Reaction of IrCl3 with Hhpp in refluxing ethanol (Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyramido[1,2-a]pyrimidine) yields Ir2(hpp)4Cl2, the first paddlewheel complex of IrIII, with a short Ir–Ir distance of 2.495(1) Å, an average Ir–Cl distance of 2.643[6] Å, an Ir26+ core bridged by four hpp ligands with two axial chlorine atoms, and a double bond between the Ir atoms.