Abstract
A8Tl11 (A = alkali metal) compounds have been known since the investigations of Corbett et al. in 1995 and are still a matter of current discussions as the compound includes one extra electron referred to the charge of the Tl117− cluster. Attempts to substitute this additional electron by incorporation of a halide atom succeeded in the preparation of single crystals for the lightest triel homologue of the group, Cs8Ga11Cl, and powder diffraction experiments for the heavier homologues also suggested the formation of analogous compounds. However, X-Ray single crystal studies on A8Tl11X to prove this substitution and to provide a deeper insight into the influence on the thallide substructure have not yet been performed, probably due to severe absorption combined with air and moisture sensitivity for this class of compounds. Here, we present single crystal X-Ray structure analyses of the new compounds Cs8Tl11Cl0.8, Cs8Tl11Br0.9, Cs5Rb3Tl11Cl0.5, Cs5.7K2.3Tl11Cl0.6 and K4Rb4Tl11Cl0.1. It is shown that a (partial) incorporation of halide can also be indirectly determined by examination of the Tl-Tl distances, thereby the newly introduced cdd/cdav ratio allows to evaluate the degree of distortion of Tl117− clusters.
Highlights
Naked cluster anions of the main group elements are well-known for group 14 and 15 elements in solid-state [1,2,3,4]
All compounds crystallize in the K8 In11 structure type and especially for the mixed alkali metal compounds many of the crystals happened to form typical
The materials naturally possess very high absorption coefficients (μ > 60 mm−1 ), small single crystals have been chosen for the X-ray analyses
Summary
Olex adapted from [23], with maps, generated by Olex2 [23]). 2011 Olex Wiley. The resulting coordination sphere of the halide is best described as distorted cubic, where the position of A2.are. This distance shortens significantly for X-A2 by introducing positions (same s.o.f. longer distances along the room diagonal of the cubic arrangement from thesplit halide to the position longer distances are along the room diagonal of the cubic arrangement from the halide to the as halide), resulting in a less distorted cubic arrangement. This distance shortens significantly for X-A2 by introducing split positions (same s.o.f. as halide), position of A2. Tables and 5 lists distances within the the distorted cubic arrangements as well as the s.o.f. values for the halide/split.
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