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Pu3I is Uranium Silicide-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pu is bonded in a distorted see-saw-like geometry to four equivalent I atoms. There are two shorter (3.32 Å) and two longer (3.41 Å) Pu–I bond lengths. I is bonded to twelve equivalent Pu atoms to form a mixture of corner and face-sharing IPu12 cuboctahedra.
Pu3I is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Pu sites. In the first Pu site, Pu is bonded to four equivalent I atoms to form a mixture of distorted edge and corner-sharing PuI4 cuboctahedra. All Pu–I bond lengths are 3.28 Å. In the second Pu site, Pu is bonded in a square co-planar geometry to four equivalent I atoms. All Pu–I bond lengths are 3.17 Å. I is bonded to twelve Pu atoms to form a mixture of edge, corner, and face-sharing IPu12 cuboctahedra.