Alpha-crystalline Al2O3 displays a hexagonal closed packing structure (HCP) formed of Al3+ and O2- ions. Each Al3+ ion is surrounded by six O2- ions. The larger-sized O2- ions occupy octahedral voids while the smaller Al3+ ions occupy tetrahedral voids, altogether occupying 74% of the interstitial space, leaving the remainder empty.
Besides the hexagonal α-phase, other metastable phases of Al2O3 include the hexagonal χ-phase, the cubic η- and γ-phases, and the orthorhombic κ-phase.