skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA) 2MCl 6 (M = U, Np, Pt, Sn, Hf, Zr)

Abstract

A study of the phase transitions occurring in tetramethylammonium hexachlorometalate compounds with M = U IV, Np IV, Zr IV, Sn IV, Hf IV and Pt IV were performed using single-crystal X-ray diffraction across the temperature range 120 - 400K. When the crystals were cooled, movement of the octahedral [MCl 6] 2- anions induces a phase transition from Fm3m to Fd3c with a doubling of the unit cell. For the actinide compounds, no correlation between the f-electron configuration and the transition temperature was observed, instead, a correlation between the transition temperatures and both the [MCl 6] 2- anion and the TMA cation size is highlighted. Two phase transitions were observed and characterized. The first phase transition occurs with the ordering of the TMA cation and the second from a rotation of the [MCl 6] 2- octahedra. A third phase transition was observed at lower temperatures and was ascribed to a tetragonal distortion of the [MCl 6] 2- anions. Synthesis and study of their deuterated compounds did not show a significant isotope effect. As a result, Raman spectra performed on the protonated and deuterated compounds indicate only weak hydrogen bonding interactions between the TMA cations and the [MCl 6] 2- octahedra.

Authors:
 [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1422404
Alternate Identifier(s):
OSTI ID: 1408148
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2017; Journal Issue: 41; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Phase transitions; Actinides; Structure elucidation; Raman spectroscopy

Citation Formats

Autillo, Matthieu, and Wilson, Richard E. Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr). United States: N. p., 2017. Web. doi:10.1002/ejic.201700764.
Autillo, Matthieu, & Wilson, Richard E. Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr). United States. doi:10.1002/ejic.201700764.
Autillo, Matthieu, and Wilson, Richard E. Fri . "Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)". United States. doi:10.1002/ejic.201700764. https://www.osti.gov/servlets/purl/1422404.
@article{osti_1422404,
title = {Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)},
author = {Autillo, Matthieu and Wilson, Richard E.},
abstractNote = {A study of the phase transitions occurring in tetramethylammonium hexachlorometalate compounds with M = UIV, NpIV, ZrIV, SnIV, HfIV and PtIV were performed using single-crystal X-ray diffraction across the temperature range 120 - 400K. When the crystals were cooled, movement of the octahedral [MCl6]2- anions induces a phase transition from Fm3m to Fd3c with a doubling of the unit cell. For the actinide compounds, no correlation between the f-electron configuration and the transition temperature was observed, instead, a correlation between the transition temperatures and both the [MCl6]2- anion and the TMA cation size is highlighted. Two phase transitions were observed and characterized. The first phase transition occurs with the ordering of the TMA cation and the second from a rotation of the [MCl6]2- octahedra. A third phase transition was observed at lower temperatures and was ascribed to a tetragonal distortion of the [MCl6]2- anions. Synthesis and study of their deuterated compounds did not show a significant isotope effect. As a result, Raman spectra performed on the protonated and deuterated compounds indicate only weak hydrogen bonding interactions between the TMA cations and the [MCl6]2- octahedra.},
doi = {10.1002/ejic.201700764},
journal = {European Journal of Inorganic Chemistry},
number = 41,
volume = 2017,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Low temperature vibrational spectroscopy. I. Hexachlorotellurates
journal, January 1977

  • Berg, Rolf W.; Poulsen, Finn W.; Bjerrum, Niels J.
  • The Journal of Chemical Physics, Vol. 67, Issue 5
  • DOI: 10.1063/1.435139

Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2–
journal, September 2014

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501553m

Effect of spin-orbit coupling on the actinide dioxides AnO 2 (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study
journal, October 2012

  • Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E.
  • The Journal of Chemical Physics, Vol. 137, Issue 15
  • DOI: 10.1063/1.4757615

Experimental Vibrational Zero-Point Energies: Diatomic Molecules
journal, June 2007

  • Irikura, Karl K.
  • Journal of Physical and Chemical Reference Data, Vol. 36, Issue 2
  • DOI: 10.1063/1.2436891

Thermodynamics of ammonium haloplatinates V. Heat capacity, phase transitions and thermodynamic properties of(ND4)2PtBr6fromT= 5 K toT= 350 K
journal, September 2000

