CeRhAl4Si2 crystallizes in the tetragonal P4/mmm space group. Ce(1) is bonded in a 16-coordinate geometry to eight equivalent Al(1) and eight equivalent Si(1) atoms. Rh(1) is bonded in a body-centered cubic geometry to eight equivalent Al(1) atoms. Al(1) is bonded to two equivalent Ce(1), two equivalent Rh(1), and two equivalent Si(1) atoms to form a mixture of distorted edge, face, and corner-sharing AlCe2Si2Rh2 tetrahedra. Si(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), four equivalent Al(1), and one Si(1) atom.
CeRhAl4Si2 crystallizes in the tetragonal P4/mmm space group. Ce(1) is bonded in a 16-coordinate geometry to eight equivalent Al(1) and eight equivalent Si(1) atoms. All Ce(1)-Al(1) bond lengths are 3.36 Å. All Ce(1)-Si(1) bond lengths are 3.21 Å. Rh(1) is bonded in a body-centered cubic geometry to eight equivalent Al(1) atoms. All Rh(1)-Al(1) bond lengths are 2.52 Å. Al(1) is bonded to two equivalent Ce(1), two equivalent Rh(1), and two equivalent Si(1) atoms to form a mixture of distorted edge, face, and corner-sharing AlCe2Si2Rh2 tetrahedra. Both Al(1)-Si(1) bond lengths are 2.58 Å. Si(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), four equivalent Al(1), and one Si(1) atom. The Si(1)-Si(1) bond length is 2.28 Å.