Structural and Magnetic Properties of M(mnt)₂Salts (M = Ni, Pt, Cu) with a Ferrocene-Based Cation, [FcCH₂N(CH₃)₃]⁺. Interplay between M···M and M···S Intermolecular Interactions

Abstract

A series of metal bis-mnt complexes (mnt = 1,2-dithiolatomaleonitrile) with the trimethylammonium methylferrocene cation have been synthesized and characterized using X-ray diffraction, magnetic susceptibility, and differential scanning calorimetry measurements. The complexes have the formulas (FcCH(2)NMe(3))[Ni(mnt)(2)] (2), (FcCH(2)NMe(3))[Pt(mnt)(2)] (3), and (FcCH(2)NMe(3))(2)[Cu(mnt)(2)] (4) (where Fc = ferrocene). At 300 K, the crystal structures of 1:1 complexes 2 and 3 are very similar. They consist of pairs of [M(mnt)(2)](-) in a slipped configuration packed in stacks. Each [M(mnt)(2)](-) stack is separated from adjacent stacks by two columns of cations. Within the pairs, the [M(mnt)(2)](-) anions interact via short M.S contacts, while there are no short contacts between the pairs. Complex 4, which has a 2:1 stoichiometry, exhibits a markedly different packing arrangement of the anionic units. Due to the special position of the Cu atom in the asymmetric unit cell, [Cu(mnt)(2)](2)(-) dianions are completely isolated from each other. The magnetic susceptibility behavior of the nickel complex is consistent with the presence of magnetically isolated, antiferromagnetically (AF) coupled [Ni(mnt)(2)](-) pairs with the AF exchange parameter, J = -840 cm(-)(1). The platinum complex undergoes an endothermic structural phase transition (T(p)) at 247 K. Below T(p) its structure is characterized by the formation of magnetically isolated [Pt(mnt)(2)](2)(2)(-) dimers in an eclipsed configuration with short Pt.Pt and S.S contacts between monomers. In the magnetic properties, the structural changes reveal themselves as an abrupt susceptibility drop implying a substantial increase of the AF exchange parameter. A mechanism of the phase transition in the platinum compound is proposed. For compound 4, paramagnetic behavior is observed.