We report the synthesis and characterization of four new tetranuclear Ni(ii) complexes, C1-C4, all of which exhibit defective dicubane cores. C1-C4 are derived from the same salicylaldoxime derived ligand, H2L1. Complexes C1 and C4 have isostructural cores, differing in structure only by solvate molecules. Magnetic and computational analyses have revealed that complexes C1, C2, and C4 exhibit competing ferro- and antiferromagnetic interactions, however the different solvated species in C1 and C4 leads to notably different magnitudes in their magnetic coupling constants. Theoretical magneto-structural studies show that the pairwise magnetic exchange interaction is highly dependent on the Ni-X-Ni angle, as revealed by orbital overlap calculations.