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Title: Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F

Abstract

Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: 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 MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~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 Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})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)more » 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 Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in antiferromagnetic ordering. Display Omitted - Highlights: • Single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}, (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown hydrothermally. • The use of fluoride mineralizers in the synthesis led to the formation of new compounds without OH{sup −} groups. • The structure of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} features zigzag chains of MnO{sub 4}F{sub 2} units. • Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} exhibits antiferromagnetic ordering with a Neel temperature of ~3 K. • Mn{sub 2}VO{sub 4}F possesses a condensed framework structure with disordered fluorine atoms.« less

Authors:
 [1];  [2]; ;  [1];  [3]; ;  [1];  [1]
  1. Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC 29634-0973 (United States)
  2. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)
  3. Quantum Condensed Matter Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)
Publication Date:
OSTI Identifier:
22584192
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 241; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; FLUORIDES; HYDROTHERMAL SYNTHESIS; MAGNETIC SUSCEPTIBILITY; MANGANESE IONS; MANGANESE OXIDES; MONOCLINIC LATTICES; MONOCRYSTALS; NEEL TEMPERATURE; POWDERS; SPACE GROUPS; TEMPERATURE DEPENDENCE; VANADATES; VANADIUM OXIDES; X RADIATION; X-RAY DIFFRACTION

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., E-mail: kjoseph@clemson.edu. Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F. 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., E-mail: kjoseph@clemson.edu. Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F. 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., E-mail: kjoseph@clemson.edu. Thu . "Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F". United States. doi:10.1016/J.JSSC.2016.05.008.
@article{osti_22584192,
title = {Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F},
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., E-mail: kjoseph@clemson.edu},
abstractNote = {Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: 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 MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~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 Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})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 Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in antiferromagnetic ordering. Display Omitted - Highlights: • Single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}, (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown hydrothermally. • The use of fluoride mineralizers in the synthesis led to the formation of new compounds without OH{sup −} groups. • The structure of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} features zigzag chains of MnO{sub 4}F{sub 2} units. • Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} exhibits antiferromagnetic ordering with a Neel temperature of ~3 K. • Mn{sub 2}VO{sub 4}F possesses a condensed framework structure with disordered fluorine atoms.},
doi = {10.1016/J.JSSC.2016.05.008},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 241,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
  • In large single crystals of A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F 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 MnO 4F 2 building blocks. The A 2Mn 2V 2O 7F 2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb 2Mn 2V 2O 7F 2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs 2Mn 2V 2O 7F 2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed ofmore » zigzag chains of edge-sharing MnO 4F 2 units running along the a-axis, and interconnected through V 2O 7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn 2+ indicated that Cs 2Mn 2V 2O 7F 2 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 Cs 2Mn 2V 2O 7F 2. Mn 2(VO 4)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 Mn 2+. Our interpenetrating chains are additionally connected through isolated VO 4 tetrahedra to form the condensed structure.« less
  • We synthesized manganese vanadate fluorides using high-temperature hydrothermal techniques with BaF 2 as a mineralizer. Ba 3Mn 2(V 2O 7) 2F 2 crystallizes in space group C2/c and consists of dimers built from edge-sharing MnO 4F 2 trigonal prisms with linking V 2O 7 groups. Ba 7Mn 8O 2(VO 4) 2F 23 crystallizes in space group Cmmm, with a manganese oxyfluoride network built from edge- and corner-sharing Mn 2+/3+(O,F) 6 octahedra. The resulting octahedra form alternating Mn 2+ and Mn 2+/3+ layers separated by VO 4 tetrahedra. This latter compound exhibits a canted antiferromagnetic order below TN = 25 K.
  • The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solidmore » state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less
  • New uranyl vanadates A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O (M=Li (1), Na (2), Ag (3)) have been synthesized by solid-state reaction and their structures determined from single-crystal X-ray diffraction data for 1 and 3. The tetragonal structure results of an alternation of two types of sheets denoted S for {sub {infinity}}{sup 2}[UO{sub 2}(VO{sub 4}){sub 2}]{sup 4-} and D for {sub {infinity}}{sup 2}[(UO{sub 2}){sub 2}(VO{sub 4}){sub 3}]{sup 5-} built from UO{sub 6} square bipyramids and connected through VO{sub 4} tetrahedra to {sub {infinity}}{sup 1}[U(3)O{sub 5}-U(4)O{sub 5}]{sup 8-} infinite chains of edge-shared U(3)O{sub 7} and U(4)O{sub 7} pentagonal bipyramids alternatively parallel tomore » a- and b-axis to construct a three-dimensional uranyl vanadate arrangement. It is noticeable that similar {sub {infinity}}[UO{sub 5}]{sup 4-} chains are connected only by S-type sheets in A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O and by D-type sheets in A(UO{sub 2}){sub 4}(VO{sub 4}){sub 3}, thus A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O appears as an intergrowth structure between the two previously reported series. The mobility of the monovalent ion in the mutually perpendicular channels created in the three-dimensional arrangement is correlated to the occupation rate of the sites and by the geometry of the different sites occupied by either Na, Ag or Li. Crystallographic data: 293 K, Bruker X8-APEX2 X-ray diffractometer equipped with a 4 K CCD detector, MoK{alpha}, {lambda}=0.71073 A, tetragonal symmetry, space group P4-bar m2, Z=1, full-matrix least-squares refinement on the basis of F{sup 2}; 1,a=7.2794(9) A, c=14.514(4) A, R1=0.021 and wR2=0.048 for 62 parameters with 782 independent reflections with I{>=}2{sigma}(I); 3, a=7.2373(3) A, c=14.7973(15) A, R1=0.041 and wR2=0.085 for 60 parameters with 1066 independent reflections with I{>=}2{sigma}(I). - Abstract: A view of the three-dimensional structure of Li{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O. Display Omitted.« less
  • In a new series of transition metal vanadates, namely, Ba 2M(VO 4) 2(OH) (M = V 3+, Mn 3+, and Fe 3+), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 °C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba 2V(VO 4) 2(OH) is monoclinic in space group P2 1/m, a = 7.8783(2) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å 3. Moreover, the other structures are similar and consist of one-dimensional trans edge-shared distortedmore » octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba 2Mn(VO 4) 2(OH) analogue yielded a new understanding of the Jahn–Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Finally, single-crystal temperature-dependent magnetic studies on Ba 2V(VO 4) 2(OH) reveal a broad feature over a wide temperature range with maximum at ~100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.« less