Abstract Dibenzylhydroxylamine, (PhCH 2) 2NOH, is readily monolithiated to yield an unsolvated product, 1. In the solid state 1 is hexameric, with a core of two stacked (OLi) 3 rings. The metal centres are further coordinated by virtue of intra-monomer chelation using hydroxylamide N-centres, yielding three-membered NOLi rings. Ab initio M.O. calculations have been used to probe the structural options available for lithium hydroxylamide itself, [H 2NOLi] n ( n=1–4,6,8,9). The calculational findings shed light on why a hexameric structure is found in the experimental system.