The synthesis, structures, and magnetic properties of four cyano-bridged (MRu2lll)-Ru-ll compounds prepared from the paramagnetic Ru-lll building blocks, trans-[Ru(salen)(CN)(2)](-1) [H(2)salen = N,N'-(-ethylenebis(salicylideneimine)] and trans-[Ru(acac)(2)(CN)(2)](-) (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)(4)[Ru(salen)(CN)(2)](2)}center dot 6CH(3)OH-2H(2)O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn-ll and Ru-lll centers. Compound 3, {Mn(H2O)(2)[Ru(salen)(CN)(2)](2)(H2O2)-H-.}(n), has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acaC)(2)(CN)(2)](2)}center dot 2CH(3)OH center dot(2)H(2)O (cyclam = 1,4,8,11 -tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)(2)(CN)(2)](2)}(n), has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru-lll and M-ll (Mn-ll, Ni-ll) ions.