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Title: Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F

Abstract

In large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. We utilized single crystal X-ray diffraction and powder X-ray diffraction in order to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs2Mn2V2O7F2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. Our interpenetrating chains are additionally connected through isolated VO4 tetrahedra tomore » form the condensed structure.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [1];  [1];  [1]
  1. Clemson Univ., SC (United States). Dept. of Chemistry and Center for Optical Materials Science and Engineering Technologies
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1352766
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 241; Journal Issue: C; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Hydrothermal; Vanadate; Manganese(II); Antiferromagnetism

Citation Formats

Sanjeewa, Liurukara D., McGuire, Michael A., Smith Pellizzeri, Tiffany M., McMillen, Colin D., Ovidiu Garlea, V., Willett, Daniel, Chumanov, George, and Kolis, Joseph W. Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F. United States: N. p., 2016. Web. doi:10.1016/j.jssc.2016.05.008.
Sanjeewa, Liurukara D., McGuire, Michael A., Smith Pellizzeri, Tiffany M., McMillen, Colin D., Ovidiu Garlea, V., Willett, Daniel, Chumanov, George, & Kolis, Joseph W. Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F. United States. doi:10.1016/j.jssc.2016.05.008.
Sanjeewa, Liurukara D., McGuire, Michael A., Smith Pellizzeri, Tiffany M., McMillen, Colin D., Ovidiu Garlea, V., Willett, Daniel, Chumanov, George, and Kolis, Joseph W. Tue . "Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F". United States. doi:10.1016/j.jssc.2016.05.008. https://www.osti.gov/servlets/purl/1352766.
@article{osti_1352766,
title = {Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F},
author = {Sanjeewa, Liurukara D. and McGuire, Michael A. and Smith Pellizzeri, Tiffany M. and McMillen, Colin D. and Ovidiu Garlea, V. and Willett, Daniel and Chumanov, George and Kolis, Joseph W.},
abstractNote = {In large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. We utilized single crystal X-ray diffraction and powder X-ray diffraction in order to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs2Mn2V2O7F2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. Our interpenetrating chains are additionally connected through isolated VO4 tetrahedra to form the condensed structure.},
doi = {10.1016/j.jssc.2016.05.008},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 241,
place = {United States},
year = {2016},
month = {5}
}

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Works referencing / citing this record:

Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8
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  • Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Kolis, Joseph W.
  • Chemistry – A European Journal, Vol. 26, Issue 3
  • DOI: 10.1002/chem.201904193

Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8
journal, May 2019

  • Pellizzeri, Tiffany M. Smith; McMillen, Colin D.; Ivey, Kimberly
  • Journal of Chemical Crystallography, Vol. 49, Issue 3
  • DOI: 10.1007/s10870-019-00787-4

Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties
journal, January 2018

  • Smith Pellizzeri, Tiffany M.; McGuire, Michael A.; McMillen, Colin D.
  • Dalton Transactions, Vol. 47, Issue 8
  • DOI: 10.1039/c7dt04642a

Low temperature synthesis, structure and magnetic properties of Mn 2 [VO 4 ]F
journal, December 2017