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PuAu3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pu3+ is bonded to twelve equivalent Au1- atoms to form a mixture of corner and face-sharing PuAu12 cuboctahedra. There are six shorter (3.10 Å) and six longer (3.19 Å) Pu–Au bond lengths. Au1- is bonded in a distorted see-saw-like geometry to four equivalent Pu3+ atoms.
PuAu3 is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Pu3+ is bonded in a distorted body-centered cubic geometry to fourteen Au1- atoms. There are eight shorter (3.00 Å) and six longer (3.47 Å) Pu–Au bond lengths. There are two inequivalent Au1- sites. In the first Au1- site, Au1- is bonded to four equivalent Pu3+ and four equivalent Au1- atoms to form a mixture of distorted edge, face, and corner-sharing AuPu4Au4 tetrahedra. All Au–Au bond lengths are 3.00 Å. In the second Au1- site, Au1- is bonded in a 8-coordinate geometry to six equivalent Pu3+ and eight equivalent Au1- atoms.