  • Callanan,, Jane E.; Weir, Ron D.; Westrum, Jr, Edgar F.
  • The Journal of Chemical Thermodynamics, Vol. 32, Issue 9
  • DOI: 10.1006/jcht.1999.0567

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Neutron Diffraction Study on Orientational Disorder of ND + 4 Ions in (ND 4 ) 2 SeCl 6 Crystal
journal, August 1995

  • Yamamuro, Osamu; Muraoka, Hiroki; Ohta, Tomoko
  • Journal of the Physical Society of Japan, Vol. 64, Issue 8
  • DOI: 10.1143/JPSJ.64.2722

Thermodynamics of ammonium halogenated tellurides
journal, March 1995

  • Callanan, Jane E.; Weir, Ron D.; Westrum, Jr., Edgar F.
  • The Journal of Chemical Thermodynamics, Vol. 27, Issue 3
  • DOI: 10.1006/jcht.1995.0029

Synthesis and Structure of (Ph 4 P) 2 MCl 6 (M = Ti, Zr, Hf, Th, U, Np, Pu)
journal, May 2012

  • Minasian, Stefan G.; Boland, Kevin S.; Feller, Russell K.
  • Inorganic Chemistry, Vol. 51, Issue 10
  • DOI: 10.1021/ic300179d

Hard and soft acids and bases, HSAB, part II: Underlying theories
journal, October 1968

  • Pearson, Ralph G.
  • Journal of Chemical Education, Vol. 45, Issue 10
  • DOI: 10.1021/ed045p643

van der Waals Volumes and Radii
journal, March 1964

  • Bondi, A.
  • The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
  • DOI: 10.1021/j100785a001

Structural properties and lattice dynamics of 5d transition metal antifluorite crystals
journal, January 1980


Theoretical Considerations Concerning the Separation of Isotopes
journal, June 1933

  • Eyring, Henry; Sherman, Albert
  • The Journal of Chemical Physics, Vol. 1, Issue 6
  • DOI: 10.1063/1.1749301

Hard and soft acids and bases, HSAB, part 1: Fundamental principles
journal, September 1968

  • Pearson, Ralph G.
  • Journal of Chemical Education, Vol. 45, Issue 9
  • DOI: 10.1021/ed045p581

Crystal Structure of Tetramethylammonium Hexachloroplatinate(IV).
journal, January 1978


Influence of d-electron configuration on phase transitions in A2MX6 (Hexahalometallates IV)
journal, March 1977


Phase Transitions in Tetramethylammonium Hexachloroplatinate(IV), -tellurate(IV), and -stannate(IV) as Studied by 35 Cl NQR and Powder X-Ray Diffraction
journal, April 1982

  • Furukawa, Yoshihiro; Prabhumirashi, Laxman S.; Ikeda, Ryuichi
  • Bulletin of the Chemical Society of Japan, Vol. 55, Issue 4
  • DOI: 10.1246/bcsj.55.995

Neutron diffraction study of (ND4)2SeCl6, (ND4)2PtCl6, and (ND4)2PtBr6 crystals: The origin of the strong deuterium substitution effect on the phase transitions
journal, November 1997

  • Yamamuro, Osamu; Okishiro, Kenji; Matsuo, Takasuke
  • The Journal of Chemical Physics, Vol. 107, Issue 19
  • DOI: 10.1063/1.475063

Vibrational spectra of halides and complex halides. Part I. Hexahalogenoplatinates
journal, January 1967

  • Adams, D. M.; Morris, D. M.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19670001666

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Structure, Phase Transitions, and Isotope Effects in [(CH 3 ) 4 N] 2 PuCl 6
journal, July 2015


Thermodynamics of ammonium haloplatinates IV. Heat capacity, phase transitions, and thermodynamic properties of (NH4)2PtBr6fromT=6 K toT=320 K
journal, December 1998

  • Callanan, Jane E.; Weir, Ron D.; Westrum, Jr., Edgar F.
  • The Journal of Chemical Thermodynamics, Vol. 30, Issue 12
  • DOI: 10.1006/jcht.1998.0430

