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

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.