1-(2,3-Di­methyl­phen­yl)piperazine-1,4-diium tetra­chlorido­cuprate(II)

Safa Ben Mabrouk; Iness Ameur; Sonia Abid; Mohamed Rzaigui

doi:10.1107/S1600536813021454

. 2013 Aug 10;69(Pt 9):m485. doi: 10.1107/S1600536813021454

1-(2,3-Dimethylphenyl)piperazine-1,4-diium tetrachloridocuprate(II)

Safa Ben Mabrouk ^a, Iness Ameur ^a, Sonia Abid ^a,^*, Mohamed Rzaigui ^a

PMCID: PMC3884381 PMID: 24426985

Abstract

In the title salt, (C₁₂H₂₀N₂)[CuCl₄], the Cu^II atom occupies a general position in a flattened tetrahedral environment by Cl ligands, characterized by Cl—Cu—Cl angles of 134.04 (3) and 137.18 (4)°. The six-membered piperazinediium ring adopts a chair conformation. The organic cation and inorganic anion interact through N—H⋯Cl and C—H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For general background to the properties of tetrahalidocuprate(II) compounds, see: Solomon et al. (1992 ▶); Kim et al. (2001 ▶); Panja et al. (2005 ▶); Lee et al. (2004 ▶); Turnbull et al. (2005 ▶); Shapiro et al. (2007 ▶). For general background to the geometry of the tetrahalidocuprate(II) species, see: Halvorson et al. (1990 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-69-0m485-scheme1.jpg

Experimental

Crystal data

(C₁₂H₂₀N₂)[CuCl₄]
M _r = 397.64
Triclinic,
a = 7.1986 (15) Å
b = 7.7611 (11) Å
c = 15.635 (4) Å
α = 77.035 (16)°
β = 79.311 (19)°
γ = 81.845 (14)°
V = 831.9 (3) Å³
Z = 2
Ag Kα radiation
λ = 0.56087 Å
μ = 1.01 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ▶) T _min = 0.786, T _max = 0.863
9228 measured reflections
8079 independent reflections
4600 reflections with I > 2σ(I)
R _int = 0.020
2 standard reflections every 120 min intensity decay: 7%

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.129
S = 1.00
8079 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.68 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: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813021454/ru2053sup1.cif

e-69-0m485-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021454/ru2053Isup2.hkl

e-69-0m485-Isup2.hkl^{(387.2KB, 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—H1⋯Cl3ⁱ	0.91	2.48	3.1610 (18)	132
N2—H2A⋯Cl2ⁱⁱ	0.90	2.35	3.144 (2)	147
N2—H2B⋯Cl1ⁱⁱⁱ	0.90	2.30	3.152 (2)	159
N2—H2B⋯Cl2ⁱⁱⁱ	0.90	2.80	3.271 (2)	114
C2—H2D⋯Cl1ⁱ	0.97	2.74	3.666 (3)	159
C3—H3B⋯Cl1^iv	0.97	2.78	3.585 (2)	141
C4—H4B⋯Cl4ⁱⁱ	0.97	2.66	3.616 (2)	168
C6—H6⋯Cl4ⁱⁱ	0.93	2.71	3.572 (2)	154
C12—H12C⋯Cl3ⁱ	0.96	2.71	3.568 (3)	149

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

Acknowledgments

This work was supported by the Tunisian Ministry of HEScR.

supplementary crystallographic information

1. Comment

Cuprates are chemical compounds in which copper forms complex anions where the overall charge is negative. In such complexes, the ligands are generally cyanides, hydroxides or halides. Due to their important properties, the cuprates still constitute a research axis in many laboratories (Solomon et al., 1992; Kim et al., 2001; Lee et al., 2004; Panja et al., 2005; Turnbull et al., 2005; Shapiro et al., 2007). We report here synthesis and crystal structure of a new cuprate, (C₁₂H₂₀N₂)[CuCl₄] (I). Crystal structure of (I) gives another illustration of this type of material. The asymmetric unit within the unit cell is build of one tetrahedral [CuCl₄]^2- anion and one 1-(2,3-dimethylphenyl)piperazine-1,4-diium cation (Fig. 1). The copper(II) anion exhibits a coordination geometry intermediate between tetrahedral and square–planar. However we can tell that the configuration adopted by this anion is a flattened tetrahedral where the two trans bond angles, Cl(1)—Cu—Cl(4) = 137.18 (4)° and Cl(2)—Cu—Cl(3) = 134.04 (3)°, are very near to the minimum of the potential curve describing the angular deformation of isolated [CuCl₄]^2- anion (θ min = 135.95°) (Halvorson et al., 1990). The phenyl ring (C5—C10) of 1-(2,3-dimethylphenyl)piperazine-1,4-diium is planar with an r.m.s. deviation of 0.0111. The 6-membered piperazinium ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q_T = 0.581 (2) Å, θ = 5.3 (2)° and φ = 328 (3)°. The dihedral angle between the piperazine (N1–N2/C1–C4) ring and the benzene (C5–C10) ring is 65.41 (7) °. In the crystal, neighboring molecules are linked by N—H···Cl and C—H···Cl hydrogen bonds, forming a three-dimensional network (Figure 2).

2. Experimental

To an aqueous solution (10 ml) of HCl (0.2M) was added 1-(2,3-dimethylphenyl)piperazine (0.19 g, 1 mmol). To the obtained solution, a blue aqueous solution (10 ml) of CuCl₂.6H₂O (0.170 g, 1 mmol) was added slowly with stirring. The resulting solution was submitted to a slow evaporation at room temperature until the formation of yellow crystals of the title compound.