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LuB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Lu is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Lu–B bond lengths are 2.99 Å. B is bonded in a 1-coordinate geometry to four equivalent Lu and five equivalent B atoms. There is one shorter (1.62 Å) and four longer (1.74 Å) B–B bond length.
LuB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Lu is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing LuB12 cuboctahedra. All Lu–B bond lengths are 2.64 Å. B is bonded in a 9-coordinate geometry to six equivalent Lu and three equivalent B atoms. All B–B bond lengths are 1.87 Å.
LuB4 crystallizes in the tetragonal P4/mbm space group. The structure is three-dimensional. Lu is bonded in a 4-coordinate geometry to eighteen B atoms. There are a spread of Lu–B bond distances ranging from 2.70–3.04 Å. There are three inequivalent B sites. In the first B site, B is bonded in a 1-coordinate geometry to four equivalent Lu and five B atoms. There is one shorter (1.61 Å) and four longer (1.74 Å) B–B bond length. In the second B site, B is bonded in a 9-coordinate geometry to four equivalent Lu and five B atoms. There is one shorter (1.69 Å) and two longer (1.80 Å) B–B bond length. In the third B site, B is bonded in a distorted trigonal planar geometry to six equivalent Lu and three B atoms. The B–B bond length is 1.72 Å.