In the present work, five new Ni-5 clusters employing the versatile 2-pyridylcyanoxime ligand have been synthesized and chemically, structurally, and magnetically characterized. The crystallographic examination of these Ni-5 clusters together with those already published in the literature, giving a total number of 14 complexes, exhibiting up to 8 different topologies for which the relationship between topology, reaction conditions and magnetic response has been analyzed. DC magnetic measurements were carried in the 300-2 K range for the new complexes and the analysis of the experimental data revealed an antiferromagnetic response for the oximato mediated interactions with a variety of ground states (S = 0, 1, 3) as function of the cluster topology.