Reaction of the complex [Ni(rac-CTH)](2+) (rac-CTH = rac5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) with [Fe(CN)(6)](3-) leads to a novel cyano-bridged Ni3Fe2 complex, {[Ni(rac-CTH)](3)[Fe(CN)(6)](2)}(4). The structure consists of an alternating arrangement of {Fe(CN)(6)Ni(rac-CTH)}(2) squares and trans-planar [Ni(rac-CTH)](2+) units bridged by cyanide groups to give a neutral 1D chain running along the a axis. Magnetic measurements reveal the occurrence of ferromagnetic coupling between Fe-III and Ni-II ions and 3D magnetic ordering at 3 K due to interchain interactions. Canting of the moments is inferred from the low value of the magnetization of the saturation below T-c.