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The high-nuclearity coordination clusters of transition metal cations have been receiving growing attention due to their interesting electronic and magnetic properties which contribute to their potential as nanoelectronic components,metalloenzyme models,nanoscale catalysts,and molecular magnets.1-6 Based on the previous study,we have synthesized a novel complex with a {Co32} cluster core capped by six p-tert-butylthiocalix[4] arene molecules by a solvothermal method and its three isomers were observed.