Über Cs2TlBr5 – ein Pentabromothallat (III) mit tetraedrischen TlBr4− ‐ und oktaedrischen TlBr63− ‐Anionen

Zimmermann, Klaus; Thiele, G.

doi:10.1002/zaac.19875531032

Cited by 6 publications

(4 citation statements)

References 11 publications

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“…The realised spacesaving integration of the TlBr 6 octahedra into the Tl I 14 -polyhedra results inevitably in rather short Tl I ϪBr distances and as a consequence of this in more intense distortions of the TlBr 6 anions. Albeit, as mentioned above, in case of Cs 2 TlBr 5 and Cs 3 Tl 2 Br 9 [12,14] intensely deformed TlBr 6 groups were detected with distortions even drastically, and Z. Anorg. Allg.…”

Section: Structure Description For α-Tl 2 Brmentioning

confidence: 60%

“…From the solutions, the hydrates TlX 3 ·4H 2 O [10], or in the presence of suitable counter cations halogenothallates(III) can be crystallised. Thus numerous halogenothallates(III) that contain univalent cations of the alkali metals were synthesised and characterised, besides the tetrahalogeno-and hexahalogenothallates(III), in particular those of the type A 2 [TlX 5 ] [11,12] and A 3 [Tl 2 X 9 ] [13,14]. The corresponding mixed-valence thallium halides Tl 3 X 5 ϭ Tl I 2 [TlX 5 ] and Tl 5 X 9 ϭ Tl I 3 [Tl 2 X 9 ] are unknown yet.…”

Section: Introductionmentioning

confidence: 99%

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Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Ackermann

Hirschle

Rotter

et al. 2002

Z. anorg. allg. Chem.

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Thallium sesquibromide Tl 2 Br 3 is dimorphic. Scarlet coloured crystals of α-Tl 2 Br 3 were obtained by reactions of aqueous solutions of TlBr 3 and Tl 2 SO 4 in agarose gel. In case of rapid crystallisation of hydrous TlBr 3 /TlBr solutions and from TlBr/TlBr 2 melts ß-Tl 2 Br 3 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) Tl 3 [TlBr 6 ]. In the monoclinic unit cell of α-Tl 3 [TlBr 6 ] (a ϭ 26.763(7) Å ; b ϭ 15.311(6) Å ; c ϭ 27.375(6) Å ; ß ϭ 108.63(2)°, Z ϭ 32, space gr. C2/c) the 32 Tl III -cations are found in strongly distorted octahedral TlBr 6 groups. The 96 Tl I cations are surrounded either by four or six TlBr 6 groups with contacts to 8 or 9 Br neighbors. Crystals of ß-Tl 3 [TlBr 6 ] by contrast show almost hexagonal metrics Gemischtvalente Thallium(I,III)-bromide. Die Kristallstruktur von α-Tl 2 Br 3InhaltsübersichtThalliumsesquibromid Tl 2 Br 3 ist dimorph. Dunkelrote Kristallblättchen von α-Tl 2 Br 3 wurden durch Umsetzungen von wässrigen Tl 2 SO 4 /TlBr 3 -Lösungen in Agarose-Gel erhalten. β-Tl 2 Br 3 entsteht in Form extrem dünner, roter Lamellen bei raschen Kristallisationen aus wässrigen TlBr/TlBr 3 -Lösungen oder TlBr/ TlBr 2 -Schmelzen. Beide Formen besitzen einen ähnlichen Aufbau; sie sind als gemischtvalente Thallium(I)-hexabromothallate(III) Tl 3 [TlBr 6 ] zu beschreiben. In der monoklinen Elementarzelle von α-Tl 2 Br 3 (a ϭ 26,763(7) Å ; b ϭ 15,311(6) Å ; c ϭ 27,375(6) Å ; β ϭ 108,63(2)°, Z ϭ 32, Raumgruppe C2/c) sind 32 Tl III -Kationen in stark verzerrten, oktaedrischen TlBr 6 -Baugruppen enthalten. Die 96 Tl I -Kationen sind von vier oder sechs TlBr 6 -Baugruppen umgeben und bilden Kontakte zu 8 oder 9 Br-Nachbarn aus. 2675(a ϭ 13.124(4) Å , b ϭ 13.130(4) Å , c ϭ 25.550(7) Å , γ ϭ 119.91(9)°, Z ϭ 12, P2 1 /m). Refinements of the parameters revealed structural disorder of TlBr 6 units, possibly resulting from multiple twinning. Both structures are composed of Tl 2 [TlBr 6 ] Ϫ and Tl 4 [TlBr 6 ] ϩ multilayers, which alternate parallel (001). The structural relationships of the complicated structures of α-and ß-Tl 3 [TlBr 6 ] to the three polymorphous forms of Tl 2 Cl 3 as well as to the structures of monoclinic hexachlorothallates M 3 TlCl 6 (M ϭ K,Rb) and the cubic elpasolites are discussed.

