Abstract: | The cyano‐bridged heteronuclear coordination polymer polytris(5,12‐dimethyl‐7,14‐diphenyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene)copper(II)]‐hexa‐μ‐cyano‐bistricyanocobalt(III)] dimethylformamide solvate trihydrate], {Cu3Co2(CN)12(C24H32N4)3]·C3H7NO·3H2O}n, was synthesized by the assembly reaction of CuL]2+ (L is 5,12‐dimethyl‐7,14‐diphenyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene) and Co(CN)6]3? in a dimethylformamide–water solution. The structure consists of neutral cyano‐bridged Cu3Co2 units with the unique Co atom in a general position and all three Cu atoms on independent inversion centres. Each Co(CN)6]3? ion connects three CuII ions via three cyano groups to form a novel cyano‐bridged two‐dimensional stair‐shaped‐layer structure. The water and dimethylformamide molecules are situated in the inter‐fragment spaces. |