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2005
Structure
D 2000
30- 008
New Barium Antimonide Oxides Containing Zintl Ions [Sb]3-, [Sb2]4-, and ∞1[Sbn]n-.
— The compounds Ba3Sb4O (I), RbBa4Sb3O (II), Ba8M4OH2 (M: Sb, Bi) (III), and
Rb2Ba 6Sb5OH (IV) are obtained from melts of elemental Rb, Ba and Sb/Bi using
Sb2O3/Bi2O3, BaH2 and Ba(OH) 2 as sources for oxide/hydride (argon, corundum crucible, ≤900 °C). The structures of these compounds are determined by single crystal
XRD. (I) crystallizes in the monoclinic space group P21/c with Z = 4 and contains a
new kind of chiral ∞1[Sbn]n- chains and O2- ions tetrahedrally coordinated by Ba. In (II)
(tetragonal, space group I4/mcm, Z = 4), also formulated as RbBa4[Sb2][Sb][O], the oxide ions also occupy tetrahedral voids, but the Zintl ions in this case are isolated [Sb]3anions and [Sb2]4- dumbbells. The new hydrid-oxides (III) (tetragonal, space group
I4/mmm, Z = 4) and (IV) (tetragonal, space group I4/mcm, Z = 4) can be structurally
derived from the oxides Ba4Sb2O and RbBa4[Sb 2][Sb][O] by intercalation (chemical
twinning) of hydride antimonides. 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. — (BOSS, M.; PETRI, D.;
PICKHARD, F.; ZOENNCHEN, P.; ROEHR*, C.; Z. Anorg. Allg. Chem. 631 (2005)
6-7, 1181-1190; Inst. Anorg. Anal. Chem., Albert-Ludwigs-Univ., D-79104 Freiburg/
Br., Germany; Ger., Abstr. Eng.) — Schramke
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