NaSc3 is beta Cu3Ti-like structured and crystallizes in the tetragonal I4/mmm space group. Na(1) is bonded to four equivalent Sc(2) and eight equivalent Sc(1) atoms to form NaSc12 cuboctahedra that share corners with four equivalent Na(1)Sc12 cuboctahedra, corners with eight equivalent Sc(2)Na4Sc8 cuboctahedra, edges with eight equivalent Na(1)Sc12 cuboctahedra, edges with sixteen equivalent Sc(1)Na4Sc8 cuboctahedra, faces with four equivalent Na(1)Sc12 cuboctahedra, faces with six equivalent Sc(2)Na4Sc8 cuboctahedra, and faces with eight equivalent Sc(1)Na4Sc8 cuboctahedra. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to four equivalent Na(1), four equivalent Sc(1), and four equivalent Sc(2) atoms to form distorted ScNa4Sc8 cuboctahedra that share corners with twelve equivalent Sc(1)Na4Sc8 cuboctahedra, edges with eight equivalent Na(1)Sc12 cuboctahedra, edges with eight equivalent Sc(1)Na4Sc8 cuboctahedra, edges with eight equivalent Sc(2)Na4Sc8 cuboctahedra, faces with four equivalent Na(1)Sc12 cuboctahedra, faces with four equivalent Sc(2)Na4Sc8 cuboctahedra, and faces with ten equivalent Sc(1)Na4Sc8 cuboctahedra. In the second Sc site, Sc(2) is bonded to four equivalent Na(1) and eight equivalent Sc(1) atoms to form distorted ScNa4Sc8 cuboctahedra that share corners with four equivalent Sc(2)Na4Sc8 cuboctahedra, corners with eight equivalent Na(1)Sc12 cuboctahedra, edges with eight equivalent Sc(2)Na4Sc8 cuboctahedra, edges with sixteen equivalent Sc(1)Na4Sc8 cuboctahedra, faces with four equivalent Sc(2)Na4Sc8 cuboctahedra, faces with six equivalent Na(1)Sc12 cuboctahedra, and faces with eight equivalent Sc(1)Na4Sc8 cuboctahedra.
NaSc3 is beta Cu3Ti-like structured and crystallizes in the tetragonal I4/mmm space group. Na(1) is bonded to four equivalent Sc(2) and eight equivalent Sc(1) atoms to form NaSc12 cuboctahedra that share corners with four equivalent Na(1)Sc12 cuboctahedra, corners with eight equivalent Sc(2)Na4Sc8 cuboctahedra, edges with eight equivalent Na(1)Sc12 cuboctahedra, edges with sixteen equivalent Sc(1)Na4Sc8 cuboctahedra, faces with four equivalent Na(1)Sc12 cuboctahedra, faces with six equivalent Sc(2)Na4Sc8 cuboctahedra, and faces with eight equivalent Sc(1)Na4Sc8 cuboctahedra. All Na(1)-Sc(2) bond lengths are 3.31 Å. All Na(1)-Sc(1) bond lengths are 3.36 Å. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to four equivalent Na(1), four equivalent Sc(1), and four equivalent Sc(2) atoms to form distorted ScNa4Sc8 cuboctahedra that share corners with twelve equivalent Sc(1)Na4Sc8 cuboctahedra, edges with eight equivalent Na(1)Sc12 cuboctahedra, edges with eight equivalent Sc(1)Na4Sc8 cuboctahedra, edges with eight equivalent Sc(2)Na4Sc8 cuboctahedra, faces with four equivalent Na(1)Sc12 cuboctahedra, faces with four equivalent Sc(2)Na4Sc8 cuboctahedra, and faces with ten equivalent Sc(1)Na4Sc8 cuboctahedra. All Sc(1)-Sc(1) bond lengths are 3.31 Å. All Sc(1)-Sc(2) bond lengths are 3.36 Å. In the second Sc site, Sc(2) is bonded to four equivalent Na(1) and eight equivalent Sc(1) atoms to form distorted ScNa4Sc8 cuboctahedra that share corners with four equivalent Sc(2)Na4Sc8 cuboctahedra, corners with eight equivalent Na(1)Sc12 cuboctahedra, edges with eight equivalent Sc(2)Na4Sc8 cuboctahedra, edges with sixteen equivalent Sc(1)Na4Sc8 cuboctahedra, faces with four equivalent Sc(2)Na4Sc8 cuboctahedra, faces with six equivalent Na(1)Sc12 cuboctahedra, and faces with eight equivalent Sc(1)Na4Sc8 cuboctahedra.