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This paper presents results from our exploratory work in the systems K-Cd-Ge, Rb-Cd-Ge, and Cs-Cd-Ge, which yielded the novel type-I clathrates with refined compositions K₈Cd 3.77(7) Ge 42.23 , Rb₈Cd 3.65(7) Ge 42.35 , and Cs 7.80(1) Cd 3.65(6) Ge 42.35 . The three compounds represent rare examples of clathrates of germanium with the alkali metals, where a d 10 element substitutes a group 14 element. The three structures, established by single-crystal X-ray diffraction, indicate that the framework-building Ge atoms are randomly substituted by Cd atoms on only one of the three possible crystallographic sites. This and several other details of the crystal chemistry are elaborated.

Synthesis and Structural Characterization of the New Clathrates K8Cd4Ge42, Rb8Cd4Ge42, and Cs8Cd4Ge42