New barium antimonide oxides containing zintl ions [Sb](3-), [Sb-2](4-), and (1)(infinity)[Sb-n](n-)

A new kind of chiral chains (1)(infinity)[Sb-n](n-) and O2- ions tetrahedrally coordinated by Ba are the characteristic anions in Ba-3[Sb-4][O] (monoclinic, space group P2(1)/c, a = 696.4(2), b = 1280.7(3), c = 1294.1(3) pm, beta = 112.39(1)degrees, Z = 4, R1 = 0.0399). Similarly, in RbBa4[Sb-2][Sb][O], that crystallizes isotypic with KBa4[Sb-2][Sb][O] (stuffed Cr5B3-Typ, tetragonal, space group I4/mcm, a = 893.7(4), c = 1642.7(9) pm, Z = 4, R1 = 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 I4/mmm, a = 515.34(12)/519.12(12), c = 3791.7(3)/3837.6(3) pm, Z = 4, R1 = 0.0319/0.0460) and Rb2Ba6[Sb-2](2)[Sb][O][H] (tetragonal, space group I4/mcm, a = 879.71(4), c = 2742.4(2) pm, Z = 4, R1 = 0.0592) can be structurally derived from the oxides Ba4Sb2O and RbBa4[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 Sb2O3/Bi2O3, BaH2 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.