Crystal Growth of Ag3 MO x F6−x (M = V, x = 2; M = Mo, x = 3)

Understanding the complex relationship between synthesis conditions, in particular temperature and composition, led to single crystals of the cryolite type phases Ag3MoO3F3 and Ag3VO2F4. These crystals form in a reversible thermodynamic process from dissolved species when the solution is heated. Single crystal structural data reveal the Mo6+ cation distorted toward facially coordinated oxides for Ag3MoO3F3, and the V5+ cation toward the edge of the cis-oxide positions for Ag3VO2F4. Local ordering of oxide and fluoride ligands is observed for both structures.