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• W2950871454 abstract "Thallium sesquibromide Tl2Br3 is dimorphic. Scarlet coloured crystals of α-Tl2Br3 were obtained by reactions of aqueous solutions of TlBr3 and Tl2SO4 in agarose gel. In case of rapid crystallisation of hydrous TlBr3/TlBr solutions and from TlBr/TlBr2 melts ß-Tl2Br3 is formed as scarlet coloured, extremely thin lamellae. The crystal structures of both forms are very similar and can be described as mixed-valence thallium(I)-hexabromothallates(III) Tl3[TlBr6]. In the monoclinic unit cell of α-Tl3[TlBr6] (a = 26.763(7) Å; b = 15.311(6) Å; c = 27.375(6) Å; β = 108.63(2)°, Z = 32, space gr. C2/c) the 32 TlIII-cations are found in strongly distorted octahedral TlBr6 groups. The 96 TlI cations are surrounded either by four or six TlBr6 groups with contacts to 8 or 9 Br neighbors. Crystals of β-Tl3[TlBr6] by contrast show almost hexagonal metrics (a = 13.124(4) Å, b = 13.130(4) Å, c = 25.550(7) Å, γ = 119.91(9)°, Z = 12, P21/m). Refinements of the parameters revealed structural disorder of TlBr6 units, possibly resulting from multiple twinning. Both structures are composed of Tl2[TlBr6]— and Tl4[TlBr6]+ multilayers, which alternate parallel (001). The structural relationships of the complicated structures of α- and β-Tl3[TlBr6] to the three polymorphous forms of Tl2Cl3 as well as to the structures of monoclinic hexachlorothallates M3TlCl6 (M = K, Rb) and the cubic elpasolites are discussed. Gemischtvalente Thallium(I, III)-bromide. Die Kristallstruktur von α—Tl2Br3 Thalliumsesquibromid Tl2Br3 ist dimorph. Dunkelrote Kristallblättchen von α-Tl2Br3 wurden durch Umsetzungen von wässrigen Tl2SO4/TlBr3-Lösungen in Agarose-Gel erhalten. β-Tl2Br3 entsteht in Form extrem dünner, roter Lamellen bei raschen Kristallisationen aus wässrigen TlBr/TlBr3-Lösungen oder TlBr/TlBr2-Schmelzen. Beide Formen besitzen einen ähnlichen Aufbau; sie sind als gemischtvalente Thallium(I)-hexabromothallate(III) Tl3[TlBr6] zu beschreiben. In der monoklinen Elementarzelle von α-Tl2Br3 (a = 26, 763(7) Å; b = 15, 311(6) Å; c = 27, 375(6) Å; β = 108, 63(2)°, Z = 32, Raumgruppe C2/c) sind 32 TlIII-Kationen in stark verzerrten, oktaedrischen TlBr6-Baugruppen enthalten. Die 96 TlI-Kationen sind von vier oder sechs TlBr6-Baugruppen umgeben und bilden Kontakte zu 8 oder 9 Br-Nachbarn aus. Bei Kristallen von β-Tl2Br3 wurde eine monokline Zelle mit nahezu exakt hexagonaler Metrik gefunden (a = 13.124(4) Å, b = 13.130 (4) Å , c = 25.550(7) Å, γ = 119.91(9)°, Z = 12, Raumgruppe P21/m). Die Verfeinerungen der Parameter ergaben strukturelle Fehlordnungen für TlBr6-Baugruppen, was auf das Vorliegen von Viellingen zurückgeführt wird. Beide Strukturen sind aus Schichtpaketen Tl2[TlBr6]— und Tl4[TlBr6]+ aufgebaut, die alternierend parallel (001) verlaufen. Die strukturellen Verwandtschaftsbeziehungen der komplizierten Strukturen von α- und β-Tl3[TlBr6] zu den drei polymorphen Formen von Tl2Cl3 sowie zum Aufbau der monoklinen Hexachlorothallate A3TlCl6 (A = K, Rb) und zum kubischen Elpasolith-Typ werden diskutiert." @default.
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• W2950871454 date "2002-12-01" @default.
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• W2950871454 title "Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3" @default.
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• W2950871454 doi "https://doi.org/10.1002/1521-3749(200212)628:12<2675::aid-zaac2675>3.0.co;2-4" @default.
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