Synthesis, spectroscopic and magnetic resonance studies of mercury (II) and methylmercury (II) complexes of azathioprine, a biologically active mercaptopurine derivative.

Synthetic and spectroscopic studies of the Hg(II) and MeHg(II) complexes of azathioprine (AZA), a biologically active 6-mercaptopurine derivative, were undertaken. The altered coordination behavior of AZA with respect to the parent mercaptopurine, with sulfur no longer being the primary donor atom, was confirmed. As concluded by the 1H NMR, 13C NMR, and IR spectroscopic data, Hg(II) binds to the N(9) position of deprotonated AZA, while in the MeHg(II) compound, coordination occurs through the N(3) and N(9) positions of the purine ring. The values of the coupling constants 2J (199Hg-1H), 1J(199Hg-13C) for the MeHg(II) compound further support complexation via nitrogen atoms of the purine. Elemental analyses confirmed the compounds to be Hg(AZA)2 (1) and [(MeHg)2(AZA)](NO3) (2); conductivity measurement values show that 1 is a nonelectrolyte and 2 is a 1:1 electrolyte. Furthermore, the FAB-MS of the compounds confirms direct binding of the metal to the ligand, and in the case of the MeHg(II) compound, the successive loss of one and two MeHg(II) moieties can be clearly observed.