Cyano-Complexes and Salts With Tetracyanonickellate II and N,N-Bis(2 Synthesis, IR Spectra, Magnetic Properties, Thermal Analyses, and Crystal Structures

Abstract

Four cyano complexes, [Ni(N-bishydeten)Ni(CN) <inf>4</inf>] <inf>n</inf> (c1), [Cu(N-bishydeten) <inf>2</inf>][Ni(CN) <inf>4</inf>] (c2), [Zn <inf>2</inf>(N-bishydeten) <inf>2</inf>Ni(CN) <inf>4</inf>] <inf>n</inf> (c3), and [Cd(N-bishydeten) <inf>2</inf>][Ni(CN) <inf>4</inf>] (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 [Ca(N-bishydeten) <inf>2</inf>] 2+ with octahedrally coordinated Cu II and diamagnetic [Ni(CN) <inf>4</inf>] <inf>2</inf>, but c4 consists of [Cd(N-bishydeten) <inf>2</inf>] 2+, in which Cd II is eight coordinate with two tetradentate N-bishydeten and diamagnetic [Ni(CN) <inf>4</inf>] 2-. The value of the shape measure S (°) indicates that the coordination geometry around Cd II lies along D <inf>2d</inf> [dodecahedron; (dd)], C <inf>2v</inf> [bicapped trigonal prism; (btp)], and D <inf>4d</inf> [square antiprism; (sap)] but close to D <inf>2d</inf> and D <inf>4d</inf>. 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. © 2012 Taylor & Francis.