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°.

Trans‐[CoCl2(en)2] [TlCl4] kristallisiert monoklin in der Raum‐gruppe P21/m; die zwei Formeleinheiten enthaltende Elementarzelle besitzt die Abmessungen a = 6,431 Å, b = 19,11 Å, c = 6,472 Å und β = 90,0°. Die Struktur wird aus den isolierten Bausteinen des pseudooktraedrischen trans‐[CoCl2(en)2]⊕‐Kations und des leicht verzerrten tetraedrischen TlCl 4⊖‐Anions aufgebaut. Das TlCl4‐Anion besitzt die Punktsymmetrie Cs; es liegen annähernd gleichlange Tl–Cl‐Abstände (2,41 Å) vor.

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

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