Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me2mal)2} Fragment

Mononuclear dianion {Cu(Me2mal)2}2- have been used as building block for synthesis of six new coordination polymers: {Li2(H2O)2(μ-H2O)[Cu(μ4-Me2mal)(μ-Me2mal)]}n (1), {Na2(μ-EtOH)2[Cu(μ5-Me2mal)2]}n (2), {K8(μ-H2O)6[Cu(μ-H2O)(μ3-Me2mal)(μ6-Me2mal)]2[Cu2(μ5-Me2mal)4]}n (3), {K2M(H2O)5(μ-H2O)3[Cu(μ-Me2mal)(μ3-Me2mal)][Cu(μ-H2O)(μ-Me2mal)(μ3-Me2mal)]}n (M = MgII (4) or NiII (5); isostructural compounds), and {K4Co3(Н2О)8(μ-Н2О)4(μ3-OH)2[Cu(Н2О)(μ-Me2mal)(μ3-Me2mal)]2[Cu(μ-Н2О)(μ3-Me2mal)2]2]}n (6). It was shown, that the structure of the compounds depends on nature and ionic radius of heterometal. In particular, the complex dimensionality growths from 1D to 2D and 3D with increasing the radius of s-metal in compounds 1, 2, and 3, respectively. Partial replacement of K+ in 3 by Mg2+, Ni2+ and Co2+ leads to formation of heterometallic coordination polymers 4 and 5 with 2D structure, and 3D complex 6. The compounds were characterized by single crystal X-Ray diffraction and ESR spectroscopy, as well as the magnetic properties of compounds 1, 4-6 were studied. Further, the topological analysis of the structures and other 794 known mal-derivatives complexes from CSD (version 5.36) have been performed. The main regularities driving coordination modes of ligands and metal cations in relation to structure topology have been established and discussed.