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PuB12 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Pu6+ is bonded in a 1-coordinate geometry to twenty-four equivalent B+0.50- atoms. All Pu–B bond lengths are 2.78 Å. B+0.50- is bonded in a 7-coordinate geometry to two equivalent Pu6+ and five equivalent B+0.50- atoms. There is one shorter (1.71 Å) and four longer (1.79 Å) B–B bond length.
PuNpB4 is hexagonal omega structure-derived structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Pu3+ is bonded to twelve equivalent B+1.50- atoms to form PuB12 cuboctahedra that share edges with twelve equivalent NpB12 cuboctahedra, faces with two equivalent NpB12 cuboctahedra, and faces with six equivalent PuB12 cuboctahedra. All Pu–B bond lengths are 2.69 Å. Np3+ is bonded to twelve equivalent B+1.50- atoms to form NpB12 cuboctahedra that share edges with twelve equivalent PuB12 cuboctahedra, faces with two equivalent PuB12 cuboctahedra, and faces with six equivalent NpB12 cuboctahedra. All Np–B bond lengths are 2.68 Å. B+1.50- is bonded in a 3-coordinate geometry to three equivalent Pu3+, three equivalent Np3+, and three equivalent B+1.50- atoms. All B–B bond lengths are 1.79 Å.
PuB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Pu6+ is bonded to twelve equivalent B3- atoms to form a mixture of edge and face-sharing PuB12 cuboctahedra. All Pu–B bond lengths are 2.70 Å. B3- is bonded in a 9-coordinate geometry to six equivalent Pu6+ and three equivalent B3- atoms. All B–B bond lengths are 1.82 Å.