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NdB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-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 3.04 Å. B is bonded in a 1-coordinate geometry to four equivalent Nd and five equivalent B atoms. There is one shorter (1.65 Å) and four longer (1.76 Å) B–B bond length.
Nd(RuB)2 crystallizes in the orthorhombic Fddd space group. The structure is three-dimensional. Nd2+ is bonded to six equivalent B3- atoms to form distorted NdB6 octahedra that share corners with four equivalent NdB6 octahedra, corners with twelve equivalent RuB4 tetrahedra, edges with four equivalent NdB6 octahedra, and edges with six equivalent RuB4 tetrahedra. The corner-sharing octahedral tilt angles are 23°. There are two shorter (2.90 Å) and four longer (3.06 Å) Nd–B bond lengths. Ru2+ is bonded to four equivalent B3- atoms to form distorted RuB4 tetrahedra that share corners with six equivalent NdB6 octahedra, corners with six equivalent RuB4 tetrahedra, edges with three equivalent NdB6 octahedra, and edges with three equivalent RuB4 tetrahedra. The corner-sharing octahedra tilt angles range from 39–95°. There are two shorter (2.09 Å) and two longer (2.16 Å) Ru–B bond lengths. B3- is bonded in a 7-coordinate geometry to three equivalent Nd2+ and four equivalent Ru2+ atoms.