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Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8

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Abstract

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.

Graphical Abstract

Crystals of Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8 were synthesized from hydrothermal brines and their structures determined by single crystal X-ray diffraction, revealing preferential, ordered site substitution of the alkali metals.

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Acknowledgements

We are indebted to the National Science Foundation NSF-DMR-1808371 for financial support of this work.

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Authors and Affiliations

  1. Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, 485 H.L. Hunter Laboratories, Clemson, SC, 29634-0973, USA

    Tiffany M. Smith Pellizzeri, Colin D. McMillen & Joseph W. Kolis

  2. Department of Materials Science and Engineering, Clemson University, Clemson, SC, 29634-0973, USA

    Kimberly Ivey

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Correspondence to Joseph W. Kolis.

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Pellizzeri, T.M.S., McMillen, C.D., Ivey, K. et al. Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8. J Chem Crystallogr 49, 186–192 (2019). https://doi.org/10.1007/s10870-019-00787-4

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