When n-hexane solutions of an excess of sodium bis(trimethylsilyl)amide (NaHMDS) are combined with cesium halide (halide = Cl, Br, or I) in the presence of the tetradentate donor molecule [tris [2-(dimethylamino)ethynamine] (Me6TREN), the isolation and characterization of a series of sodium amide/sodium halide mixed aggregates was forthcoming. Cesium halide was employed because it efficiently reacted with NaHMDS to produce a molecular, soluble source of sodium halide salt (which was subsequently captured by an excess of NaHMDS) via a methathetical reaction. These mixed sodium amide/sodium halide complexes are formally sodium sodiates, are deficient in halide with respect to the amide, and have the general formula [{Na-5(mu-HMDS)(5)(mu(5)-X)}{Na(Me6TREN)}] [where X = Cl (1), Br (2), or I (3)]. The influence of the donor ligand was studied for the NaI/NaHMDS system, and when n-hexane solutions of this composition were treated with tridentate donors such as N,N,N',N '',N ''-pentamethyldiethylenetriamine (PMDETA) or N,N,M,N'-tetramethyldiaminoethyl ether (TMDAE), solvent-separated ion-pair cocomplexes [Na-5(mu-HMDS)(5)(mu(5)-I](-)[Na-3(mu-HMDS)(2)(PMDETA)(2)](+) (4) and [Na-5(mu-HMDS)(5)(mu(5)-I](-)[Na(TMDAE)(2)](+) (5) were isolated. However, upon reaction with bidentate proligands such as the chiral diamine (R,R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] or N,N,N',N'-tetramethylethylenediamine (TMEDA), neutral complexes [Na-4(y-HMDS)(3)(mu(4)-I)(donor)(2)] [donor = (R,R)-TMCDA (6) and TMEDA (7)] were produced. To illustrate the generality of the latter reaction with other halides, [Na-4(mu-HMDS)(3)(mu(4)-Br)(TMEDA)(2)] (8) was also prepared by employing NaBr in the synthesis instead of NaI.