Denticity and Mobility of the Carbonate Groups in AMCO3F Fluorocarbonates: A Study on KMnCO3F and High Temperature KCaCO3F Polymorph

Rousse, Gwenaelle; Ahouari, Hania; Pomjakushin, Vladimir; Tarascon, Jean-Marie; Recham, Nadir; Abakumov, Artem M.

doi:10.1021/acs.inorgchem.7b01926

Denticity and Mobility of the Carbonate Groups in AMCO₃F Fluorocarbonates: A Study on KMnCO₃F and High Temperature KCaCO₃F Polymorph

Journal Article · Wed Oct 18 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b01926· OSTI ID:1410124

Rousse, Gwenaelle ^[1]; Ahouari, Hania ^[2]; Pomjakushin, Vladimir ^[3]; Tarascon, Jean-Marie ^[1]; Recham, Nadir ^[2]; ^[4]

College de France, Paris Cedex (France); Sorbonne Univ.-UPMC Univ. Paris (France); Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens Cedex (France)
Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens Cedex (France); Lab. de Réactivité et Chimie des Solides, Amiens Cedex (France); ALISTORE-European Research Inst., Amiens (France)
Paul Scherrer Inst., Villigen (Switzerland)
Skolkovo Inst. of Science and Technology, Moscow (Russia)

We report on a thorough structural study on two members of layered fluorocarbonates KMCO₃F (M = Ca, Mn). The Ca-based member demonstrates a phase transition at ~320 °C, evidenced for the first time. The crystal structure of the high temperature phase (HT-KCaCO₃F) was solved using neutron powder diffraction. A new Mn-based phase KMnCO₃F was synthesized, and its crystal structure was solved from electron diffraction tomography data and refined from a combination of X-ray synchrotron and neutron powder diffraction. In contrast to other members of the fluorocarbonate family, the carbonate groups in the KMnCO₃F and HT-KCaCO₃F structures are not fixed to two distinct orientations corresponding to mono- and bidentate coordinations of the M cation. In KMnCO₃F, the carbonate group can be considered as nearly “monodentate”, forming one short (2.14 Å) and one long (3.01 Å) Mn–O contact. This topology provides more flexibility to the MCO₃ layer and enables diminishing the mismatch between the MCO₃ and KF layers. This conclusion is corroborated by the HT-KCaCO₃F structure, in which the carbonate groups can additionally be tilted away from the layer plane thus relieving the strain arising from geometrical mismatch between the layers. The correlation between denticity of the carbonate groups, their mobility, and cation size variance is discussed. KMnCO₃ orders antiferromagnetically below T_N = 40 K.

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1410124

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 21 Vol. 56; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cations
chemical structure
crystal structure
inorganic carbon compounds
phase transitions

CCDC 1565415: Experimental Crystal Structure Determination Rousse, Gwenaelle; Ahouari, Hania; Pomjakushin, Vladimir https://doi.org/10.5517/ccdc.csd.cc1pjy8f The current record is supplemented by this dataset	dataset	January 2017
CCDC 1565416: Experimental Crystal Structure Determination Rousse, Gwenaelle; Ahouari, Hania; Pomjakushin, Vladimir https://doi.org/10.5517/ccdc.csd.cc1pjy9g The current record is supplemented by this dataset	dataset	January 2017
CCDC 1565417: Experimental Crystal Structure Determination Rousse, Gwenaelle; Ahouari, Hania; Pomjakushin, Vladimir https://doi.org/10.5517/ccdc.csd.cc1pjybh The current record is supplemented by this dataset	dataset	January 2017