The reaction of Ni(ClO4)2·6H2O with 3-ethoxy-2-hydroxybenzaldehyde
(Hemp), methylamine, and NaN3 in DMF solution, under solvothermal conditions, leads to the formation of the heterotetrametallic cluster [Ni2Na2(μ1,1,1-N3)2(emimp)4(DMF)2] (I) (emimp = 2-ethoxy-6-formyl-phenolate anion, DMF = N,N-dimethyl-formamide). Compound I displays dominant ferromagnetic interactions through μ1,1,1-N3 bridging mode.