Structural and Vibrational Properties of U(VI)O 2 Cl 4 2- and Pu(VI)O 2 Cl 4 2- Complexes
journal, November 2013

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 52, Issue 24
  • DOI: 10.1021/ic401991n

Raman spectroscopic study of a phase transition in (TMA)2UCl6 and (TMA)2SnCl6 
journal, January 1975

  • von der Ohe, W.
  • The Journal of Chemical Physics, Vol. 63, Issue 7
  • DOI: 10.1063/1.431705

The Raman spectrum of (TMA) 2 UCl 6 and (TMA) 2 SnCl 6 crystals and of TMACl in solution
journal, May 1975

  • von der Ohe, W.
  • The Journal of Chemical Physics, Vol. 62, Issue 10
  • DOI: 10.1063/1.430314

Supramolecular Interactions in PuO 2 Cl 4 2– and PuCl 6 2– Complexes with Protonated Pyridines: Synthesis, Crystal Structures, and Raman Spectroscopy
journal, December 2013

  • Wilson, Richard E.; Schnaars, David D.; Andrews, Michael B.
  • Inorganic Chemistry, Vol. 53, Issue 1
  • DOI: 10.1021/ic4023294

Thermodynamics of Ammonium Halopallidates II. Heat Capacity and Thermodynamic Properties of (ND4)2PdCl6 at Temperatures from 5 K to 325 K
journal, November 1992

  • Callanan, Jane E.; Weir, Ron D.; Westrum, Edgar F.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 96, Issue 11
  • DOI: 10.1002/bbpc.19920961113

THE CRYSTAL STRUCTURE OF K 2 TeBr 6
journal, December 1964

  • Brown, I. D.
  • Canadian Journal of Chemistry, Vol. 42, Issue 12
  • DOI: 10.1139/v64-409

Structural changes in the antifluorite crystal (NH 4 ) 2 SnBr 6
journal, July 1983

  • Armstrong, Robin L.; Morra, Rose M.; Powell, Brian M.
  • Canadian Journal of Physics, Vol. 61, Issue 7
  • DOI: 10.1139/p83-124

Neutron diffraction study of the structural changes in the antifluorite crystals Rb 2 PtI 6 , (NH 4 ) 2 PtBr 6 , and (NH 4 ) 2 PtI 6
journal, March 1981

  • Sutton, Mark; Armstrong, Robin L.; Powell, Brian M.
  • Canadian Journal of Physics, Vol. 59, Issue 3
  • DOI: 10.1139/p81-056

Deuteration effect in the phase transition of (NH4)2PbCl6
journal, February 1995


Neutron diffraction study of the structure of the antifluorite crystal (NH 4 ) 2 PbCl 6
journal, November 1989

  • Armstrong, Robin L.; Lo, Bryan; Powell, Brian M.
  • Canadian Journal of Physics, Vol. 67, Issue 11
  • DOI: 10.1139/p89-182

Adiabatic heat capacity and related properties of ammonium hexachlororuthenate, (NH4)2RuCl6, at temperatures from 5⩽T/K⩽325
journal, June 2014


Hydrolytic Metal-Mediated Coupling of Dialkylcyanamides at a Pt(IV) Center Giving a New Family of Diimino Ligands
journal, November 2003

  • Bokach, Nadezhda A.; Pakhomova, Tatyana B.; Kukushkin, Vadim Yu.
  • Inorganic Chemistry, Vol. 42, Issue 23
  • DOI: 10.1021/ic034800x

The Deuterium Isotope Effect
journal, August 1955


    Works referencing / citing this record:

    Thermodynamics of Ammonium Halopallidates II. Heat Capacity and Thermodynamic Properties of (ND4)2PdCl6 at Temperatures from 5 K to 325 K
    journal, November 1992

    • Callanan, Jane E.; Weir, Ron D.; Westrum, Edgar F.
    • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 96, Issue 11
    • DOI: 10.1002/bbpc.19920961113

    Thermodynamics of ammonium halogenated tellurides
    journal, March 1995

    • Callanan, Jane E.; Weir, Ron D.; Westrum, Jr., Edgar F.
    • The Journal of Chemical Thermodynamics, Vol. 27, Issue 3
    • DOI: 10.1006/jcht.1995.0029

