Na3Rh is alpha bismuth trifluoride 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 in a 4-coordinate geometry to four equivalent Na(2) and four equivalent Rh(1) atoms. In the second Na site, Na(2) is bonded to eight equivalent Na(1) and four equivalent Rh(1) atoms to form distorted NaNa8Rh4 cuboctahedra that share corners with four equivalent Na(2)Na8Rh4 cuboctahedra, corners with eight equivalent Rh(1)Na12 cuboctahedra, edges with eight equivalent Na(2)Na8Rh4 cuboctahedra, faces with four equivalent Na(2)Na8Rh4 cuboctahedra, and faces with six equivalent Rh(1)Na12 cuboctahedra. Rh(1) is bonded to four equivalent Na(2) and eight equivalent Na(1) atoms to form RhNa12 cuboctahedra that share corners with four equivalent Rh(1)Na12 cuboctahedra, corners with eight equivalent Na(2)Na8Rh4 cuboctahedra, edges with eight equivalent Rh(1)Na12 cuboctahedra, faces with four equivalent Rh(1)Na12 cuboctahedra, and faces with six equivalent Na(2)Na8Rh4 cuboctahedra.
Na3Rh is alpha bismuth trifluoride 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 in a 4-coordinate geometry to four equivalent Na(2) and four equivalent Rh(1) atoms. All Na(1)-Na(2) bond lengths are 3.14 Å. All Na(1)-Rh(1) bond lengths are 3.14 Å. In the second Na site, Na(2) is bonded to eight equivalent Na(1) and four equivalent Rh(1) atoms to form distorted NaNa8Rh4 cuboctahedra that share corners with four equivalent Na(2)Na8Rh4 cuboctahedra, corners with eight equivalent Rh(1)Na12 cuboctahedra, edges with eight equivalent Na(2)Na8Rh4 cuboctahedra, faces with four equivalent Na(2)Na8Rh4 cuboctahedra, and faces with six equivalent Rh(1)Na12 cuboctahedra. All Na(2)-Rh(1) bond lengths are 3.24 Å. Rh(1) is bonded to four equivalent Na(2) and eight equivalent Na(1) atoms to form RhNa12 cuboctahedra that share corners with four equivalent Rh(1)Na12 cuboctahedra, corners with eight equivalent Na(2)Na8Rh4 cuboctahedra, edges with eight equivalent Rh(1)Na12 cuboctahedra, faces with four equivalent Rh(1)Na12 cuboctahedra, and faces with six equivalent Na(2)Na8Rh4 cuboctahedra.