The reaction of LiN(SiMe3)(2) with 1 equiv of HOCH2CMe3 (HONep) in toluene led to the formation of [Li(mu (3)-ONep)](8) (1). The complex adopts a novel dual-edge fused hexagon-square prismatic structure with a C-2 nu axis of rotation that relates the top and bottom eight-membered rings. Substituting the noncoordinating solvent toluene for a Lewis basic solvent (THF or py) led to the isolation of compounds of the general formula [Li(mu (3)-ONep)](4)-(solv)(3), where solv = THF (2) or py (3). The cube structures of 2 and 3 have one Li which is not solvated because of steric crowding of the ONep ligands. Multinuclear solid-state (Li-6, Li-7, and C-13) MAS and solution-state (H-1, Li-7, and C-13) NMR studies were undertaken to verify the identity of the bulk powder and to determine the solution behavior of these compounds.