Structural variations in Ni(II) complexes of salen type di-Schiff base ligands

Abstract

Three di-Schiff-base ligands, N,N′-bis(salicylidene)-1,3-propanediamine (H₂Salpn), N,N′-bis(salicylidene)-1,3-pentanediamine (H₂Salpen) and N,N′-bis(salicylidine)-ethylenediamine (H₂Salen) react with Ni(SCN)₂ • 4H₂O in 2:3 molar ratios to form the complexes; mononuclear [Ni(HSalpn)(NCS)(H₂O)] • H₂O (1a), trinuclear [{Ni(Salpen)} ₂Ni(NCS) ₂] (2b) and trinuclear [{Ni(Salen)} ₂Ni(NCS) ₂] (3) respectively. All the complexes have been characterized by elemental analyses, IR and UV–vis spectra, and room temperature magnetic susceptibility measurements. The structures of 1a and 2b have been confirmed by X-ray single crystal analysis. In complex 1a, the Ni(II) atom is coordinated equatorially by the tetradentate, mononegative Schiff-base, HSalpn. Axial coordination of isothiocyanate group and a water molecule completes its octahedral geometry. The hydrogen atom attached to one of the oxygen atoms of the Schiff base is involved in a very strong hydrogen bond with a neighboring unit to form a centrosymmetric dimer. In 2b, two square planar [Ni(Salpen)] units act as bidentate oxygen donor ligands to a central Ni(II) which is also coordinated by two mutually cis N-bonded thiocyanate ligands to complete its distorted octahedral geometry. Complex 3 possesses a similar structure to that of 2b. A dehydrated form of 1a and a hydrated form of 2b have been obtained and characterized. The importance of electronic and steric factors in the variation of the structures is discussed.