An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb-10[Si6O17], Cs-8[Si6O16] and Na3Y[Si6O15] by viewing them in light of the extended Zintl-Klemm concept

作者：Vegas Angel^*

来源：Acta Crystallographica Section B-Structural Science, 2013, 69(4): 356-361.

DOI：10.1107/S2052519213013183

The structures of the three dimeric cyclotrisilicate anions [Si6O17](10-), [Si6O16](8-) and [Si6O15](6-) forming part of the compounds Rb-10[Si6O17] or Rb-14[Si-4][Si6O17], Cs-8[Si6O16] and Na3Y[Si6O15], respectively, have been described as different ways of condensing the more elemental cyclotrisilicate anions [Si3O9](6-) [Hlukhyy & Fassler (2013). Z. Anorg. Allg. Chem. 639, 231-233]. Such a description prevents a rational explanation of the connectivity between the Si atoms. So, in this article the Si skeletons of the above silicate anions are put on a common basis in light of the extended Zintl-Klemm concept. Their connectivity is directly related to the ratio Psi-S/Psi-P resulting from the number of electrons transferred from the electropositive Na, Y, Rb and Cs atoms, offering a new example of the fact that there exists a univocal link between chemical composition (in terms of pseudo-atoms) and structure: the generalized Zintl-Klemm concept. The three skeletons fit the connectivity of hypothetical Zintl polyanions of composition [Psi-S4P2](10-), [Psi-S2P4](8-) and [Psi-P-6](6-) respectively.

• 出版日期2013-8