Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties

Tiffany M Smith Pellizzeri; Michael A McGuire; Colin D McMillen; Yimei Wen; George Chumanov; Joseph W Kolis

doi:10.1039/c7dt04642a

Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties

Dalton Trans. 2018 Feb 20;47(8):2619-2627. doi: 10.1039/c7dt04642a.

Authors

Tiffany M Smith Pellizzeri¹, Michael A McGuire, Colin D McMillen, Yimei Wen, George Chumanov, Joseph W Kolis

Affiliation

¹ Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC 29634-0973, USA. kjoseph@clemson.edu.

PMID: 29393314
DOI: 10.1039/c7dt04642a

Abstract

Two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs₃Mn(VO₃)₄Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar noncentrosymmetric space group Cmm2, with a = 16.7820(8) Å, b = 8.4765(4) Å, c = 5.7867(3) Å. This structure is built from sinusoidal zig-zag (VO₃)_n chains that run along the b-axis and are coordinated to Mn²⁺ containing (MnO₄Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs₂Mn(VO₃)₃F, (2) crystallizes in space group Pbca with a = 7.4286(2) Å, b = 15.0175(5) Å, c = 19.6957(7) Å, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn²⁺ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO₃)_n vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integral part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(ii) within the crystal structure.