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The new ternary alkali pentelides A 11 M 6  (A = Rb, Cs; M = Sb/Bi) all contain non electron-precise isolated dumbbells statistically composed of Sb/Bi. Their phase ranges as determined from single crystal data were found to be on the Sb-rich side of the overall composition A 11 Sb 6−x Bix in the case of the Rb compound (i. e. Rb 11 Sb 5.4 Bi 0.6 : orthorhombic Immm, a = 766.7(3), b = 1052.2(3), c = 1732.7(6) pm, Z = 4, R1 = 0.0554), and on the Bi-rich side of the overall composition A 11 Sb 6−x Bix in the case of A = Cs (i.e. Cs 11 Sb 1.6 Bi 4.4 ). In the series of known alkaline earth compounds A 11 M 10 , containing pentelide dumbbells among isolated Zintl anions, a redetermination of the structure of Ba 11 Sb 10  (orthorhombic, Immm, a = 1265.3(2), b = 1316.1(3), c =1947.2(5) pm, Z = 4, R1 = 0.0724) shows, that it represents a distorted variant of the tetragonal Ho 11 Ge 10  structure type. This distortion is not only of crystallographic importance, as it results in a major change in the nature of the anions and their bonding, which is supported by DFT band-structure calculations. Likewise, the Zintl phase BaSb 2  (monoclinic, P2 1 /m, a = 1167.9(9), b = 438.1(5), c = 1257.1(9) pm, β = 100.53(2)°, Z = 6, R1 = 0.0648) crystallizes with a superstructure of the CaSb 2 -type previously reported.

zeitschrift für naturforschung b

Verbindungen mit Pentelid-Hanteln M2: A I  II  M 6  und A II  11 M 10  (A = Rb, Cs, Ba; M = Sb, Bi) / Compounds with Pentelide Dumbbells M 2 : A I  11 M 6  and A II  11 M 10  (A = Rb, Cs, Ba; M = Sb, Bi)