Coordination complexes of thallium (III) chloride

X-ray crystal structures are reported for two coordination complexes of thallium(III) chloride. In the neutral, monomeric complex [TlCl3(dmpu)(2)] (dmpu = N,N'-dimethylpropylene urea), the coordination geometry around the thallium centre is essentially trigonal bipyramidal with equatorial chlorines and axial dmpu ligands similar to a number of other bis-ligand complexes previously characterised; crystal data, orthorhombic, space group Fdd2, a = 17.632(2), b = 27.257(3), c = 8.0353(9) Angstrom, D-calc = 1.951 Mg/m(3), R = 0.028. With the chelating ligand dppmO(2) (Ph2P(O)CH2P(O)Ph-2), the ionic compound [TlCl2(dppmO(2))(2)] [TlCl4].2thf is obtained, which comprises an octahedrally coordinated thallium cation with trans chlorines and a tetrahedral [TlCl4](-) anion; crystal data, triclinic, space group P (1) over bar, a = 10.7067(9), b = 16.190(2), c = 19.114(2) Angstrom, alpha = 103.55(1), beta = 93.710 (8), gamma = 95.98(1)degrees, D-calc = 1.664 Mg/m(3), R = 0.090.