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

Abstract: 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 β 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. [Copyright &y& Elsevier]