The crystal structures of intermetallic phases offer a wealth of geometrical features (helices, multishelled clusters, and host guest motifs) whose formation has yet to be explained or predicted by chemical theory. A recently developed extension of the acid base concept to metallic systems, the mu(3)-acidity model, provides an avenue for developing this understanding for intermetallics formed from transition metals. In this Article, we illustrate how this approach can be used to understand one of the most striking geometrical entities to emerge in intermetallic chemistry, the Mackay cluster of icosahedral quasicrystals. We present mu(3)-acidity analyses, based on DFT-calibrated Huckel calculations, for a series of Sc-Ir intermetallics: ScIr (CsCl-type), Sc2Ir (Ti2Ni-type), Sc11Ir4, and the Mackay cluster containing phases Sc57Ir13 and Sc44Ir7. We begin by illustrating that a mu(3)-acidity model correctly predicts that each of these phases is stable relative to disproportionation into their neighboring compounds when a common set of Huckel parameters and d-orbital occupancies is used. Next, we explain these results by developing a relationship between the distance distribution of homoatomic contacts within an atom's coordination sphere and the mu(3)-neutralization it experiences. For a given average homoatomic distance, the role of heteroatomic contacts is higher when the distribution of homoatomic contacts is narrower. This effect is key to the strength of the acid base neutralization of the Sc-rich phases, where the Sc atoms find a scarcity of Ir atoms from which to obtain neutralization. Under these circumstances, Sc-Ir contacts should be maximized, whereas the number and distance variations of the Sc Sc contacts should be minimized. These expectations are borne out by the observed crystal structures. In particular, the Mackay clusters of Sc57Ir13 and Sc44Ir7, in which a central Ir atom is icosahedrally coordinated by a pentagonal dodecahedral array of face-sharing Sc octahedra, represent a natural way of merging the competing needs for enhancing Sc-Ir interactions while diminishing those between the Sc atoms.