LiSm(CuP)2 crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to six equivalent Cu(1) and six equivalent P(1) atoms to form distorted LiCu6P6 cuboctahedra that share corners with twelve equivalent Sm(1)P6 octahedra, faces with six equivalent Li(1)Cu6P6 cuboctahedra, and faces with two equivalent Sm(1)P6 octahedra. The corner-sharing octahedral tilt angles are 48°. Sm(1) is bonded to six equivalent P(1) atoms to form distorted SmP6 octahedra that share corners with twelve equivalent Li(1)Cu6P6 cuboctahedra, edges with six equivalent Sm(1)P6 octahedra, and faces with two equivalent Li(1)Cu6P6 cuboctahedra. Cu(1) is bonded in a 7-coordinate geometry to three equivalent Li(1) and four equivalent P(1) atoms. P(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), three equivalent Sm(1), and four equivalent Cu(1) atoms.
LiSm(CuP)2 crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to six equivalent Cu(1) and six equivalent P(1) atoms to form distorted LiCu6P6 cuboctahedra that share corners with twelve equivalent Sm(1)P6 octahedra, faces with six equivalent Li(1)Cu6P6 cuboctahedra, and faces with two equivalent Sm(1)P6 octahedra. The corner-sharing octahedral tilt angles are 48°. All Li(1)-Cu(1) bond lengths are 2.55 Å. All Li(1)-P(1) bond lengths are 2.79 Å. Sm(1) is bonded to six equivalent P(1) atoms to form distorted SmP6 octahedra that share corners with twelve equivalent Li(1)Cu6P6 cuboctahedra, edges with six equivalent Sm(1)P6 octahedra, and faces with two equivalent Li(1)Cu6P6 cuboctahedra. All Sm(1)-P(1) bond lengths are 2.92 Å. Cu(1) is bonded in a 7-coordinate geometry to three equivalent Li(1) and four equivalent P(1) atoms. There are three shorter (2.37 Å) and one longer (2.61 Å) Cu(1)-P(1) bond length. P(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), three equivalent Sm(1), and four equivalent Cu(1) atoms.