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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.
SmRu4B4 crystallizes in the tetragonal I4_1/acd space group. The structure is three-dimensional. Sm3+ is bonded to twelve equivalent B3- atoms to form distorted SmB12 cuboctahedra that share corners with twelve equivalent RuB5 trigonal bipyramids, edges with twelve equivalent SmB12 cuboctahedra, edges with four equivalent RuB5 trigonal bipyramids, and faces with twelve equivalent RuB5 trigonal bipyramids. There are a spread of Sm–B bond distances ranging from 2.99–3.23 Å. Ru+2.25+ is bonded to five equivalent B3- atoms to form distorted RuB5 trigonal bipyramids that share corners with three equivalent SmB12 cuboctahedra, corners with eight equivalent RuB5 trigonal bipyramids, an edgeedge with one SmB12 cuboctahedra, edges with six equivalent RuB5 trigonal bipyramids, and faces with three equivalent SmB12 cuboctahedra. There are a spread of Ru–B bond distances ranging from 2.16–2.31 Å. B3- is bonded in a 6-coordinate geometry to three equivalent Sm3+, five equivalent Ru+2.25+, and one B3- atom. The B–B bond length is 1.80 Å.
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.