Transition metal complexes with the thiosemicarbazide-based ligands-I. Nickel(II) complexes with the quadridentate ligands based on S-methylisothiosemicarbazide; X-ray crystal structure of (acetyl-acetone N(1)-salicylidene-S-methylizothiosemicarbazonato) nickel(II)

Abstract

The reaction of a warm ethanolic solution of [Ni(SALSMeTSC-H)Py]Cl·0.5Py (SALSMeTSC = salicylaldehyde S-methylisothiosemicarbazone) with salicylaldehyde and acetylacetone (HACAC), yielded the corresponding square-planar complexes [Ni(SAL2SMeTSC-2H)] (A) and [Ni(SALACACSMeTSC-2H)] (B) (SAL2SMeTSC, and SALACACSMeTSC = quadridentate 2O2N ligand: N(1),N(3)-bis(salicylidene)-S-methylisothiosemicarbazide, and acetylacetone N(1)-salicylidene-S-methylisothiosemicarbazone, respectively). An X-ray analysis of complex B showed that in the reaction of the starting complex with HACAC a rearrangement of the salicylaldehyde moiety takes place (while the CN(3) bond of the azomethine group is ruptured) and its binding to the N(1) nitrogen. At the same time, HACAC is simultaneously bonded to the liberated N(3)-nitrogen of the hydrazine fragment. Crystal data for the complex B (NiC14H15N3O2S) are: Mr = 348.0, orthorhombic, space group Pna21, a = 7.484(3), b = 21.995(8), c = 8.866(3) Å; V = 1459.44 Å3, Z = 4, F(000) = 720, Dc = 1.58 g cm-1, Do = 1.56 g cm-1, μ(MoKα) = 14.45 cm-1. The structure was solved by the heavy-atom method and refined anisotropically to an R value of 0.078 for 1174 non-zero reflections. The complex molecules are planar, the NiNi distance of nearest molecules being about 3.76 Å. The compounds have been characterized by elemental analysis as well as by IR and electronic spectra. © 1987.