Cyano-complexes and salts with tetracyanonickellateII and N,N-bis(2-hydroxyethyl)-ethylenediamine: synthesis, IR spectra, magnetic properties, thermal analyses, and crystal structures

Four cyano complexes, [Ni(N-bishydeten)Ni(CN)4]n (c1), [Cu(N-bishydeten)2][Ni(CN)4] (c2), [Zn2(N-bishydeten)2Ni(CN)4]n (c3), and [Cd(N-bishydeten)2][Ni(CN)4] (c4), have been synthesized and characterized by FT-IR, elemental, and thermal analyses. The structures of c2 and c4 were determined by single-crystal X-ray diffraction studies; both structures contain isolated cations and anions. The c2 consists of [Cu(N-bishydeten)2]2þ with octahedrally coordinated CuII and diamagnetic [Ni(CN)4]2–, but c4 consists of [Cd(N-bishydeten)2]2þ, in which CdII is eight coordinate with two tetradentate N-bishydeten and diamagnetic [Ni(CN)4]2–. The value of the shape measure S (o) indicates that the coordination geometry around CdII lies along D2d [dodecahedron; (dd)], C2v [bicapped trigonal prism; (btp)], and D4d [square antiprism; (sap)] but close to D2d and D4d. Variable temperature magnetic susceptibility measurements of c1 and c2 show the presence of little antiferromagnetic interaction below 20 K. Thermal analyses reveal that first neutral N-bishydeten and then cyano ligands were liberated from the complexes.TUB_ITAK, Grant TBAG-104T205) Gaziosmanpas¸a University Research Foundation (Grant 2007-24