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A disproportionation process of a metastable AlCl solution with a simultaneous ligand exchange-Cl is substituted by N(SiMe(3))(2)-leads to a [Al(69)N(SiMe(3))(2)](3-) cluster compound that can be regarded as an intermediate on the way to bulk metal formation. The cluster was characterized by an X-ray crystal structural analysis. Regarding its structure and the packing within the crystal, this metalloid cluster with 4 times more Al atoms than ligands is compared to the Al(77)N(SiMe(3))(2)](2-) cluster that has been published four years ago. Although there is a similar packing density of the Al atoms in both clusters as well as in Al metal, the X-ray structural analysis shows significant differences in topology and distance proportions. The differences between these-at a first glance almost identical-Al clusters demonstrate that results of physical measuring, e.g., of nanostructured surfaces which carry supposedly identical cluster species, have to be interpreted with great caution. [on SciFinder (R)]