Three bimetallic assemblies, PPh4[Ni(pn)(2)] [M(CN)(6)]. H2O (M = Fe (1), Cr (2), Co (3); pn = rac-1,2-diaminopropane), have been prepared and structurally and magnetically characterized. Assembly a crystallizes in the monoclinic system of the space group P2/c (No. 13) with a = 12.927(2) Angstrom, b = 8.454(2) Angstrom, c = 17.564(2) Angstrom, beta = 100.15(1)degrees, V = 1889.5(6) Angstrom(3) and Z = 2, and 3 crystallizes in the same space group with a = 12.971(1) Angstrom, b = 8.437(1) Angstrom, c = 17.118(1) Angstrom, beta = 99.84(1)degrees, V = 1845.7(3) Angstrom(3), and Z = 2. The crystal structure analyses of 2 and 3 reveal a one-dimensional zigzag chain structure extending through the M-CN-NI-NC-M linkages.as previously found for 1. Assemblies 1 and 2 show a ferromagnetic intrachain interaction based on the strict orthogonality of the magnetic orbitals between adjacent Ni-II and M-III (M = Fe, Cr) ions. Assembly 3 is essentially paramagnetic within the chain. All the assemblies show a weak antiferromagnetic interchain interaction and hence no magnetic ordering over the lattice.