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Complexes of the type [Co(LL)₂Cl₂]Cl, where LL=N,N′-ethylenediamine (en), 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 1,10-phenanthroline-5,6-dione (phendione) and dipyrido[3,2-a:2′,3′-c]phenazine (dppz) have been synthesized and characterized by elemental analyses, IR, UV–visible and NMR spectroscopy. Crystal structure of [Co(phendione)₂Cl₂]Cl·0.5HCl·3.5H₂O has been solved and refined to R=0.0552. The crystal is monoclinic with space group C₂/c; a=25.730(2)Å, b=12.375(1)Å, c=18.979(2)Å, β=119.925(1)° and Z=8. The DNA binding characteristics of the complexes, investigated by covalent binding assay, viscosity measurements and competitive binding fluorescence measurements show that the complexes interact with DNA covalently except the complex containing the planar dppz ligand which intercalates within the base pairs of DNA. The complexes containing en, phen and …