Phase formation in Cs2MoO4-MMoO4-Zr(MoO4)2 (M = Mn, Mg, Co, Zn) systems and crystal structure of new double molybdates Cs2MnZr2(MoO4)6 and Cs2MnZr(MoO4)4

Subsolidus phase relations in the Cs₂MoO₄-MMoO₄-Zr(MoO₄)₂ (M = Mn, Zn) ternary systems were determined, and two groups of new isostructural triple molybdates were synthesized: Cs₂MZr(MoO₄)₄ and Cs₂MZr₂(MoO₄)₆ (M = Mn, Mg, Co, Zn). Cs₂MnZr₂(MoO₄)₆ and Cs₂MnZr(MoO₄)₄ crystals were grown by spontaneous flux crystallization and used in structure solution for both groups of compounds. The Cs₂MnZr₂(MoO₄)₆ structure (a =13.4322(2) ?, c = 12.2016(3) ?, group R3, Z = 3, R = 0.0367) is a new structure type characterized by a mixed three-dimensional framework built of corner-sharing MoO₄ tetrahedra and (M, Zr)O₆ octahedra where large channels are occupied by cesium cations. Cs₂MnZr₂(MoO₄)₄ (a =5.3890(1) ?, c = 8.0685(3) ?, space group P $ \bar 3 $ \bar 3 m1, Z = 0.5, R = 0.0247) has the layered glaserite-like KAl(MoO₄)₂ type structure, where Al³⁺ octahedral positions are randomly occupied by a 0.5M²⁺ + 0.5Zr⁴⁺ mixture.