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ScB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Sc is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing ScB12 cuboctahedra. All Sc–B bond lengths are 2.53 Å. B is bonded in a 9-coordinate geometry to six equivalent Sc and three equivalent B atoms. All B–B bond lengths are 1.82 Å.
ScB2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Sc is bonded in a 12-coordinate geometry to twelve equivalent B atoms. All Sc–B bond lengths are 2.54 Å. B is bonded to six equivalent Sc and six equivalent B atoms to form a mixture of face, edge, and corner-sharing BSc6B6 cuboctahedra. All B–B bond lengths are 2.17 Å.