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PuB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Pu6+ is bonded in a 1-coordinate geometry to twenty-four equivalent B1- atoms. All Pu–B bond lengths are 3.02 Å. B1- is bonded in a 1-coordinate geometry to four equivalent Pu6+ and five equivalent B1- atoms. There is one shorter (1.63 Å) and four longer (1.75 Å) B–B bond length.
BPu is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Pu3+ is bonded to six equivalent B3- atoms to form a mixture of corner and edge-sharing PuB6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Pu–B bond lengths are 2.58 Å. B3- is bonded to six equivalent Pu3+ atoms to form a mixture of corner and edge-sharing BPu6 octahedra. The corner-sharing octahedral tilt angles are 0°.