Stuffed diamond structure

The limitations of the simple Zintl-Klemm concept can be illustrated by differences in the two [MT1] intermetallics (M = Na [79] and Cs [80]). Complete electron transfer from M to T1 leads to [ M TI, where the Tl anion with four valence electrons is isoelectronic with a neutral group 14 atom and four bonds and needed to attain the octet configuration. Hence, the Tl- anion should form structures similar to allotropes of carbon or heavier group 14 elements. Indeed, [NaTl] has a stuffed diamond structure [79] with internal Na and an anionic (Tl-) lattice similar to diamond. However, the Tl- anions in [CsTl] form tetragonally compressed octahedra [80] unlike any structures of the allotropes of carbon or its heavier congeners. 

Further examples of formally subvalent main group compounds that contain element-element bonds but not necessarily clusters are the Zintl phases. The bonding in these has been described as the octet rule for all atoms . The archetypal Zintl compound is NaTl, in which charges are assigned as Na+ and Tl, representing a formal transfer of electrons from the more to the less electropositive element. The Tl ion can be considered to be a group 14 pseudoelement, and in fact exists in NaTl as a three-dimensional polyanionic diamond framework (TN) stuffed with Na+ cations. The Zintl concept is extended more broadly to other binary and ternary solid-state compounds, whose structures show the formation of element-element bonds in one, two, or three dimensions. ... 

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