unit of (I) is built up from two 2,5-xylidinium cations and one tetrachlorozincate (II) anion. The Zn (II) ion is in a tetrahedral coordination environment composed of four Cl anions (Table 1). The Cl—Zn—Cl bond angles range from 106.13 (8) to 112.46 (8)°. These values indicate that the anionic [ZnCl₄]^2- tetrahedron is slightly distorted (Guo et al., 2007). The examination of the organic cation shows that the values of the N—C, C—C distances and N—C—C, C—C—C angles range from 1.343 (12) to 1.512 (11) Å and 115.90 (7) to 123.0 (6)°, respectively. These values show no significant difference from those obtained in other crystals involving the same organic groups (Smirani and Rzaigui, 2009).

A projection of the structure along the direction a shows that the [ZnCl₄]^2- anions are connected via N—H···Cl hydrogen bonds originating from NH₃⁺ groups, so as to built inorganic ribbons at x = 0 and x = 1/2 (Fig. 2, Table 2). The 2,5-xylidinium cations are anchored onto the successive ribbons via hydrogen bonds and electrostatic and van der Waals interactions, to compensate their negative charges.

Experimental

An aqueous solution of 2,5-xylidine, HCl and ZnCl₂ in a 2:2:1 molar ratio was prepared and colourless blocks of (I) grew as the water evaporated over the course of a few days.