The monometallic precursors (LCu)-Cu-1 and (LCU)-C-2 ((LH2)-H-1 standing for 1,3-bis((3-ethoxysalicylidene)amino) propane and (LH2)-H-1 standing for 1,2-bis((3-methoxysalicylidene)amino) ethane) react with sodium dicyanamide (dca) (NaN3C2), a mixture of gadolinium nitrate, and sodium dicyanamide to yield heterodinuclear (LCuNa)-Cu-2(NCNCN) and (LCuGd)-Cu-1(NO3)(NCNCN)(2) entities. The structural determination shows that two Cu-Na entities are linked by dca with an original mu(1,1) coordination mode, evidenced here for the first time, to yield tetranuclear complexes. Two hydrogen bonds operate between the water molecule coordinated to one of the sodium ions and the free nitrogen atoms of two dca ligands, yielding infinite zigzag chains. The structural determination of the Cu-Gd entities indicates that they are held together by two dca ligands, bridging alternately Cu to Gd and Gd to Gd cations, in the more common mu(1,5) mode to yield a one-dimensional (1D) network. The dca ligands are not able to transmit interaction between the magnetically active centers in these chains, which are the unique example of structurally characterized Cu-Gd complexes involving dca ligands.