Synthesis and Characterization of Lithium Pyrocarbonate (Li[CO]) and Lithium Hydrogen Pyrocarbonate (Li[HCO]).

The anhydrous pyrocarbonate and the first hydrogen pyrocarbonate Li[HCO] have been synthesized in a laser-heated diamond anvil cell at moderate pressures (  GPa). The structures of the two compounds have been obtained from single crystal X-ray diffraction data. Raman spectroscopy and DFT calculations have been employed to further characterize their structure-property relations. The present results significantly enlarge the group of inorganic pyrocarbonates by the discovery of the hydrogenated pyrocarbonate anion Li[HCO]. In the structure of Li[HCO] there is a symmetric O-H-O arrangement at high pressures, which converts to a conventional O-H O hydrogen bond upon pressure release.