Reaction of dimethylhydroxythallium(III) with 2-thioorotic acid. Crystal structure of dimethyl(2-thioorotato)thallium(III) monohydrate

Abstract

Reacting 2-thioorotic acid (H 3Tot) and its monosodium salt with dimethylthallium(III) hydroxide yielded the compounds TlMe 2H 2Tot·H 2O and (TlMe 2) 2HTot·2H 2O, respectively. The monometallated compound crystallizes in the P2 1/ n space group with a=9.539(4), b=10.725(3), c=10.892(3) Å, β=94.55(3)° and Z=4. The thallium atom is bonded to the methyl carbons and to one of the oxygens of the carboxylate group of a ligand molecule, and forms further weak bonds with a carbonylic oxygen, a carboxylic oxygen and a thiocarbonylic sulfur of other ligands, as well as with the oxygen of a water molecule. The coordination polyhedron about the thallium atom is a deformed pentagonal bipyramid with the methyl groups in the axial positions. In DMSO solution the compound behaves as a 1:1 electrolyte and the ligand signals of its 1H and 13C NMR spectra are analogous to those of NaH 2Tot. The coordination characteristics of (TlMe 2) 2HTot·2H 2O are compared with those of the monometallated compound on the basis of spectroscopic properties in the solid state (IR and Raman) and in solution ( 1H and 13C NMR).