Structure and Properties of Mono- and Heterometallic Cadmium, Zinc, and Nickel Complexes Containing Diethyldithiocarbamate Ions and Ethylenediamine Molecules
Journal of Structural Chemistry
, E-ISSN: 1573-8779
Nikolaev Institute of Inorganic Chemistry SB RAS
The crystal structure of the mono- and heterometallic complexes [MEn3]L2 (M = Zn2+,M2+) and [MEn3 ][CdL3]2 (M = Cd2+, Zn2+, Ni2+) containing ethylenediamine (En) molecules and diethyldithio-carbamate ions (L = (C2H5)2NCS2−) is investigated. The three heterometallic complexes are isostructural; their structure consists of discrete mononuclear ions. In the [MEn3]2+ cation, the central M atom lies on the twofold axis; therefore, two of the three metallocycles MN2C2 of the [MEn3]2+ cation are independent. One of the two has a gosh-configuration. In the coordinated En molecules, the N-M-N chelate angles are 77.0 and 82.9‡ (M = Cd2+); 80.0 and 80.5‡ (M = Zn2+); 79.7 and 80.8‡ (M = Ni2+). The nitrogen atoms form a distorted octahedron around M. The average M-N bond lengths for the complexes are 2.35, 2.19, and 2.16 å for M = Cd2+, Zn2+, and Ni2+, respectively. All the atoms of the [CdL3]− complex anion are in the general position; the central atom coordinates three cyclic bidentate L− ligands. The S atoms form a distorted trigonal prism, where the S...S distances in the vertical edges are nearly the same in all the complexes (2.94(1)-3.00(2) å). It was shown by1H,14N, and113Cd NMR that the ionic complexes [ZnEn3]L2 and [CdEn3][CdL3]2 in solution are transformed into nonelectrolyte type mixed-ligand complexes.