Self-assembly of the [Mo-III(CN)7](4-) anion and the Mn-II unit with a macrocyclic ligand results in the first example of a one-dimensional (1D) chain compound based on the heptacyanomolybdate, [Mn(L-NSC10)](2)[Mo-(CN)(7)]center dot 2H(2)O (L-NSC10 = 1,4,7,10,13-pentaazacyclopenta-decane). Because of the existence of the interchain magnetic coupling, long-rang magnetic ordering was observed in this compound.