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PmAu3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pm3+ is bonded to twelve equivalent Au1- atoms to form a mixture of corner and face-sharing PmAu12 cuboctahedra. There are six shorter (3.12 Å) and six longer (3.22 Å) Pm–Au bond lengths. Au1- is bonded in a distorted rectangular see-saw-like geometry to four equivalent Pm3+ atoms.
PmAu3 is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Pm3+ is bonded in a distorted body-centered cubic geometry to fourteen Au1- atoms. There are eight shorter (3.05 Å) and six longer (3.52 Å) Pm–Au bond lengths. There are two inequivalent Au1- sites. In the first Au1- site, Au1- is bonded to four equivalent Pm3+ and four equivalent Au1- atoms to form a mixture of distorted face, edge, and corner-sharing AuPm4Au4 tetrahedra. All Au–Au bond lengths are 3.05 Å. In the second Au1- site, Au1- is bonded in a 8-coordinate geometry to six equivalent Pm3+ and eight equivalent Au1- atoms.