The synthesis of a new {Ni₈} cluster bearing tetrazolate- and azido-bridging ligands, and supported by chelating α-methyl-2-pyridine-methanol (mpmH) groups, is described herein. The reported compound has a unique trapezoidal prismatic topology, resulting from an unexpected in situ click reaction between the MeCN reaction solvent and the N₃^- ions under mild, room-temperature conditions. Such a click chemistry approach to the preparation of 0-D compounds is relatively unexplored and represents a fruitful strategy for the synthesis of new coordination clusters and molecule-based magnetic materials.