Über zwei Modifikationen von "Tl₂Cl₃"-valenzgemischten Thallium(I)-hexahalogenothallaten(III) Tl₃ [TlCl₆] / On Two Modifications of "Tl₂Cl₃"-Mixed Valence Thallium(I)-hexahalogenothallates(III)

Abstract

<jats:p>The mixed valence thallium chloride "Tl<jats:sub>2</jats:sub>Cl<jats:sub>3</jats:sub>" is polymorphous. Raman spectra and comparable lattice translations suggest similar structures of both modifications. </jats:p><jats:p>The crystal structure of the rhombic α-Tl<jats:sub>2</jats:sub>Cl<jats:sub>3</jats:sub> 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) Tl<jats:sub>3</jats:sub>[TlCl<jats:sub>6</jats:sub>] 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.</jats:p><jats:p>β-Tl<jats:sub>3</jats:sub>[TlCl<jats:sub>6</jats:sub>] 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°.</jats:p>

New thallium iodates—Synthesis, characterization, and calculations of Tl(IO3)3 and Tl4(IO3)6, [Tl+3Tl3+(IO3)6]

“…With respect to mixed-valent thallium compounds, i.e. those that contain Tl + and Tl 3 + , a few compounds have been reported, for example Tl 2 (CrO 4 ) 2 [16], Tl 4 O 3 [17], TlCl 1.805 Br 0.915 [18], Tl 2 Cl 4 [19], TlPd 3 O 4 [20], Tl 2 Cl 3 [21], Tl 3 (OH)(SO 4 ) 2 [22] [27], and Tl 2 Br 3 [28]. Of these Tl 2 (CrO 4 ) 2 , Tl 3 (OH) (SO 4 ) 2 , and Tl 4 O 3 are of particular relevance to our work, since the materials have a crystallographically unique Tl + and Tl 3 + sites.…”

Crystal chemistry of complex indium(III) and other M(III) halides, with a discussion of M—Cl bond lengths in complex M(III) chlorides and of the structures of and hydrogen bonding in (NH4)2[InCl5(H2O)], K3InCl6•nH2O, (MeNH3)4[InCl6]Cl, and (Me2NH2)4[InCl6]Cl

“…At the same time, the volume V, per formula unit of the hydrate should not be smaller than the V1 of anhydrous K31nC16. We also know, from comparison with In31nC16 and Tl3T1Cl6 (14,65), that V1(K31nC16) must be of the order of 290 .A3. This indicates that for the anhydrous low-temperature phases Z = 8, i.e.…”

“…The literature statements concerning A31nC16 (A = K, Rb, Cs, NH,) require a more detailed comment and are discussed separately below. The orthorhombic, pseudotrigonal In2C13 (Pnma, Z = 32) is essentially In3[InC16] (14), isostructural with a-TI3[T1Cl6] (65).…”

Fehlordnung von Kationen und Kristallwasser bei kubischen Alkalitetrabromo- und -iodothallaten(III)/Disorder of Cations and Water Molecules in Cubic Tetrabromo- and -iodothallates

“…• nH20 die Anionen TlCljj-, T12C1IO 2 " oder TlCl5(OH2) 2~ mit oktaedrisch koordiniertem Thallium auf [6,7,9]. Bei Bromo-und Iodothallaten sollte auf Grund der stärkeren kovalenten Bindungsanteile die Ausbildung von tetraedrischen Baugruppen bevorzugt sein.…”

“…In vorausgegangenen Arbeiten untersuchten wir das Koordinationsverhalten des d 10 -Kations Thallium(III) in Chlorothallaten [1][2][3][4][5][6][7][8][9]. Während bei den im tetragonalen Scheelittyp kristallisierenden, wasserfreien Tetrachlorothallaten MT1C14 (M = K, Rb, NH4, TI) [4,5] und in gemischten Tetrachlorobromothallaten [3] tetraedrische Anionen gefunden wurden, treten bei Hexachlorothallaten M3TICI6 und kristallwasserhaltigen Pentachlorothallaten…”