New complexes of 2-thione-4,6-diamino-5-hydroxypyrimidine (HTDAHP) with Fe(III), Ni(II), Ag(I) and Ru (II) are described. IR, 1 H-NMR and mass spectra, conductivity, magnetic and thermal measurements of the complexes are reported and their structures discussed. HTDAHP behaves as a bidentate ligand, forming five membered hydroxyl-amino chelates or four-membered cyclic nitrogen-sulphur chelates without any participation of the pendant amino or hydroxy groups in complexation. The biological activities of the Ag(I) complexes against fungi (Aspergillus niger and Candida albicans) and bacteria (Staphylococcus aureus and Pseudomonas aeruginosa) have been investigated.