Die Perthioborate RbBS3, TIBS3 und TI3B3S10†

TLDR: In this article, Farblose et al. present a sample of the composition Tl2S · 2 B2S3, which is isotypic with RbBS3.

Abstract: Farblose, plattchenformige Kristalle von RbBS3 (P21/c, a=7,082(2) A, b=11,863(4) A, c=5,794(2) A, β=106,54(2)°) entstehen aus einem stochiometrischen Ansatz von Rubidiumsulfid, Bor und Schwefel bei 600°C und anschliesendem Tempern. Die zu RbBS3 isotype Phase TlBS3 (P21/c, a=6,874(3) A, b=11,739(3) A, c=5,775(2) A, β=113,08(2)°) erhalt man aus dem Ansatz Tl2S · 2 B2S3. Das nach 7 h bei 850°C erhaltene glasige Produkt wird in einem Zweizonenofen 400 h bei 400350°C ausgelagert. Gelbe Kristalle der Verbindung bilden sich in der warmeren Ofenzone. Das ebenfalls gelbe Tl3B3S10 (P1, a=6,828(2) A, b=7,713(2) A, c=13,769(5) A, α=104,32(2)°, β=94,03(3)β, γ=94,69(2)°) bildet sich aus stochiometrischen Mengen von Thalliumsulfid, Bor und Schwefel bei 850°C und anschliesendem Tempern. Die ausschlieslich tetraedrisch koordiniertes Bor enthaltenden Verbindungen bilden polymere Kettenstrukturen, die sich im Fall des RbBS3 und TlBS3 aus spirocyclisch uber die Boratome verknupften, nichtplanaren Trithiadiborolan-Ringen aufbauen. Ersetzt man in diesen Anionenketten jeden dritten B2S3-Funfring durch einen B(S2)2B-Sechsring, so erhalt man die Anionenstruktur des Tl3B3S10. The Perthioborates RbBS3, TIBS3, and Tl3B3S10. RbBS3 (P21/c, a=7.082(2) A, b=11.863(4) A, c=5.794(2) A, β=106.54(2)°) was prepared as colourless, plate-shaped crystals by reaction of stoichiometric amounts of rubidium sulfide, boron, and sulfur at 600°C and subsequent annealing. TlBS3 (P21/c, a=6.874(3) A, b=11.739(3) A, c=5.775(2) A, β=113.08(2)°) which is isotypic with RbBS3 was synthesized from a sample of the composition Tl2S · 2 B2S3. The glassy product which was obtained after 7 h at 850°C was annealed in a two zone furnace for 400 h at 400350°C. Yellow crystals of TlBS3 formed at the warmer side of the furnace. Tl3B3S10 (P1, a=6.828(2) A, b=7.713(2) A, c=13.769(5) A, α=104.32(2)°, β=94.03(3)°, γ=94.69(2)°) was prepared as yellow plates from stoichiometric amounts of thallium sulfide, boron, and sulfur at 850°C and subsequent annealing. All compounds contain tetrahedrally coordinated boron. The crystal structures consist of polymeric anion chains. In the case of RbBS3 and TlBS3 nonplanar five-membered B2S3 rings are spirocyclically connected via the boron atoms. To obtain the anionic structure of Tl3B3S10 every third B2S3 ring of the polymeric chains of MBS3 is to be substituted by a six-membered B(S2)2B ring.