Synthesis, structure, and characterization of a cubic thallium cluster phase of the Bergman type, Na13(Cd∼0.70Tl∼0.30)27

Samples of Na-13(Cd1-xTlx)(27) crystallize with a cubic Bergman-type Im (3) over bar structure (formerly called the R-phase) (Z = 4, a similar or equal to 15.92 Angstrom) and exhibit a small phase width, 0.24 < x < 0.33. The crystal structure exhibits a Cd/Tl (=M) network of concentric empty M-12 and Cd-12 icosahedra and M-60 buckyball clusters, with the sodium cations in the annuli between clusters. The compound is unusually electron deficient with respect to electron counting rules applied to most Bergman phases with less electropositive cations, and because of the sodium component it is probably better described as an electron-poor Zintl phase. The new compound is metallic according to both EHTB band calculations for the anion and the measured resistivities and magnetic susceptibilities. Site preferences observed for Na, Cd, and Tl among the seven crystallographic sites are consistent with their relative Mulliken electron populations.