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Lorenz, Corinna ; Gärtner, Stefanie ; Korber, Nikolaus

Ammoniates of Zintl phases: Similarities and differences of binary phases A4E4 and their corresponding solvates

Lorenz, Corinna , Gärtner, Stefanie and Korber, Nikolaus (2018) Ammoniates of Zintl phases: Similarities and differences of binary phases A4E4 and their corresponding solvates. Crystals 8, p. 276.

Date of publication of this fulltext: 29 Aug 2018 13:16
Article
DOI to cite this document: 10.5283/epub.37615


Abstract

The combination of electropositive alkali metals A (A = Na-Cs) and group 14 elements E (E = Si-Pb) in a stoichiometric ratio of 1:1 in solid state reactions results in the formation of polyanionic salts, which belong to a class of intermetallics for which the term Zintl compounds is used. Crystal structure analysis of these intermetallic phases proved the presence of tetrahedral tetrelide ...

The combination of electropositive alkali metals A (A = Na-Cs) and group 14 elements E (E = Si-Pb) in a stoichiometric ratio of 1:1 in solid state reactions results in the formation of polyanionic salts, which belong to a class of intermetallics for which the term Zintl compounds is used. Crystal structure analysis of these intermetallic phases proved the presence of tetrahedral tetrelide tetraanions [E-4](4-) precast in solid state, and coulombic interactions account for the formation of a dense, three-dimensional cation-anion network. In addition, it has been shown that [E-4](4-) polyanions are also present in solutions of liquid ammonia prepared via different synthetic routes. From these solutions crystallize ammoniates of the alkali metal tetrahedranides, which contain ammonia molecules of crystallization, and which can be characterized by X-ray crystallography despite their low thermal stability. The question to be answered is about the structural relations between the analogous compounds in solid state vs. solvate structures, which all include the tetrahedral [E-4](4-) anions. We here investigate the similarities and differences regarding the coordination spheres of these anions and the resulting cation-anion network. The reported solvates Na(4)Sn(4)13NH(3), Rb4Sn4 center dot 2NH(3), Cs4Sn4 center dot 2NH(3), Rb4Pb4 center dot 2NH(3) as well as the up to now unpublished crystal structures of the new compounds Cs4Si4 center dot 7NH(3), Cs4Ge4 center dot 9NH(3), [Li(NH3)(4)](4)Sn-4 center dot 4NH(3), Na4Sn4 center dot 11.5NH(3) and Cs4Pb4 center dot 5NH(3) are considered for comparisons. Additionally, the influence of the presence of another anion on the overall crystal structure is discussed by using the example of a hydroxide co-crystal which was observed in the new compound K4.5Sn4(OH)(0.5)center dot 1.75 NH3.



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Details

Item typeArticle
Journal or Publication TitleCrystals
Publisher:MDPI
Place of Publication:BASEL
Volume:8
Page Range:p. 276
Date29 June 2018
InstitutionsChemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Nikolaus Korber
Identification Number
ValueType
10.3390/cryst8070276DOI
KeywordsALKALIMETALLE ZU HALBMETALLEN; CRYSTAL-STRUCTURE; DAS VERHALTEN; TETRAHEDRO-TETRASTANNIDE; LIQUID-AMMONIA; ANIONS; REFINEMENT; TETRASILICIDE; SN-4(4-); CLUSTERS; Zintl compounds; liquid ammonia; crystal structure
Dewey Decimal Classification500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgYes
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-376159
Item ID37615

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