Abstract: | The crystal structure of [Tl2(sac)2(H2O)]n (sac = saccharinate anion) has been solved using single crystal X‐ray diffraction. It crystallizes in the triclinic space group P 1 with Z = 2 and presents a polymeric structure formed by two saccharinate anions, one water molecule and two chemically different TlI cations, one 8‐coordinate and the other 5‐coordinate. Saccharinate shows an unprecedented coordination behavior as it acts as chelating ligand through its N and carbonyl O atoms with the N atom interacting simultaneously with both metal centers, and participation of sulphonyl oxygen atoms in bonding. The most important features of the IR spectrum of the complex are discussed on the basis of the structural peculiarities. |