Polytypism of Layered Alkaline Hydroxides: Crystal Structure of TlOH

Siidra, O. I., Britvin, S. N., Krivovichev, S. V. and Depmeier, W. (2010) Polytypism of Layered Alkaline Hydroxides: Crystal Structure of TlOH Zeitschrift Fur Anorganische Und Allgemeine Chemie, 636 (3-4). pp. 595-599. DOI 10.1002/zaac.200900367.

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The crystal structure of TlOH was solved by direct methods: monoclinic, space group C121, a = 5.949(2), b = 6.220(2), c = 21.232(6) angstrom, beta = 91.590(5)degrees, V = 785.3(4) angstrom(3), R(1) = 0.075 for 439 unique reflecTlons with vertical bar F(o)vertical bar > 4 sigma(F). There are four symmetrically independent Tl(+) caTlons and four oxygen atoms of OH(-) groups in the structure. Each of the OH(-) groups forms three short Tl(+)-O bonds thus forming OHTl(3) triangles, which, in turn, share common edges to form [OH(2)Tl(4)](2+) dimeric groups. These hydroxocentercd units are interconnected with each other through common corners into layers. The layers are posiTloned so that hydrogen bonds are formed between two OH anionic planes. The structure of TlOH is significantly more complicated than those of the AOH (A = Na, K, Rb, Cs) hydroxides. The appearance of such complexity is induced by the presence of the stereochemically acTlve lone electron pair on the Tl(+) caTlons. Structural distorTlons occur in order to minimize destabilizing interacTlons. The stacking sequence in layered AOH hydroxides may involve one (KOH, RbOH), two (NaOH, CsOH) and four (TlOH) layers per unit cell. This feature may be considered as a special case of chemically induced polytypism.

Document Type: Article
Keywords: Thallium Alkaline hydroxides Lone pairs Polytypism Solid-state structures Layered compounds chemistry
Research affiliation: Kiel University
DOI etc.: 10.1002/zaac.200900367
ISSN: 0044-2313
Date Deposited: 22 Dec 2011 05:57
Last Modified: 08 Oct 2012 10:00
URI: http://eprints.uni-kiel.de/id/eprint/15715

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