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Ionic Crystal Structures02:42

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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Stable Aqueous Suspensions of Manganese Ferrite Clusters with Tunable Nanoscale Dimension and Composition
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Sodium manganese fluorosulfate with a triplite structure.

Prabeer Barpanda1, Chris D Ling, Gosuke Oyama

  • 1Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.

Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials
|November 21, 2013
PubMed
Summary

The crystal structure of NaMnSO4F was determined using X-ray diffraction. Random cation distribution prevents sodium-ion conduction, making this fluorosulfate electrochemically inactive.

Keywords:
disorderfluorosulfatessodium-ion battery cathodestriplite

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Area of Science:

  • Solid-state chemistry
  • Crystallography
  • Materials science

Background:

  • Understanding the crystal structure of novel inorganic compounds is crucial for predicting their properties.
  • Fluorosulfates are an emerging class of materials with potential applications in energy storage.
  • The triplite mineral family provides a structural template for designing new inorganic materials.

Purpose of the Study:

  • To determine the crystal structure of the NaMnSO4F fluorosulfate phase.
  • To investigate the cation distribution within the crystal lattice.
  • To assess the potential for Na-ion conduction and electrochemical activity.

Main Methods:

  • Low-temperature solid-state synthesis.
  • Rietveld refinement of synchrotron X-ray powder diffraction data.
  • Crystallographic analysis.

Main Results:

  • NaMnSO4F crystallizes in the monoclinic C2/c space group, isostructural to triplite minerals.
  • The structure features edge-sharing MO4F2 octahedra interconnected by SO4 tetrahedra, forming a 3D framework.
  • Na and Mn cations randomly occupy the MO4F2 octahedra with a near 1:1 ratio.
  • The random cation distribution precludes the formation of channels for Na-ion conduction.

Conclusions:

  • The determined crystal structure of NaMnSO4F explains its lack of electrochemical activity.
  • The random occupancy of Na and Mn sites is a key factor limiting ion transport.
  • This study provides insights into structure-property relationships in alkali metal fluorosulfates and triplite-type compounds.