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Four geometric mer-isomers in the [Co(2,3-tri)(cmen)Cl]2+ system have been synthesized and well separated (2,3-tri = N-(3-aminoethyl)-1,3-propanediamine; cmen = 1,2-di- aminopropane). Their structures in DMSO-d6 solution have been uniquely assigned by using 2D- NMR techniques (gCOSY and NOESY).