The electrochemical oxidation of anodic manganese in an acetonitrile solution of pyrimidine-2-thione (pymtH) or 4,6-dimethylpyrimidine-2-thione (4,6-Me 2 pymtH) and nitrogen donor bidentate ligands such as 1,10-phenanthroline (phen) or 2,2 -bipyridine (bipy), yielded mixed complexes [Mn(pymt) 2 phen], [Mn(4,6-Me 2 pymt) 2 phen] and [Mn(4,6-Me 2 pymt) 2 bipy]. The crystal structures of bis-4,6-dimethylpyrimidyl-2-2 disulphide and 1,10-phenanthroline-bis-(4,6-dimethylpyrimidine-2-thiolato)manganese(II) have been determined by X-ray diffraction. In the manganese complex the metal has a distorted octahedral trans-MnS 2 N 4 geometry with one nitrogen atom of each pyrimidine ligand uncoordinated.