A tridentate ligand p-chloro-2-{(2-(dimethylamino)ethylimino)methyl}phenol (HL) was used to generate an octahedral nickel complex [Ni(L)Cl(H 2O)2] 1 which was further converted into a square-planar nickel complex [Ni(L)(N3)] 2. The [2 + 3] cycloaddition reaction between metal coordinated azide 2 and different organonitriles under microwave irradiation afforded tri- and pentanuclear nickel(ii) complexes 4a-4c. Reaction with benzonitrile and 3-cyano pyridine furnished the trinuclear species [Ni 3L2(5-phenyltetrazolato)4(DMF)2] 4a and [Ni3L2{5-(3-pyridyl)-tetrazolato}4(DMF) 2]2H2O 4b, respectively. The nickel centers were found to be linearly disposed to each other and the complex is formed by a 2,3-tetrazolate bridge and a phenoxo bridge between central and terminal nickel atoms. Compound 2 when treated with 1,2-dicyanobenzene under identical conditions furnished a pentanuclear complex [Ni5L4{5-(2- cyanophenyl)-tetrazolato}4(OH)2(H2O) 2]3H2ODMF 4c. In this pentanuclear compound two dimeric nickel units are connected to the central nickel center by a μ3-hydroxo bridge and a tetrazolate ligand operating via a relatively rare 1,2,3-bridging mode. The compounds were characterized by IR, elemental analysis, thermogravimetric analysis and single crystal X-ray crystallography. The magnetic susceptibility data for compounds 4a-4c show dominant antiferromagnetic interactions between the nickel centers for all the complexes. DFT calculations were performed to investigate the magnetic parameter in one of the complexes 4b by a broken symmetry approach. This journal is © the Partner Organisations 2014.