Brønsted acid–base reactions with anhydrous sulfamates as a pathway to [SO3N]3−-containing compounds: Preparation of Li3SO3N

Li3SO3N has been prepared by the mechanochemical reaction between lithium sulfamate (LiSO3NH2) and lithium amide or lithium hydride. This is the first example of an anhydrous compound containing the rare [SO3N]3− polyanion. Li3SO3N adopts the low-temperature Pmn21Pmn21β structure of isoelectronic Li3PO4. Structural refinement from neutron powder diffraction data supports disordering of nitrogen over two of the three anion sites, although a fully disordered model cannot be conclusively refuted. While the compound is a poor ionic conductor, it is electrochemically stable to at least 5 V vs. Li+/Li0. This simple mechanochemical pathway should be suitable for preparing a host of other alkali-rich nitrogen-containing polyanionic compounds.

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