Dichlorido(4-meth­oxy-2-{[2-(piperazin-4-ium-1-yl)eth­yl]imino­meth­yl}phenol­ate)cadmium

Muhammad Saleh Salga; Hamid Khaledi; Hapipah Mohd Ali

doi:10.1107/S1600536811022100

. 2011 Jun 18;67(Pt 7):m927. doi: 10.1107/S1600536811022100

Dichlorido(4-methoxy-2-{[2-(piperazin-4-ium-1-yl)ethyl]iminomethyl}phenolate)cadmium

Muhammad Saleh Salga ^a, Hamid Khaledi ^a,^*, Hapipah Mohd Ali ^a

PMCID: PMC3151769 PMID: 21836911

Abstract

In the title compound, [CdCl₂(C₁₄H₂₁N₃O₂)], the Schiff base ligand chelates the Cd^II ion in an N,N,O-tridentate fashion. Two Cl atoms complete a distorted square-pyramidal coordination environment around the metal atom. In the crystal, adjacent molecules are linked through C—H⋯π interactions into infinite chains along the a axis. The molecules are further connected into a three-dimensional network via N—H⋯O, N—H⋯Cl and C—H⋯Cl interactions. The ethylene group is disordered over two sets of sites in a 0.520 (10):0.480 (10) ratio.

Related literature

For similar structures, see: Mukhopadhyay et al. (2003 ▶); Xu et al. (2008 ▶); Saleh Salga et al. (2010 ▶). For a description of the geometry of complexes with five-coordinated metal ions, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[CdCl₂(C₁₄H₂₁N₃O₂)]
M _r = 446.64
Monoclinic,
a = 10.1173 (9) Å
b = 16.2686 (15) Å
c = 10.3486 (10) Å
β = 103.069 (1)°
V = 1659.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.65 mm⁻¹
T = 100 K
0.25 × 0.18 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.684, T _max = 0.937
14540 measured reflections
3624 independent reflections
3138 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.061
S = 1.07
3624 reflections
225 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022100/xu5230sup1.cif

e-67-0m927-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022100/xu5230Isup2.hkl

e-67-0m927-Isup2.hkl^{(177.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—O1	2.241 (2)
Cd1—N1	2.245 (3)
Cd1—N2	2.475 (2)
Cd1—Cl1	2.4584 (8)
Cd1—Cl2	2.4797 (8)

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱ	0.92 (2)	1.80 (2)	2.705 (3)	166 (4)
N3—H3B⋯Cl2ⁱⁱ	0.90 (2)	2.33 (2)	3.222 (3)	174 (4)
C9—H9A⋯Cl1ⁱⁱⁱ	0.99	2.64	3.454 (8)	139
C8—H8A⋯Cl2^iv	0.98	2.82	3.777 (3)	167
C8—H8B⋯Cl1^v	0.98	2.76	3.514 (3)	134
C13—H13A⋯Cl1ⁱ	0.99	2.71	3.542 (4)	142
C12—H12A⋯Cg1^vi	0.99	2.48	3.408 (4)	156
C9′—H9D⋯Cg1^iv	0.99	2.72	3.620 (8)	151

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

Acknowledgments

The authors thank the University of Malaya for funding this study (FRGS grant No. FP004/2010B).

supplementary crystallographic information

Comment

The ligands containing a piperazine ring have been reported to possess ambidentate character, capable of binding metal centers through one or both piperazine N atoms (Mukhopadhyay et al., 2003; Xu et al., 2008; Saleh Salga et al., 2010). The coordination mode depends largely on the conformation (chair or boat) adopted by the ring which, in turn, depends on the metal salt entity and remote substituations in the ligand. In the present structure, the piperazine ring assumes a chair conformation and employs only one of the ring N atoms to bind to the metal center. The Schiff base ligand chelates the metal atom in an N,N,O-mode, along with two Cl atoms makes a distorted square-pyramidal cadmium(II) complex. The distortion from the ideal geometry is evident from the τ index of 0.30 (τ is 0 for an ideal square-pyramid and is 1 for a perfect trigonal-bipyramid, Addison et al., 1984). The other ring N atom stays away from the chelation, and is protonated to keep the electronutrality of the molecule, thus the complex can be described as a zwitterion. In the crystal, C—H···π interactions link the molecules into infinite chains along the a axis and these are connected into a three-dimensional network via N—H···O, N—H···Cl and C—H···Cl hydrogen bonds (Table 1).

Experimental

A mixture of 5-methoxysalicylaldehyde (0.35 g, 2.3 mmol) and aminoethylpiperazine (0.3 g, 2.3 mmol) in ethanol (20 ml) was refluxed for 2 h, followed by addition of a solution of cadmium(II) chloride (0.42 g, 2.3 mmol) in a minimum amount of ethanol. The resulting solution was refluxed for 1 h and then left at room temperature for one day to give the X-ray quality crystals of the title compound.