The cocrystallization of [Cu(SCN)](n) chains and [Cu-2(4,4'-bpy)(CN)(2)](n) (4,4 '-bpy = 4,4 '-bipyridine) layers generated a 3-D pseuclopoly-rotaxane compound, [Cu-2(4,4'-bpy)(CN)(2)]center dot[Cu(SCN)] (1), which can also be viewed as a 3-D network constructed by linkages of 2-D sheets and 1-D chains via unsupported Cu '-Cu ' interactions. The Cu '-Cu ' contact of 2.651(4) angstrom in 1 is the shortest unsupported Cu '-Cu ' distance documented to date, indicating cuprophilic attractions.