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The two new deeply coloured, air stable, isotypic compounds Ag 6 GeS 4 X 2  (X: Cl, Br) were obtained in the course of a series of experiments to prepare new “non-metallic filled Laves phases (= argyrodites)”. Although the chemical compositions of the new compounds are in accordance with the desired rare type of doubly halide (X) substituted argyrodites Ag 6 GeS 4 X 2 , their crystal structures are not of the argyrodite type. Instead they are the first members of the new family of “non-metallic filled NaHg 2  phases”,  i.e.  the partial structure of the non-metal atoms S and X (Cl, Br) corresponds to the arrangement of Na and Hg atoms in NaHg 2  (= X 2 S 4 ) with Ge located in tetrahedral holes exclusively and Ag located in tetrahedral as well as octahedral holes. The lattice constants of the new phases are (both space group  Pnma ,  Z  = 4): Ag 6 GeS 4 Cl 2  ( a  = 643.0(1) pm,  b  = 761.0(2) pm,  c  = 2266.0(5) pm), Ag 6 GeS 4 Br 2  ( a  = 654.0(1) pm,  b  = 772.7(2) pm,  c  = 2289.9(5) pm). High temperature X-ray powder studies show an irreversible loss of halogen resulting in inhomogeneous decomposition products with argyrodite structure.

Ag 6 GeS 4 X 2 (X: Cl, Br): surprisingly no filled Laves phases but the first representatives of a new structure type