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A Systematic Study on the Crystal Structures of TlMX 4 (M = Al, Ga; X = Cl, Br, I)
Author(s) -
Timofte Tudor,
Mudring AnjaVerena
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200801375
Subject(s) - crystallography , structure type , crystal structure , alkali metal , lone pair , thallium , gallate , chemistry , structural type , tetrahedron , type (biology) , materials science , inorganic chemistry , molecule , ecology , organic chemistry , biology , nuclear chemistry
TlAlCl 4 and TlGaCl 4 crystallize isotypic in the BaSO 4 structure type. Both, TlAlI 4 and TlGaI 4 crystallize isotypic in a distorted LiAlCl 4 structure type. In contrast to the tetrachloro and tetraiodo compounds, the tetrabromoaluminate and ‐gallate crystallize not isotypic with each other. TlAlBr 4 is found to crystallize isotypic with KAlBr 4 whilst TlGaBr 4 crystallizes in its own structure type. Despite the high diversity in structure types adopted by the studied TlMX 4 compounds, all of them can be regarded as distortions from the BaSO 4 structure type resulting from rotation of the MX 4 tetrahedra against each other. Because of this, low symmetry coordination environments around the thallium cation are generated. Comparison with isotypic alkali metal compounds shows that the strongly distorted thallium surroundings cannot be attributed to a stereochemical activity of the 6s 2 lone pair.