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NdB12 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Nd is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Nd–B bond lengths are 2.82 Å. B is bonded in a 7-coordinate geometry to two equivalent Nd and five equivalent B atoms. There is one shorter (1.75 Å) and four longer (1.80 Å) B–B bond length.
NdB4 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Nd is bonded to twelve equivalent B atoms to form a mixture of face and edge-sharing NdB12 cuboctahedra. There are a spread of Nd–B bond distances ranging from 2.60–2.84 Å. B is bonded in a 5-coordinate geometry to three equivalent Nd and two equivalent B atoms. There is one shorter (1.67 Å) and one longer (1.70 Å) B–B bond length.