Oxathioamidates (CSNR1R2COOKR1=R2=H (A),R1=H andR2=CH3 (B),R1,=R2=CH3 (C)) can act as O, S donors and form pentaatomic ring systems with divalent metals (M(II)=Mn, Fe, Co, Ni, Cu, Zn). Vibrational spectra and thermal analysis provide information on the amount and nature of associated water molecules. The dehydration of MA2(H2O)2 (M=Mn, Fe, Co, Ni) can be very well explained by the C.F.S.E. (crystal field stabilization energy) for weak field octahedral complexes. The complexes with ligand A and B decompose to form polymers by deprotonation on the thioamide group. The proposed structures are confirmed by the vibrational spectra. For ligand C no stable intermediates are formed during heating, degradation proceeds until metal sulphide remains.