Relation between tetrahedron connections and composition for structures with tetrahedral anion complexes

Parthé, E.; Engel, N.

doi:10.1107/s0108768186097732

Cited by 12 publications

(24 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The classical book of Liebau (1985) on silicates and that of Durif (1995) on phosphates provides proof of the efforts made by numerous scientists to classify, and further understand, these apparent 'capricious networks' that are observed in these families of compounds. Also worthy of mention in this context are the works of Parthé and co-workers (Parthé & Engel, 1986;Parthé & Chabot, 1990) who also sought to provide a general classification of all the known types of tetrahedral structures. These authors realised that the Zintl-Klemm concept was embodied in those compounds and they tried to The structure of (NH 4 ) 2 Ge [6] [Ge [4] 6 O 15 ] projected onto the ab plane showing the Ge-O network formed by Ge [4] (yellow spheres) and O atoms (small red spheres).…”

Section: Introductionmentioning

confidence: 99%

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

Vegas

Jenkins

2017

Acta Crystallogr B Struct Sci Cryst Eng Mater

View full text Add to dashboard Cite

The structure of (NH4)2Ge7O15 recently described as being a microporous material containing rings, in which GeO6 octahedra coexist with GeO4 tetrahedra, is re-examined in the light of the Extended Zintl–Klemm Concept as applied to cations in oxides. The Ge[6] atoms together with the NH4 + groups act as true cations, transferring their 6 valence electrons to the acceptor Ge2O5 moiety, so converting it into the [Ge6O15]6−[triple-bond]3(Ψ-As2O5) ion (where Ψ refers to a pseudo-lattice) and yielding threefold connectivity. The tetrahedral Ge network shows similarities with the Sb2O3 analogue. At the same time, the Ge[6] atoms are connected to other Ge[4] atoms forming blocks that are part of a rutile-type GeO2 structure. Such an analysis shows that both substructures (the Zintl polyanion and the rutile fragments) must be satisfied simultaneously as has already been illustrated in previous articles which considered stuffed-bixbyites [Vegas et al. (2009). Acta Cryst. B65, 11–21] as well as the compound FeLiPO4 [Vegas (2011). Struct. Bond. 138, 67–91]. This new insight conforms well to previous (differential thermal analysis) DTA–TGA (thermogravimetric analysis) experiments [Cascales et al. (1998). Angew. Chem. Int. Ed. 37, 129–131], which show endothermic loss of NH3 and H2O to give rise to the metastable structure Ge7O14, which further collapses to the rutile-type GeO2 structure. We analyze the stability change in terms of ionic strength, I, and so provide a means of rationalizing the driving force behind this concept capable of explaining the atomic arrangements found in these types of crystal structures. Although the concept was formulated in 2003, later than the publication of the germanate structure, it was not used or else ignored by colleagues who solved this crystal structure.

show abstract

Section: Introductionmentioning

confidence: 99%

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

Vegas

Jenkins

2017

Acta Crystallogr B Struct Sci Cryst Eng Mater

View full text Add to dashboard Cite

show abstract

“…Beginning with the attempts of Parthé & Engel (1986) and Parthé & Chabot (1990) and extending to the works devoted to aluminates and silicates by Santamaría-Pé rez & Vegas (2003) and Santamaría-Pé rez et al (2005), the polyanions of these p-block elements can be rationalized when they are regarded as being true Zintl polyanions. Fig.…”

Section: Discussionmentioning

confidence: 99%

An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb₁₀[Si₆O₁₇], Cs₈[Si₆O₁₆] and Na₃Y[Si₆O₁₅] by viewing them in light of the extended Zintl–Klemm concept

Vegas

2013

Acta Crystallogr Sect B

View full text Add to dashboard Cite

The structures of the three dimeric cyclotrisilicate anions [Si6O17](10-), [Si6O16](8-) and [Si6O15](6-) forming part of the compounds Rb10[Si6O17] or Rb14[Si4][Si6O17], Cs8[Si6O16] and Na3Y[Si6O15], respectively, have been described as different ways of condensing the more elemental cyclotrisilicate anions [Si3O9](6-) [Hlukhyy & Fässler (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 Ψ-S/Ψ-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 [Ψ-S4P2](10-), [Ψ-S2P4](8-) and [Ψ-P6](6-) respectively.

