An unusual mixed crystal of a square-pyramidal oxorhenium(V), [ReOCl(Hdua)], and an octahedral imidorhenium(V) complex, [Re(dua)Cl 2 (PPh 3 )], was prepared from the reaction of trans-[ReOCl 3 (PPh 3 ) 2 ] and (6Z)-6-(2-aminobenzylideneamino)-5-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (H 3 dua) in ethanol. Characterization was performed by single crystal X-ray structure determination and IR spectroscopy. The chelate Hdua is coordinated as a tridentate diamido-imine, and dua is chelated as an imido-imino-amide.