Hydrothermal synthesis of single crystals of transition metal vanadates in the glaserite phase

•The hydrothermal synthesis of glaserite-type vanadates is demonstrated.•Synthesis from stoichiometric component reactions yields 0.2–0.5 mm size crystals.•Hydrothermal recrystallization of glaserite powder yields 2–3 mm size crystals.•The structure varies according to the alkali and alkaline earth metals selected.•Ideal (P-3m1) and distorted (P-3 and P21/c) glaserite structures are observed.

A series of transition metal vanadate crystals were prepared using a high temperature (580 °C) hydrothermal method. The compounds all had the general formula A2AEM(VO4)2 (A=K, Na, Li; AE=Ba, Sr; M=Co, Fe, Mn). They are all variations of the glaserite structural type and range in symmetry from P-3m1 to P-3 to P21/c. Most of the derivatives contain a planar three-fold rotation operation, making them possible spin frustration candidates. Single crystal structural analyses were performed on many of the derivatives to obtain a detailed understanding of the distortions of the tetrahedral building blocks that accommodate the symmetry distortions. A hydrothermal growth method was developed to grow high quality single crystals of sizes up to 2–3 mm/edge. This method can be generalized for large crystal growth to enable magnetic and neutron diffraction studies that require relatively large single crystals.

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