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Phosphorus Oligomerization in Zintl Phases: Synthesis, Crystal Structure, and Bonding Analysis of Mixed Alkali and Alkaline‐Earth Metal Phosphides
Author(s) -
Derrien G.,
Tillard M.,
Manteghetti A.,
Belin C.
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300086
Subject(s) - phosphide , crystallography , orthorhombic crystal system , tetragonal crystal system , crystal structure , ionic radius , valence (chemistry) , alkali metal , chemistry , valence electron , alkaline earth metal , ionic bonding , metal , ion , electron , physics , organic chemistry , quantum mechanics
Pnictides α‐Ba 5 P 4 and KBa 4 P 5 were prepared by melting the elements. The α‐Ba 5 P 4 compound crystallizes in the orthorhombic system (Sm 5 Ge 4 ‐type), space group Pnma, Z = 4, a = 8.330(3), b = 16.503(3), c = 8.405(2)Å, it contains two anionic species : P 2 4— dumbbells and P 3— . The KBa 4 P 5 compound crystallizes in the tetragonal system, space group P4 3 2 1 2, Z = 4, a = 8.559(1), c = 16.102(2)Å, it contains trimers P 3 5— and dumbbells P 2 4— . The crystal structures were solved from single crystal X‐ray data and refined by full‐matrix least‐squares to agreement factors R1 = 0.047 and 0.038, respectively. Using ionic charges, α‐Ba 5 P 4 is formulated as [5Ba 2+ , 2P 3— , P 2 4— ] and KBa 4 P 5 as [K + , 4Ba 2+ , P 2 4— , P 3 5— ]. The level of oligomerisation in these structures depends upon the overall valence electron content, bonding within the anionic oligomers has been analyzed on the basis of EHMO calculations and compared to classical or hypervalent bonding in other phosphide compounds.