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Issue 45, 2015
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AgPO2F2 and Ag9(PO2F2)14: the first Ag(I) and Ag(I)/Ag(II) difluorophosphates with complex crystal structures

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Abstract

The reaction of AgF2 with P2O3F4 yields a mixed valence AgI/AgII difluorophosphate salt with AgI4AgII5(PO2F2)14 stoichiometry – the first Ag(II)–PO2F2 system known. This highly moisture sensitive brown solid is thermally stable up to 120 °C, which points at further feasible extension of the chemistry of Ag(II)–PO2F2 systems. The crystal structure shows a very complex bonding pattern, comprising of polymeric AgII5(PO2F2)144− anions and two types of AgI cations. One particular AgII site present in the crystal structure of Ag9(PO2F2)14 is the first known example of square pyramidal penta-coordinated Ag(II) in an oxo-ligand environment. Ag(I)PO2F2 – the product of the thermal decomposition of Ag9(PO2F2)14 – has also been characterized by thermal analysis, IR spectroscopy and X-ray powder diffraction. It has a complicated crystal structure as well, which consists of infinite 1D [AgIO4/2] chains which are linked to more complex 3D structures via OPO bridges. The PO2F2 anions bind to cations in both compounds as bidentate oxo-ligands. The terminal F atoms tend to point inside the van der Waals cavities in the crystal structure of both compounds. All important structural details of both title compounds were corroborated by DFT calculations.

Graphical abstract: AgPO2F2 and Ag9(PO2F2)14: the first Ag(i) and Ag(i)/Ag(ii) difluorophosphates with complex crystal structures

  • This article is part of the themed collection: Fluorine
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Publication details

The article was received on 28 May 2015, accepted on 01 Jul 2015 and first published on 22 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT02004B
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Citation: Dalton Trans., 2015,44, 19478-19486
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    AgPO2F2 and Ag9(PO2F2)14: the first Ag(I) and Ag(I)/Ag(II) difluorophosphates with complex crystal structures

    P. J. Malinowski, D. Kurzydłowski and W. Grochala, Dalton Trans., 2015, 44, 19478
    DOI: 10.1039/C5DT02004B

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