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ThO2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Th4+ is bonded in a body-centered cubic geometry to eight equivalent O2- atoms. All Th–O bond lengths are 2.43 Å. O2- is bonded to four equivalent Th4+ atoms to form a mixture of edge and corner-sharing OTh4 tetrahedra.
Th3O2 is Corundum structured and crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Th is bonded in a distorted rectangular see-saw-like geometry to four equivalent O atoms. There are two shorter (2.54 Å) and two longer (2.64 Å) Th–O bond lengths. O is bonded to six equivalent Th atoms to form a mixture of corner, edge, and face-sharing OTh6 octahedra. The corner-sharing octahedra tilt angles range from 49–50°.
Th3O crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Th sites. In the first Th site, Th is bonded in a 12-coordinate geometry to eight Th and four equivalent O atoms. There are four shorter (3.19 Å) and four longer (3.39 Å) Th–Th bond lengths. All Th–O bond lengths are 3.39 Å. In the second Th site, Th is bonded in a square co-planar geometry to eight equivalent Th and four equivalent O atoms. All Th–O bond lengths are 3.19 Å. O is bonded to twelve Th atoms to form a mixture of edge, corner, and face-sharing OTh12 cuboctahedra.