Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8
Two new structurally related cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method utilizing halide brine mineralizers. Both structures Cs6Mn(H2O)2(VO3)8 (I) and Cs5KMn(H2O)2(VO3)8 (II) are isostructural crystallizing in the tetragonal space group P4/mnc. The first structure, Cs6Mn(H2O)2(VO3)8 (I) has unit cell dimensions of a = 13.6830(4) Å, c = 8.6476(3) Å and the second structure, Cs5KMn(H2O)2(VO3)8 (II), has unit cell dimensions of a = 13.5015(4) Å, c = 8.5372(3) Å. The structures are built from a manganese vanadate chain, which consists of [Mn(H2O)2O4] units that are coordinated to one another by a unique sinusoidal vanadate chain, (VO3)n. Both structures have well-ordered alkali metal atoms, with the potassium atoms of II exhibiting preferential site occupancy. Both compounds were characterized by single crystal X-ray diffraction and infrared spectroscopy, to identify the characteristic O–H and V–O modes.
KeywordsHydrothermal synthesis Metal vanadates Brine mineralizers Transition metal
We are indebted to the National Science Foundation NSF-DMR-1808371 for financial support of this work.
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