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Pm3I crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pm is bonded in a distorted see-saw-like geometry to four equivalent I atoms. There are two shorter (3.53 Å) and two longer (3.54 Å) Pm–I bond lengths. I is bonded to twelve equivalent Pm atoms to form a mixture of face and corner-sharing IPm12 cuboctahedra.
Pm3I is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Pm sites. In the first Pm site, Pm is bonded to four equivalent I atoms to form a mixture of distorted corner and edge-sharing PmI4 cuboctahedra. All Pm–I bond lengths are 3.65 Å. In the second Pm site, Pm is bonded in a square co-planar geometry to four equivalent I atoms. All Pm–I bond lengths are 3.46 Å. I is bonded to twelve Pm atoms to form a mixture of corner, edge, and face-sharing IPm12 cuboctahedra.