The crystallization of the SCS pincer platinum complex with secondary thioamide groups, [4-methyl-2,6-bis(anilinothiocarbonyl)-kappa S-2,S'-phenyl-kappa C-1]chloroplatinum(II), spontaneously forms a trinuclear cluster complex accompanied by liberating HCl in DMSO/EtOH mixture. The crystal structure of the SNS pincer copper complex with secondary thioamide groups, [2,5-bis(benzylaminothiocarbonyl)-kappa S-2,S'-pyrrolyl-kappa N-1] chlorocopper(II), exhibits a dimer structure bearing the bridging thioamide group. The thioamide group acts as the bridging ligand of the multimetallic complexes in different anionic and neutral manners. (C) 2010 Elsevier B. V. All rights reserved.