Abstract
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) A, c = 12.2016(3) A, 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) A, c = 8.0685(3) A, space group P \( \bar 3 \) 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.
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