Synthesis and crystal and molecular structure of a tetranuclear cluster based on the rhenium(III)-bisorganohydrazino core: [Re(HNNC(4)H(3)N(2))(NNC(4)H(3)N(2))(OCH(3))(2)](4).

Reaction of NH(4)ReO(4) with excess 2-hydrazinopyrimidine in methanol yields [Re(eta(1)-NNC(4)H(3)N(2)H)(eta(2)-HNNC(4)H(3)N(2))Cl(3)] (1). Attempts to recrystallize 1 by slow diffusion of methanol into DMF after 8 months produced black crystals of [Re(HNNC(4)H(3)N(2))(NNC(4)H(3)N(2))(OCH(3))(2)](4) (2). The structure of 2 consists of isolated tetranuclear clusters, constructed from {Re(eta(2)-HNNC(4)H(3)N(2))(eta(1)-NNC(4)H(3)N(2))(OCH(3))(2)} units linked through the beta-nitrogen of the chelating organodiazene ligand of adjacent units into a box-like aggregate.