Cu6S6 clusters as a building block for the stabilization of coordination polymers with NiAs, NaCl and related structures: synthesis, structure and catalytic studies

New three-dimensional heterometallic coordination polymers (CPs), [{Zn3(Hen)(OH)}{Cu6(6-mna)6}.(H2O)6], (I), [{Zn2(OH)(en)}{Cu6(6-mna)6}0.5.(H2O)2.EtOH], (II), [{Zn3(dap)3(H2O)} {Cu6(6-mna)6}.(H2O)4], (III) and [{Zn2(4,4'-bpy)0.5(OH)(H2O)}{Cu6(6-mna)6}0.5.(H2O)], (IV), (en = ethylenediamine, 6-H2mna = 6-mercaptonicotinic acid, dap = 1,2-diamino propane, 4,4'-bpy = 4,4'- bipyridine), were synthesized and their structures determined by single crystal X-ray crystallography. The structures of the compounds have Cu6S6 octahedral clusters linked through the carboxylates with different zinc-oxo clusters. The compounds have CuI based clusters and ZnII based clusters, which are not observed commonly in coordination polymer structures. Compound I stabilizes in NiAs-related structure, compound II and IV in a NaCl related structure and compound III forms a new type of network structure. All the compounds were active for the heterogeneous nitroaldol reaction.

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