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Crystal structure, vibrational spectra and thermal decomposition study of a new, dicationic, acidic pyrophosphate: KHMgP2O7⋅2H2O

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Abstract

Colourless crystals of a new, dicationic, hydropyrophosphate dihydrate salt, KHMgP2O7⋅ 2H2O, are formed, when a mixture of aqueous equimolar solutions of MgCl2⋅4H2O and K4P2O7, at pH 2.12, are left to stand at ambient temperature for 4 days. The new pyrophosphate salt has been characterized by single-crystal X-ray diffraction, IR and Raman spectra, and DSC-TG thermal analysis. The structure consists of alternating layers of [HP2O7]3− groups and MgO6 octahedra, joined by K+ ions and bridging hydrogen bonds. The [P2O7]4− anions exhibit a bent eclipsed conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The 31P chemical shift tensor components have been determined from the solid-state MAS NMR spectra. The structural changes occurring during thermal decomposition have been examined by TG-DSC, X-ray powder diffraction (XRD) and IR spectroscopy. When the new pyrophosphate salt is heated gradually, it first becomes amorphous and then condenses to chain metaphosphates.

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Authors and Affiliations

  1. Department of Chemistry, McGill University, Otto Maass Building, 801 Sherbrooke Street West, Montréal, Québec, Canada, H3A 2K6

    Hassane Assaaoudi & Ian S. Butler

  2. Energy and Environmental Research Group, Department of Mining, Metals and Materials Engineering, McGill University, Wong Building, Room 2290, 3610 University St., Montréal, Québec, Canada, H3A 2B2

    Hassane Assaaoudi & Janusz Kozinski

  3. Université de Montréal, C.P. 6128, Succ. Centre-ville, Montréal, Québec, Canada, H3C 3J7

    Francine Bélanger-Gariépy

Authors
  1. Hassane Assaaoudi
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  2. Ian S. Butler
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  3. Janusz Kozinski
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  4. Francine Bélanger-Gariépy
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Correspondence to Ian S. Butler.

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Assaaoudi, H., Butler, I.S., Kozinski, J. et al. Crystal structure, vibrational spectra and thermal decomposition study of a new, dicationic, acidic pyrophosphate: KHMgP2O7⋅2H2O. J Chem Crystallogr 35, 809–820 (2005). https://doi.org/10.1007/s10870-005-4551-z

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  • DOI: https://doi.org/10.1007/s10870-005-4551-z

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