Ce3(RhSi)2 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to four equivalent Rh(1), two equivalent Si(1), and three equivalent Si(2) atoms. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to four equivalent Rh(1), two equivalent Si(2), and three equivalent Si(1) atoms. Rh(1) is bonded in a 9-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), one Si(2), and two equivalent Si(1) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent Ce(1), six equivalent Ce(2), and four equivalent Rh(1) atoms to form a mixture of distorted face, corner, and edge-sharing SiCe8Rh4 cuboctahedra. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to three equivalent Ce(1), four equivalent Ce(2), and two equivalent Rh(1) atoms.
Ce3(RhSi)2 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to four equivalent Rh(1), two equivalent Si(1), and three equivalent Si(2) atoms. There are two shorter (3.03 Å) and two longer (3.12 Å) Ce(1)-Rh(1) bond lengths. Both Ce(1)-Si(1) bond lengths are 3.29 Å. There are a spread of Ce(1)-Si(2) bond distances ranging from 3.00-3.05 Å. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to four equivalent Rh(1), two equivalent Si(2), and three equivalent Si(1) atoms. There are two shorter (2.91 Å) and two longer (3.11 Å) Ce(2)-Rh(1) bond lengths. There is one shorter (3.03 Å) and one longer (3.06 Å) Ce(2)-Si(2) bond length. There are a spread of Ce(2)-Si(1) bond distances ranging from 3.24-3.37 Å. Rh(1) is bonded in a 9-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), one Si(2), and two equivalent Si(1) atoms. The Rh(1)-Si(2) bond length is 2.49 Å. There is one shorter (2.57 Å) and one longer (2.58 Å) Rh(1)-Si(1) bond length. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent Ce(1), six equivalent Ce(2), and four equivalent Rh(1) atoms to form a mixture of distorted face, corner, and edge-sharing SiCe8Rh4 cuboctahedra. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to three equivalent Ce(1), four equivalent Ce(2), and two equivalent Rh(1) atoms.