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SmB12 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Sm is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Sm–B bond lengths are 2.81 Å. B is bonded in a 7-coordinate geometry to two equivalent Sm and five equivalent B atoms. There is one shorter (1.74 Å) and four longer (1.80 Å) B–B bond length.
SmB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Sm is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing SmB12 cuboctahedra. All Sm–B bond lengths are 2.79 Å. B is bonded in a 9-coordinate geometry to six equivalent Sm and three equivalent B atoms. All B–B bond lengths are 1.92 Å.