Na3Sn is beta Cu3Ti-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent Na(2) and four equivalent Sn(1) atoms to form distorted NaNa4Sn4 cuboctahedra that share corners with eight equivalent Na(1)Na4Sn4 cuboctahedra, corners with eight equivalent Na(2)Na8Sn4 cuboctahedra, corners with eight equivalent Sn(1)Na12 cuboctahedra, edges with four equivalent Na(2)Na8Sn4 cuboctahedra, edges with four equivalent Sn(1)Na12 cuboctahedra, edges with twelve equivalent Na(1)Na4Sn4 cuboctahedra, and faces with six equivalent Na(1)Na4Sn4 cuboctahedra. In the second Na site, Na(2) is bonded to eight equivalent Na(1) and four equivalent Sn(1) atoms to form distorted NaNa8Sn4 cuboctahedra that share corners with four equivalent Na(2)Na8Sn4 cuboctahedra, corners with eight equivalent Sn(1)Na12 cuboctahedra, corners with sixteen equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(2)Na8Sn4 cuboctahedra, faces with four equivalent Na(2)Na8Sn4 cuboctahedra, and faces with six equivalent Sn(1)Na12 cuboctahedra. Sn(1) is bonded to four equivalent Na(2) and eight equivalent Na(1) atoms to form SnNa12 cuboctahedra that share corners with four equivalent Sn(1)Na12 cuboctahedra, corners with eight equivalent Na(2)Na8Sn4 cuboctahedra, corners with sixteen equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Sn(1)Na12 cuboctahedra, faces with four equivalent Sn(1)Na12 cuboctahedra, and faces with six equivalent Na(2)Na8Sn4 cuboctahedra.
Na3Sn is beta Cu3Ti-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent Na(2) and four equivalent Sn(1) atoms to form distorted NaNa4Sn4 cuboctahedra that share corners with eight equivalent Na(1)Na4Sn4 cuboctahedra, corners with eight equivalent Na(2)Na8Sn4 cuboctahedra, corners with eight equivalent Sn(1)Na12 cuboctahedra, edges with four equivalent Na(2)Na8Sn4 cuboctahedra, edges with four equivalent Sn(1)Na12 cuboctahedra, edges with twelve equivalent Na(1)Na4Sn4 cuboctahedra, and faces with six equivalent Na(1)Na4Sn4 cuboctahedra. All Na(1)-Na(2) bond lengths are 3.36 Å. All Na(1)-Sn(1) bond lengths are 3.36 Å. In the second Na site, Na(2) is bonded to eight equivalent Na(1) and four equivalent Sn(1) atoms to form distorted NaNa8Sn4 cuboctahedra that share corners with four equivalent Na(2)Na8Sn4 cuboctahedra, corners with eight equivalent Sn(1)Na12 cuboctahedra, corners with sixteen equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(2)Na8Sn4 cuboctahedra, faces with four equivalent Na(2)Na8Sn4 cuboctahedra, and faces with six equivalent Sn(1)Na12 cuboctahedra. All Na(2)-Sn(1) bond lengths are 3.44 Å. Sn(1) is bonded to four equivalent Na(2) and eight equivalent Na(1) atoms to form SnNa12 cuboctahedra that share corners with four equivalent Sn(1)Na12 cuboctahedra, corners with eight equivalent Na(2)Na8Sn4 cuboctahedra, corners with sixteen equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Na(1)Na4Sn4 cuboctahedra, edges with eight equivalent Sn(1)Na12 cuboctahedra, faces with four equivalent Sn(1)Na12 cuboctahedra, and faces with six equivalent Na(2)Na8Sn4 cuboctahedra.