1-(4-Chloro­phen­yl)piperazine-1,4-diium tetra­chlorido­zincate(II) monohydrate

Imen Ben Gharbia; Riadh Kefi; Meher El Glaoui; Erwann Jeanneau; Cherif Ben Nasr

doi:10.1107/S1600536808016590

. 2008 Jun 7;64(Pt 7):m880. doi: 10.1107/S1600536808016590

1-(4-Chlorophenyl)piperazine-1,4-diium tetrachloridozincate(II) monohydrate

Imen Ben Gharbia ^a, Riadh Kefi ^a, Meher El Glaoui ^a, Erwann Jeanneau ^b, Cherif Ben Nasr ^a,^*

PMCID: PMC2961817 PMID: 21202751

Abstract

In the crystal structure of the title compound, (C₁₀H₁₅ClN₂)[ZnCl₄]·H₂O, the Zn atom is coordinated by four Cl atoms in a tetrahedral geometry. The water molecules and the 1-(4-chlorophenyl)piperazine-1,4-diium cations interact with the [ZnCl₄]²⁻ anions through O—H⋯Cl, N—H⋯Cl, N—H⋯O and C—H⋯Cl hydrogen bonds (five simple and one bifurcated). Intermolecular π–π stacking interactions are present between adjacent aromatic rings of 1-(4-chlorophenyl)piperazine-1,4-diium cations (the centroid–centroid distance is 3.453 Å).

Related literature

For related literature, see: Ben Gharbia et al. (2005 ▶); Guo et al. (2007 ▶); Valkonen et al. (2006 ▶); Janiak (2000 ▶).

Experimental

Crystal data

(C₁₀H₁₅ClN₂)[ZnCl₄]·H₂O
M _r = 423.90
Monoclinic,
a = 7.2036 (2) Å
b = 15.1575 (5) Å
c = 15.4870 (5) Å
β = 103.012 (2)°
V = 1647.58 (9) Å³
Z = 4
Mo Kα radiation
μ = 2.29 mm⁻¹
T = 293 K
0.44 × 0.28 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T _min = 0.34, T _max = 0.59
20612 measured reflections
3901 independent reflections
3369 reflections with I > 2σ(I)
R _int = 0.085

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.063
S = 0.89
3203 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; 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, 1998 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016590/bg2190sup1.cif

e-64-0m880-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016590/bg2190Isup2.hkl

e-64-0m880-Isup2.hkl^{(195KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—Cl1	2.3036 (11)
Zn1—Cl2	2.2937 (11)
Zn1—Cl3	2.2495 (13)
Zn1—Cl4	2.2420 (12)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H15⋯O1	0.89	1.86	2.742 (6)	169
N2—H16⋯Cl4ⁱ	0.89	2.53	3.249 (4)	137
N2—H16⋯Cl2ⁱ	0.89	2.77	3.352 (3)	123
N2—H17⋯Cl1	0.89	2.42	3.261 (5)	156
O1—H1⋯Cl2ⁱⁱ	0.81	2.61	3.342 (3)	149
O1—H2⋯Cl3ⁱⁱⁱ	0.82	2.52	3.258 (4)	149
C5—H5⋯Cl4^iv	0.93	2.76	3.686 (5)	168

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

Acknowledgments

We acknowledge the Tunisian Secretariat of State for Scientific Research and Technology for financial support.

supplementary crystallographic information

Comment

The crystal structure of the title compound, (I), (Fig. 1), contains a [ZnCl₄]^2- tetrahedral anion, a 1-(4-chlorophenyl)piperazine-1,4-dium (2+) cation and a water molecule. Fig. 2 shows the atomic arrangement, which can be described as built up by [ZnCl₄] tetrahedra interconnected through water molecules via a O—H···Cl bond to form chains which evolve along the a direction. These [ZnCl₄].[H₂O] chains are interconnected into a three-dimensional network by the organic entities through N—H···Cl, C—H···Cl bonds and π-π interactions. Fig.3 shows the way in which two adjacent aromatic rings of the 1-(4-chlorophenyl)piperazine-1,4-dium cations run parallel in the opposite direction and stack each other by turns in a face-to-face mode. The nearest centroid-centroid distance is 3.453 (1) Å, less than 3.8 Å, the maximum value accepted for π-π interactions (Janiak, 2000). Generally, the Zn—Cl bond lengths and Cl—Zn—Cl bond angles in the [ZnCl₄]^2- anion are not equal to one another but vary with the environment around the Cl atoms (Valkonen et al., 2006). In the title compound, 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 103.37 (5) to 115.30 (5)°, and the bond length of the Zn—Cl lie in the range 2.2420 (12) - 2.3036 (11) Å. Owing to these differences in Zn—Cl bond lengths and Cl—Zn—Cl angles, the coordination geometry of the Zn atom can be described as a slightly distorted tetrahedron (as in Guo et al., 2007). The nearst Zn···Zn intra-chain separation is 7.204 (1) Å, while the distance between adjacent chains is 6.370 (2) Å. Examination of the organic cation geometry shows that the piperazine-1,4-dium ring adopts a typical chair conformation and its geometric parameters [d_av(C—N) = 1.501 (4) and d_av(C—C) = 1.508 (4) Å] are in full agreement with those found in phenylpiperazinium tetrachlorozincate (Ben Gharbia et al., 2005).

Experimental

ZnCl₂, aqueous 1M HCl solution and 1-(4-chlorophenyl)piperazine in a 1:2:1 molar ratio were mixed and dissolved in sufficient ethanol. Crystals of (I) grew as the ethanol evaporated at 293 K over the course of a few days.