Lorenz, Corinna and Gaertner, Stefanie and Korber, Nikolaus (2018) Ammoniates of Zintl Phases: Similarities and Differences of Binary Phases A(4)E(4) and Their Corresponding Solvates. CRYSTALS, 8 (7): 276. ISSN 2073-4352,
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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Rb4Sn4 center dot 2NH(3), Cs4Sn4 center dot 2NH(3), Rb4Pb4 center dot 2NH(3) as well as the up to now unpublished crystal structures of the new compounds Cs4Si4 center dot 7NH(3), Cs4Ge4 center dot 9NH(3), [Li(NH3)(4)](4)Sn-4 center dot 4NH(3), Na4Sn4 center dot 11.5NH(3)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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ALKALIMETALLE ZU HALBMETALLEN; CRYSTAL-STRUCTURE; DAS VERHALTEN; TETRAHEDRO-TETRASTANNIDE; LIQUID-AMMONIA; ANIONS; REFINEMENT; TETRASILICIDE; SN-4(4-); CLUSTERS; Zintl compounds; liquid ammonia; crystal structure |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Nikolaus Korber |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Mar 2020 08:09 |
| Last Modified: | 09 Mar 2020 08:09 |
| URI: | https://pred.uni-regensburg.de/id/eprint/14320 |
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