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LaB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. La is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All La–B bond lengths are 3.05 Å. B is bonded in a 1-coordinate geometry to four equivalent La and five equivalent B atoms. There is one shorter (1.66 Å) and four longer (1.77 Å) B–B bond length.
LaB4 crystallizes in the tetragonal P4/mbm space group. The structure is three-dimensional. La is bonded in a 8-coordinate geometry to eighteen B atoms. There are a spread of La–B bond distances ranging from 2.81–3.14 Å. There are three inequivalent B sites. In the first B site, B is bonded in a 9-coordinate geometry to four equivalent La and five B atoms. There is one shorter (1.72 Å) and four longer (1.79 Å) B–B bond length. In the second B site, B is bonded in a 9-coordinate geometry to four equivalent La and five B atoms. There is one shorter (1.77 Å) and two longer (1.84 Å) B–B bond length. In the third B site, B is bonded in a distorted trigonal planar geometry to six equivalent La and three B atoms. The B–B bond length is 1.84 Å.