show abstract

“…The average number N a of common Ο at Si satisfies 4m' -n = m'NJl (Coda, 1969). The Si0 2 .h 2 structure may be interpreted by the electron pair model (Parthe, Engel, 1986) or by the correlations model (Schubert, 1950(Schubert, , 1964(Schubert, , 1988; see also above: Lacuna homeotypes). However, the real problem is, which phases are stabilized on the Lewis quasi binary section and how the complex anions are packed together.…”

Section: Filling Homeotypes Of Simentioning

confidence: 99%

On some homeotypes of Si

Schubert¹

1990

Zeitschrift Für Kristallographie - Crystalline Materials

View full text Add to dashboard Cite

In the class of homeotypes of Si the model of electron pair bonds explains some phenomena such as the stability of Grimm-Sommerfeld phases. Similar explanations follow also from the model of electron spatial correlations. However, there are various phenomena, not explained so far by the pair model, but well interpreted by the correlations model, for instance stacking homeotypes of ZnS.r such as A1N. The correlations model has a more extended range because it considers more parameters than the pair model. A bonding type of the correlations model does not only classify the valence electron state but also properties of the core electron states. The bonding types based on the correlations model frequently lead to interesting experimental questions. Brought to you by | provisional account Unauthenticated Download Date | 6/26/15 12:56 PM Brought to you by | provisional account Unauthenticated Download Date | 6/26/15 12:56 PM Some homeotypes of Si 163promoted in the pair model because this model considers in first line the spin compensation and not the spatial correlation. The spins are already compensated in the lower bands and therefore these bands were of less interest. In the pair model the bond was something that tied the atoms together while in the correlations model the bond must be considered as a soft solid angle where global tensions cause an increased approach of the atoms. The short distances are generated by a global bonding (the correlation) because there are soft angles.Less serious differences in the nomenclature of the models may be bridged by the following correspondences.Normal adamantine structures (Pamplin, 1960;Goryunova, 1963): Stacking homeotypes of ZnS.r, briefly ShtpZnS.r. The set of S-homeotypisms should contain the 1-homeotypism (identical homeotypism) to ensure that the isotypes of ZnS.r are contained in ShtpZnS.r.Defect adamantine structures: L'ShtpZnS.r. The prime reminds to the conservation of N(, a .Normal tetrahedral structures (Goryunova 1963, Parthe 1964): R'ShtpSi.Defect tetrahedral structures: R'L'ShtpSi. Normal valence phases (Mooser, Pearson, 1959): Phases with N[ Xa = 8, An = anion, Lewis phases. The essential feature of Lewis phases is seen in their electron spin compensation, i.e. in the phenomenon that a +spin is surrounded mostly by -spins, but non-Lewis phases may have also spin compensation. Consequently, the name "normal valence phase" is not quite fortunate, the non Lewis phases are just as normal as the Lewis-phases.Polycationic phases (Pearson, 1964): Phases with Ni Aa >8, over-completed phases. There must be non-Lewis spin compensation, i.e. spin compensation between cations, and this causes smaller distances between cations, like as in the 8-Nl M = MmLn dist. rule of Hume-Rothery. The acceptable concept "polycationic phase" should not be interpreted by electron pair bonds, because also here these bonds imply a local spatial correlation, possibly contradicting to the overall spatial correlation. By the way, the concept is not appropriate for instance for the mixture Li...

show abstract

Relation between tetrahedron connections and composition for structures with tetrahedral anion complexes

Cited by 12 publications

References 3 publications

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb₁₀[Si₆O₁₇], Cs₈[Si₆O₁₆] and Na₃Y[Si₆O₁₅] by viewing them in light of the extended Zintl–Klemm concept

On some homeotypes of Si

Contact Info

Product

Resources

About

Relation between tetrahedron connections and composition for structures with tetrahedral anion complexes

Cited by 12 publications

References 3 publications

A revised interpretation of the structure of (NH4)2Ge7O15 in the light of the Extended Zintl–Klemm Concept

A revised interpretation of the structure of (NH4)2Ge7O15 in the light of the Extended Zintl–Klemm Concept

An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb10[Si6O17], Cs8[Si6O16] and Na3Y[Si6O15] by viewing them in light of the extended Zintl–Klemm concept

On some homeotypes of Si

Contact Info

Product

Resources

About

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

A revised interpretation of the structure of (NH₄)₂Ge₇O₁₅ in the light of the Extended Zintl–Klemm Concept

An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb₁₀[Si₆O₁₇], Cs₈[Si₆O₁₆] and Na₃Y[Si₆O₁₅] by viewing them in light of the extended Zintl–Klemm concept