    Thermodynamics of ammonium haloplatinates IV. Heat capacity, phase transitions, and thermodynamic properties of (NH4)2PtBr6fromT=6 K toT=320 K
    journal, December 1998

    • Callanan, Jane E.; Weir, Ron D.; Westrum, Jr., Edgar F.
    • The Journal of Chemical Thermodynamics, Vol. 30, Issue 12
    • DOI: 10.1006/jcht.1998.0430

    Thermodynamics of ammonium haloplatinates V. Heat capacity, phase transitions and thermodynamic properties of(ND4)2PtBr6fromT= 5 K toT= 350 K
    journal, September 2000

    • Callanan,, Jane E.; Weir, Ron D.; Westrum, Jr, Edgar F.
    • The Journal of Chemical Thermodynamics, Vol. 32, Issue 9
    • DOI: 10.1006/jcht.1999.0567

    Influence of d-electron configuration on phase transitions in A2MX6 (Hexahalometallates IV)
    journal, March 1977


    Deuteration effect in the phase transition of (NH4)2PbCl6
    journal, February 1995


    Structural properties and lattice dynamics of 5d transition metal antifluorite crystals
    journal, January 1980


    Covalency in f-element complexes
    journal, January 2013

    • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
    • Coordination Chemistry Reviews, Vol. 257, Issue 2
    • DOI: 10.1016/j.ccr.2012.04.029

    Adiabatic heat capacity and related properties of ammonium hexachlororuthenate, (NH4)2RuCl6, at temperatures from 5⩽T/K⩽325
    journal, June 2014


    Structure, Phase Transitions, and Isotope Effects in [(CH 3 ) 4 N] 2 PuCl 6
    journal, July 2015


    The Deuterium Isotope Effect
    journal, August 1955


    Hard and soft acids and bases, HSAB, part 1: Fundamental principles
    journal, September 1968

    • Pearson, Ralph G.
    • Journal of Chemical Education, Vol. 45, Issue 9
    • DOI: 10.1021/ed045p581

    Hard and soft acids and bases, HSAB, part II: Underlying theories
    journal, October 1968

    • Pearson, Ralph G.
    • Journal of Chemical Education, Vol. 45, Issue 10
    • DOI: 10.1021/ed045p643

    Hydrolytic Metal-Mediated Coupling of Dialkylcyanamides at a Pt(IV) Center Giving a New Family of Diimino Ligands
    journal, November 2003

    • Bokach, Nadezhda A.; Pakhomova, Tatyana B.; Kukushkin, Vadim Yu.
    • Inorganic Chemistry, Vol. 42, Issue 23
    • DOI: 10.1021/ic034800x

    Synthesis and Structure of (Ph 4 P) 2 MCl 6 (M = Ti, Zr, Hf, Th, U, Np, Pu)
    journal, May 2012

    • Minasian, Stefan G.; Boland, Kevin S.; Feller, Russell K.
    • Inorganic Chemistry, Vol. 51, Issue 10
    • DOI: 10.1021/ic300179d

    Structural and Vibrational Properties of U(VI)O 2 Cl 4 2- and Pu(VI)O 2 Cl 4 2- Complexes
    journal, November 2013

    • Schnaars, David D.; Wilson, Richard E.
    • Inorganic Chemistry, Vol. 52, Issue 24
    • DOI: 10.1021/ic401991n

    Supramolecular Interactions in PuO 2 Cl 4 2– and PuCl 6 2– Complexes with Protonated Pyridines: Synthesis, Crystal Structures, and Raman Spectroscopy
    journal, December 2013

    • Wilson, Richard E.; Schnaars, David D.; Andrews, Michael B.
    • Inorganic Chemistry, Vol. 53, Issue 1
    • DOI: 10.1021/ic4023294

    Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2–
    journal, September 2014

    • Schnaars, David D.; Wilson, Richard E.
    • Inorganic Chemistry, Vol. 53, Issue 20
    • DOI: 10.1021/ic501553m

    van der Waals Volumes and Radii
    journal, March 1964

    • Bondi, A.
    • The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
    • DOI: 10.1021/j100785a001

