Syntheses, crystal structures, and thermal stabilities of the first Hofmann-DMF-type complexes Zn(DMF)2M(CN)4 (M = Ni, Pd, Pt)

The first Hofmann-DMF-type complexes Zn(DMF)2M(CN)4 (M = Ni (1), Pd (2), Pt (3)) have been synthesized by solution diffusion and characterized structurally by single-crystal X-ray diffraction. The structure consists of 2-D corrugated sheets stacking along the a-axis in an ABAB packing mode without interpenetration. The octahedral Zn ions and square-planar M ions occupy special positions of 2/m site symmetry. The DMF, except for six methyl H atoms, lies on a crystallographic mirror plane; the DMF molecules coordinate to axial sites of Zn on both sides of the sheet. The framework of 1 begins to collapse with loss of coordinated DMF.