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Section: Structure Description For α-Tl 2 Brmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Ackermann

Hirschle

Rotter

et al. 2002

Z. anorg. allg. Chem.

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Section: Structure Description For α-Tl 2 Brmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mixed‐Valence Thallium(I,III) Bromides. The Crystal Structure of α‐Tl₂Br₃.

et al. 2003

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Structure Structure D 2000Mixed-Valence Thallium(I,III) Bromides. The Crystal Structure of α-Tl 2 Br 3 . -Single crystals of α-Tl 2 Br 3 are prepared by reaction of aq. solutions of TlBr 3 and Tl 2 SO 4 in agarose gel. β-Tl 2 Br 3 is obtained by rapid crystallization of aq. TlBr 3 /TlBr solutions or from TlBr/TlBr 2 melts. The structures of both modifications are very similar and can be described as mixed-valent thallium(I) hexabromothallates(III), Tl 3 [TlBr 6 ]. The α-Tl 3 [TlBr 6 ] modification crystallizes in the monoclinic space group C2/c with Z = 32, while the β-modification shows almost hexagonal metric (space group P2 1 /m, Z = 12). Both structures are composed of Tl 2 [TlBr 6 ]and Tl 4 [TlBr 6 ] + multilayers alternating parallel (001). -(ACKERMANN, R.; HIRSCHLE, C.; ROTTER, H. W.; THIELE*, G.; Z.

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ChemInform Abstract: Cs2TlBr5 ‐ a Pentabromothallate(III) with Tetrahedral TlBr4 ‐ and Octahedral TlBr3‐ 6 Anions.

Zimmermann¹,

Thiele²

1988

ChemInform

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ChemInform Abstract Addition of CsBr and HBr to an aqueous solution of TlBr3 yields Cs3Tl2Br9, which transforms within 1-2 d into Cs2TlBr5 (yield in g). The new compound crystallizes in the orthorhombic space group Pnma, Z = 8. The structure contains isolated tetrahedral TlBr4-and octahedral TlBr63-anions which are packed, together with Cs+, in an anti-CaWO4 arrangement. Cs2TlBr5 decomposes irreversibly to Cs3Tl2Br9 and CsBr at 260 rc C.

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Über Cs₂TlBr₅ – ein Pentabromothallat (III) mit tetraedrischen TlBr₄⁻ ‐ und oktaedrischen TlBr₆³⁻ ‐Anionen

Cited by 6 publications

References 11 publications

Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Mixed‐Valence Thallium(I,III) Bromides. The Crystal Structure of α‐Tl₂Br₃.

ChemInform Abstract: Cs2TlBr5 ‐ a Pentabromothallate(III) with Tetrahedral TlBr4 ‐ and Octahedral TlBr3‐ 6 Anions.

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Über Cs2TlBr5 – ein Pentabromothallat (III) mit tetraedrischen TlBr4− ‐ und oktaedrischen TlBr63− ‐Anionen

Cited by 6 publications

References 11 publications

Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3

Mixed‐Valence Thallium(I,III) Bromides. The Crystal Structure of α‐Tl2Br3.

ChemInform Abstract: Cs2TlBr5 ‐ a Pentabromothallate(III) with Tetrahedral TlBr4 ‐ and Octahedral TlBr3‐ 6 Anions.

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Über Cs₂TlBr₅ – ein Pentabromothallat (III) mit tetraedrischen TlBr₄⁻ ‐ und oktaedrischen TlBr₆³⁻ ‐Anionen

Mixed‐Valence Thallium(I,III) Bromides. The Crystal Structure of α‐Tl₂Br₃.