CeFeSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Fe(1), four equivalent Si(2), and six equivalent Si(1) atoms. Fe(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(1), and four equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to six equivalent Ce(1), one Fe(1), and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to four equivalent Ce(1) and four equivalent Fe(1) atoms.
CeFeSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Fe(1), four equivalent Si(2), and six equivalent Si(1) atoms. All Ce(1)-Fe(1) bond lengths are 3.04 Å. There are two shorter (3.07 Å) and two longer (3.08 Å) Ce(1)-Si(2) bond lengths. There are four shorter (3.07 Å) and two longer (3.23 Å) Ce(1)-Si(1) bond lengths. Fe(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(1), and four equivalent Si(2) atoms. The Fe(1)-Si(1) bond length is 2.26 Å. There are two shorter (2.36 Å) and two longer (2.37 Å) Fe(1)-Si(2) bond lengths. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to six equivalent Ce(1), one Fe(1), and two equivalent Si(1) atoms. Both Si(1)-Si(1) bond lengths are 2.41 Å. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to four equivalent Ce(1) and four equivalent Fe(1) atoms.