    Vibrational spectra of halides and complex halides. Part I. Hexahalogenoplatinates
    journal, January 1967

    • Adams, D. M.; Morris, D. M.
    • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
    • DOI: 10.1039/j19670001666

    Theoretical Considerations Concerning the Separation of Isotopes
    journal, June 1933

    • Eyring, Henry; Sherman, Albert
    • The Journal of Chemical Physics, Vol. 1, Issue 6
    • DOI: 10.1063/1.1749301

    Experimental Vibrational Zero-Point Energies: Diatomic Molecules
    journal, June 2007

    • Irikura, Karl K.
    • Journal of Physical and Chemical Reference Data, Vol. 36, Issue 2
    • DOI: 10.1063/1.2436891

    The Raman spectrum of (TMA) 2 UCl 6 and (TMA) 2 SnCl 6 crystals and of TMACl in solution
    journal, May 1975

    • von der Ohe, W.
    • The Journal of Chemical Physics, Vol. 62, Issue 10
    • DOI: 10.1063/1.430314

    Raman spectroscopic study of a phase transition in (TMA)2UCl6 and (TMA)2SnCl6 
    journal, January 1975

    • von der Ohe, W.
    • The Journal of Chemical Physics, Vol. 63, Issue 7
    • DOI: 10.1063/1.431705

    Low temperature vibrational spectroscopy. I. Hexachlorotellurates
    journal, January 1977

    • Berg, Rolf W.; Poulsen, Finn W.; Bjerrum, Niels J.
    • The Journal of Chemical Physics, Vol. 67, Issue 5
    • DOI: 10.1063/1.435139

    Neutron diffraction study of (ND4)2SeCl6, (ND4)2PtCl6, and (ND4)2PtBr6 crystals: The origin of the strong deuterium substitution effect on the phase transitions
    journal, November 1997

    • Yamamuro, Osamu; Okishiro, Kenji; Matsuo, Takasuke
    • The Journal of Chemical Physics, Vol. 107, Issue 19
    • DOI: 10.1063/1.475063

    Effect of spin-orbit coupling on the actinide dioxides AnO 2 (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study
    journal, October 2012

    • Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E.
    • The Journal of Chemical Physics, Vol. 137, Issue 15
    • DOI: 10.1063/1.4757615

    Neutron diffraction study of the structural changes in the antifluorite crystals Rb 2 PtI 6 , (NH 4 ) 2 PtBr 6 , and (NH 4 ) 2 PtI 6
    journal, March 1981

    • Sutton, Mark; Armstrong, Robin L.; Powell, Brian M.
    • Canadian Journal of Physics, Vol. 59, Issue 3
    • DOI: 10.1139/p81-056

    Structural changes in the antifluorite crystal (NH 4 ) 2 SnBr 6
    journal, July 1983

    • Armstrong, Robin L.; Morra, Rose M.; Powell, Brian M.
    • Canadian Journal of Physics, Vol. 61, Issue 7
    • DOI: 10.1139/p83-124

    Neutron diffraction study of the structure of the antifluorite crystal (NH 4 ) 2 PbCl 6
    journal, November 1989

    • Armstrong, Robin L.; Lo, Bryan; Powell, Brian M.
    • Canadian Journal of Physics, Vol. 67, Issue 11
    • DOI: 10.1139/p89-182

    THE CRYSTAL STRUCTURE OF K 2 TeBr 6
    journal, December 1964

    • Brown, I. D.
    • Canadian Journal of Chemistry, Vol. 42, Issue 12
    • DOI: 10.1139/v64-409

    Phase Transitions in Tetramethylammonium Hexachloroplatinate(IV), -tellurate(IV), and -stannate(IV) as Studied by 35 Cl NQR and Powder X-Ray Diffraction
    journal, April 1982

    • Furukawa, Yoshihiro; Prabhumirashi, Laxman S.; Ikeda, Ryuichi
    • Bulletin of the Chemical Society of Japan, Vol. 55, Issue 4
    • DOI: 10.1246/bcsj.55.995

    Crystal Structure of Tetramethylammonium Hexachloroplatinate(IV).
    journal, January 1978