Di-μ-chlorido-bis­[bis­(ethyl­enediamine-κ2 N,N′)cadmium(II)] dichloride

Christian Näther; Inke Jess

doi:10.1107/S1600536809054804

. 2009 Dec 24;66(Pt 1):m98. doi: 10.1107/S1600536809054804

Di-μ-chlorido-bis[bis(ethylenediamine-κ² N,N′)cadmium(II)] dichloride

Christian Näther ^a,^*, Inke Jess ^a

PMCID: PMC2980226 PMID: 21579987

Abstract

The crystal structure of the title compound, [Cd₂Cl₂(C₂H₈N₂)₄]Cl₂, consists of binuclear centrosymmetric [Cd₂(C₂H₈N₂)₄Cl₂]²⁺ cations and discrete chloride anions. The Cd^II cation is coordinated by four N atoms of two ethylenediamine ligands and two symmetry-related chloride anions within a distorted CdN₄Cl₂ octahedron. Two Cd^II cations are connected by two chloride anions via μ₂-coordination, forming a four-membered Cd₂Cl₂ ring. The uncoordinated chloride anions are linked to the amino groups via N—H⋯Cl hydrogen bonding. Two C atoms of one of the two crystallographically independent ethylenediamine ligands are disordered and were refined using a split model [occupancy ratio 0.674 (9):0.326 (9)].

Related literature

For the general background to this work see: Bhosekar et al. (2006 ▶); Näther et al. (2007a ▶,b ▶). For related structures, see: Cannas et al. (1980 ▶); Marsh (1999 ▶); Pauly et al. (2000 ▶); Chen et al. (2005 ▶).

Experimental

Crystal data

[Cd₂Cl₂(C₂H₈N₂)₄]Cl₂
M _r = 607.02
Monoclinic,
a = 6.3869 (8) Å
b = 11.3143 (10) Å
c = 14.8255 (19) Å
β = 92.621 (13)°
V = 1070.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.49 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998 ▶) T _min = 0.576, T _max = 0.613
6562 measured reflections
3110 independent reflections
2699 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.018
wR(F ²) = 0.047
S = 1.04
3110 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: DIF4 (Stoe & Cie, 1992 ▶); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XCIF in SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054804/wm2291sup1.cif

e-66-00m98-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054804/wm2291Isup2.hkl

e-66-00m98-Isup2.hkl^{(152.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—N2	2.3268 (15)
Cd1—N3	2.3314 (15)
Cd1—N1	2.3513 (14)
Cd1—N4	2.3971 (16)
Cd1—Cl1ⁱ	2.6200 (5)
Cd1—Cl1	2.7078 (5)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯Cl2ⁱⁱ	0.90	2.73	3.6137 (15)	168
N1—H2N1⋯Cl2ⁱ	0.90	2.54	3.3941 (15)	159
N2—H2N2⋯Cl2ⁱⁱⁱ	0.90	2.42	3.3123 (15)	171
N3—H1N3⋯Cl1^iv	0.90	2.53	3.3581 (16)	154
N3—H2N3⋯Cl2	0.90	2.67	3.4919 (17)	152
N4—H3N4⋯Cl2ⁱⁱ	0.90	2.78	3.653 (2)	164
N4—H4N4⋯Cl2ⁱⁱⁱ	0.90	2.85	3.708 (2)	161

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

Acknowledgments

This work was supported by the state of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Projekt No. NA 720/1–1). We thank Professor Dr Wolfgang Bensch for the facility to use his experimental equipment.

supplementary crystallographic information

Comment

Recently, we became interested in the synthesis, structures and thermal behaviour of coordination polymers based on zinc(II) halides and N-donor ligands. We have found out that new ligand-deficient coordination polymers can simply be prepared by thermal decomposition of suitable ligand-rich precursor compounds (Bhosekar et al., 2006; Näther et al., 2007a,b). In related studies we started to investigate the properties of the heavier homologue cadmium. As a part of this project the crystal structure of the title compound, [Cd₂(C₂H₈N₂)₄Cl₂]Cl₂, was investigated.

In the crystal structure discrete [(C₂H₈N₂)₄Cd₂Cl₂]²⁺ cations are found which are located on centres of inversion. The structure contains additional chloride anions which are not connected to the cations and are located in general positions. In the complex cation the Cd²⁺ atoms are cis-coordinated by two symmetry related chloride anions and four N atoms of two crystallographically independent ethylenediamine ligands, leading to distorted CdN₄Cl₂ octahedra (Fig. 1 and Table 1). The Cd²⁺ atoms are linked by two symmetry-related chloride anions into a 4-membered centrosymmetric and planar Cd₂Cl₂ ring. This structural motif is known and found in some other Cd halide complexes (Cannas et al., 1980; Marsh, 1999; Pauly et al., 2000). Both Cd—Cl distances (Table 1) are different but comparable to those in the related compounds. The chloride anions that are not involved in Cd coordination are connected to the H atoms of the amino groups by N—H···Cl hydrogen bonding (Table 2).

Experimental

0.1833 g CdCl₂ (1 mmol) were reacted with 0.3005 g ethylenediamine (5 mmol) in a glass tube at room temperature. After three days colourless crystals of the title compound have formed as the minor phase in a mixture with the literature known compound tris(ethylenediamine-N,N')-cadmium(II) dichloride monohydrate (Chen et al., 2005).