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The new members of the Ag 2−   x  Na  x  Mn 3 (VO 4 ) 3  (0 ≤  x  ≤ 2) solid solution were synthesized by a solid-state reaction route. The crystal structures of Ag 1.38 Na 0.62 Mn 3 (VO 4 ) 3  ( x  = 0.62) and Ag 0.15 Na 1.85 Mn 3 (VO 4 ) 3  ( x  = 1.85) were solved using single crystal X-ray diffraction. These phases crystallize with a monoclinic symmetry (space group  C 2 /c ), and their structures are new members of the well-known alluaudite family. In both compounds, the Ag + /Na + , Mn 2+ /Mn 3+  and V 5+  cations are eight-, six-, and four-coordinated to oxygen atoms, respectively. All the atoms are perfectly ordered except for the Ag and Na atoms which are statistically disordered over a 4 b  and a 4 e  atomic position. This single-crystal structural study confirms the existence of a full solid solution Ag 2−   x  Na  x  Mn 3 (VO 4 ) 3  (0 ≤  x  ≤ 1.85).

Structural properties of the alluaudite-type materials Ag 2– x Na x Mn 3 (VO 4 ) 3 ( x =0.62 and 1.85)