The mixed valence thallium chloride "Tl2Cl3" is polymorphous. Raman spectra and comparable lattice translations suggest similar structures of both modifications. The crystal structure of the rhombic α-Tl2Cl3 crystallizing in yellow, needle-shaped crystals, has been determined from three-dimensional X-ray diffraction data. The unit cell with cell parameters a= 1474.8(5) pm, b - 2508.7(6) pm and c = 1267.6(2) pm contains 16 formula units distributed on 24 independent atom positions. The compound is a mixed valence thallium(I)-hexachlorothallate(III) Tl3[TlCl6] because three of the nine independent Tl atoms are surrounded octahedrally by CI atoms in distances of 250-265 pm, while the other Tl atoms have seven, eight or nine CI neighbours variing between 306 and 383 pm.β-Tl3[TlCl6] forms pale yellow thin platelets and crystallizes monoclinic with cell parameters a = 2549.4(13) pm, 6 = 1469.9(8) pm, c = 1308.5(12) pm and β = 108.58°.

Abstract Tetrachlorothallates MTlCl4 (M=K, Rb and NH4) crystallizing in the tetragonal CaWO4 type were obtained by crystallization from highly concentrated aqueous TlCl3 solutions containing small amounts of MCI. The structural parameters of NH4TlCl4 were determined from single-crystal data. The indates MInCL4 (M=K, Rb and NH4) are isotypic. The vibrational spectra of the tetrachlorothallates were discussed.

Die Pentachlorothallate(III) K2TlCl5 · 2 H2O und M2TlCl5 · H2O (M = Rb, NH4) wurden durch Kristallisation aus wäßrigen Lösungen von TlCl3 und MCl erhalten. In der Kristallstruktur des monoklinen K2TlCl5 · 2 H2O sind dimere Anionen in Form von kantenverknüpften Tl2Cl10‐Doppeloktaeder enthalten. Die rhombischen Monohydrate sind isotyp mit Cs2[TlCl5(OH2)].

, die durch Umsetzung von festem TlCl mit wäßriger TlCl3‐Lösung (200 °C, 24 h) dargestellt werden.

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