Bis(2,3-dimethyl­anilinium) tetra­chlorido­zincate dihydrate

Sofiane Souissi; Wajda Smirani Sta; Salem S Al-Deyab; Mohamed Rzaigui

doi:10.1107/S1600536811017478

. 2011 May 14;67(Pt 6):m754. doi: 10.1107/S1600536811017478

Bis(2,3-dimethylanilinium) tetrachloridozincate dihydrate

Sofiane Souissi ^a, Wajda Smirani Sta ^a,^*, Salem S Al-Deyab ^b, Mohamed Rzaigui ^a

PMCID: PMC3120428 PMID: 21754643

Abstract

In the title compound, (C₈H₁₂N)₂[ZnCl₄]·2H₂O, the Zn atom is coordinated by four Cl atoms in a tetrahedral geometry. The water molecules and the organic cations interact with the [ZnCl₄]²⁻ complex anions, building up a two-dimensional hydrogen-bonded network parallel to (100).

Related literature

For properties of aniline derivatives, see: Hirao & Fukuhara (1998 ▶); Linden et al. (1995 ▶); MacDiamid et al. (1998 ▶); Singh et al. (1995 ▶, 2002 ▶); Wang et al. (2002 ▶); Fábry et al. (2002 ▶). For structural comparison, see: Harrison (2005 ▶); Marouani et al. (2010 ▶).

Experimental

Crystal data

(C₈H₁₂N)₂[ZnCl₄]·2H₂O
M _r = 487.57
Monoclinic,
a = 21.654 (2) Å
b = 7.432 (3) Å
c = 14.069 (2) Å
β = 90.30 (2)°
V = 2264.1 (10) Å³
Z = 4
Ag Kα radiation
λ = 0.56085 Å
μ = 0.82 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
16232 measured reflections
10928 independent reflections
5697 reflections with I > 2σ(I)
R _int = 0.041
2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.151
S = 1.03
10363 reflections
232 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017478/dn2685sup1.cif

e-67-0m754-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017478/dn2685Isup2.hkl

e-67-0m754-Isup2.hkl^{(496.6KB, 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
N1—H1A⋯Cl2ⁱ	0.89	2.61	3.488 (2)	168
N1—H1B⋯Cl4	0.89	2.38	3.239 (2)	162
N1—H1C⋯O1	0.89	1.83	2.707 (3)	168
N2—H2A⋯Cl2ⁱⁱ	0.89	2.85	3.713 (2)	165
N2—H2B⋯Cl3	0.89	2.35	3.225 (2)	168
N2—H2C⋯O2	0.89	1.82	2.696 (3)	167
O1—H22⋯Cl1ⁱⁱⁱ	0.80	2.35	3.115 (2)	160
O1—H23⋯Cl4ⁱ	0.81	2.53	3.304 (3)	162
O2—H20⋯Cl3ⁱ	0.80	2.56	3.228 (3)	142
O2—H21⋯Cl1	0.79	2.50	3.213 (2)	150

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

supplementary crystallographic information

Comment

Aniline is an useful chemical product used in various areas. Some derivatives of aniline have improving anticorrosion ability for metals (Wang et al., 2002), others show high efficiency as chemical sensors (MacDiamid et al.,1998) and catalitic oxidation (Hirao & Fukuhara, 1998). Bibliography reports some structures where the cation dimethylanilinium is associated to other anions as sulfate (Singh et al., 2002), nitrate, perchlorate (Singh et al., 1995), chloride (Linden et al., 1995), and phosphate (Fábry et al., 2002). We report here a crystal structure where this organic cation is associated to an anionic complex (I).

The asymmetric unit consists of two 2,3-dimethylanilinium cations, two water molecules and one complex anion [ZnCl₄]^2-linked by N-H···O, N-H···Cl and O-H···Cl hydrogen bonds (Fig. 1). The atomic arrangement of (2,3-(CH₃)₂C₆H₃NH₃)₂ZnCl₄.2H₂O (I) is made up of inorganic layers, parallel to the (1 0 0) plane, built up by [ZnCl₄]^2- complex and water molecules held together by O—H···Cl hydrogen bonds. The organic groups are attached to both sides of these layers through N—H···Cl and N—H···O hydrogen bonds, electrostatic and Van der walls interactions, to form a two dimensional infinite network (Fig. 2).

In the title compound (I), the four chlorine atoms of the [ZnCl₄]^2- anion are acting as acceptors of the hydrogen bonds. The bond angles Cl—Zn—Cl vary from 102.50 (3) to 113.71 (3)°, and the bond length of the Zn—Cl lie in the range 2.2071 (8) - 2.4649 (9) Å. These values indicate that the coordination geometry of the Zn atom can be considered as being a slightly distorted tetrahedron (Harrison, 2005). The nearst Zn···Zn intra-chain separation is 7.135 (1) Å, while the distance between adjacent chains is 11.050 (2) Å. The examination of the organic cations shows that the value distances and angles show no significant difference from those obtained in other crystals involving the same organic groups (Marouani et al., 2010). The phenyl rings of these cations are planar with a maximum atomic deviation of 0.00025 Å and a dihedral angle between them of 21.95°.

Experimental

A mixture of an aqueous solution of 2,3-xylidine, HCl and ZnCl₂ in a 2:2:1 molar ratio was prepared, stirred then slowly evaporated at room temperature (293 K). After few days, colourless prismatic crystals of (C₁₆H₂₈N₂) [ZnCl₄].H₂O appear with suitable size for x-ray diffraction measurements.