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Neue Barium‐Antimonid‐Oxide mit den Zintl‐Ionen [Sb] 3− , [Sb 2 ] 4− und ∞ 1 [Sb n ] n−
Author(s) -
Boss Michael,
Petri Denis,
Pickhard Frank,
Zönnchen Peter,
Röhr Caroline
Publication year - 2005
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.200400546
Subject(s) - crystallography , monoclinic crystal system , barium , tetragonal crystal system , antimony , antimonide , ion , chemistry , space group , hydride , crystal structure , x ray crystallography , metal , materials science , inorganic chemistry , physics , diffraction , organic chemistry , optics
New Barium Antimonide Oxides containing Zintl Ions [Sb] 3− , [Sb 2 ] 4− , and ∞ 1[Sb n ] n− A new kind of chiral chains ∞ 1 [Sb n ] n− and O 2− ions tetrahedrally coordinated by Ba are the characteristic anions in Ba 3 [Sb 4 ][O] (monoclinic, space group P 2 1 / c , a = 696.4(2), b = 1280.7(3), c = 1294.1(3) pm, β = 112.39(1)°, Z = 4, R 1 = 0.0399). Similarly, in RbBa 4 [Sb 2 ][Sb][O], that crystallizes isotypic with KBa 4 [Sb 2 ][Sb][O] (stuffed Cr 5 B 3 ‐Typ, tetragonal, space group I 4/ mcm , a = 893.7(4), c = 1642.7(9) pm, Z = 4, R 1 = 0.0508), the oxide ions occupy tetrahedral voids. The Zintl ions in this case are isolated [Sb] 3− anions and dumbbells [Sb 2 ] 4− respectively. The new hydrid‐oxides Ba 8 [M] 4 [O][H] 2 (M=Sb/Bi, tetragonal, space group I 4/ mmm , a = 515.34(12)/519.12(12), c = 3791.7(3)/3837.6(3) pm, Z = 4, R 1 = 0.0319/0.0460) and Rb 2 Ba 6 [Sb 2 ] 2 [Sb][O][H] (tetragonal, space group I 4/ mcm , a = 879.71(4), c = 2742.4(2) pm, Z = 4, R 1 = 0.0592) can be structurally derived from the oxides Ba 4 Sb 2 O and RbBa 4 [Sb 2 ][Sb][O] by intercalation (chemical twinning) of hydride antimonides. The synthesis of these air sensitive compounds exhibiting dark metallic luster was performed from melts of elemental Rb, Ba and Sb/Bi using Sb 2 O 3 /Bi 2 O 3 , BaH 2 and Ba(OH) 2 as sources for oxide/hydride. The detailed comparison of the structures and the results of FP‐LAPW band structure calculations show that the title compounds are electron precise Zintl phases with distinct band gaps.