In the present work, novel coordination possibilities for the system dapdoH(2)/Ni-II (dapdoH(2) = 2,6-diacetylpyridinedioxime) have been explored. Depending on the starting reagents and solution conditions, several clusters with nudearities ranging from Ni-5 to Ni-10 were achieved and structurally characterized, namely, [Ni-5(R-COO)(2)(dapdo)(2)(dapdoH)(2)(N(CN)(2))(2)(MeOH)(2)] in which R-COO- = benzoate (1) or 3-chlorobenzoate (2), [Ni-8-(dapdo)(4)(NO3)(4)(OH)(4)(MeOH)(4)] (3), and [Ni-10(dapdo)(8)(N-(CN)(2))(2)(MeO)(MeOH)](NO3) (4). For the first time, pentadentate coordination for the dapdo(2-) ligand has been established. All compounds show a combination of square-planar and octahedrally coordinated nickel atoms. According to the Ni-2(sp)Ni-3(Oh) (1 and 2), Ni-4(sp)NI4(Oh) (3), and Ni-4(sp)Ni-6(Oh) (4) environments, these systems magnetically behave as trimer, tetramer, and hexanuclear dusters, respectively. dc magnetic measurements in the 2-300 K range of temperature reveal antiferromagnetic coupling for all compounds, and the correlation of the superexchange interaction with the torsion angles involving the oximato bridges is experimentally confirmed.