Ce2Si3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(3), and four equivalent Si(2) atoms. In the second Ce site, Ce(2) is bonded in a 10-coordinate geometry to two equivalent Si(2), four equivalent Si(1), and four equivalent Si(3) atoms. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 7-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), and one Si(3) atom. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to two equivalent Ce(2), four equivalent Ce(1), and two equivalent Si(3) atoms. In the third Si site, Si(3) is bonded in a 9-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), one Si(1), and two equivalent Si(2) atoms.
Ce2Si3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(3), and four equivalent Si(2) atoms. Both Ce(1)-Si(1) bond lengths are 3.02 Å. Both Ce(1)-Si(3) bond lengths are 3.13 Å. All Ce(1)-Si(2) bond lengths are 3.03 Å. In the second Ce site, Ce(2) is bonded in a 10-coordinate geometry to two equivalent Si(2), four equivalent Si(1), and four equivalent Si(3) atoms. Both Ce(2)-Si(2) bond lengths are 3.19 Å. All Ce(2)-Si(1) bond lengths are 3.10 Å. All Ce(2)-Si(3) bond lengths are 3.06 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 7-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), and one Si(3) atom. The Si(1)-Si(3) bond length is 2.33 Å. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to two equivalent Ce(2), four equivalent Ce(1), and two equivalent Si(3) atoms. Both Si(2)-Si(3) bond lengths are 2.35 Å. In the third Si site, Si(3) is bonded in a 9-coordinate geometry to two equivalent Ce(1), four equivalent Ce(2), one Si(1), and two equivalent Si(2) atoms.