LiCeSi2 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 5-coordinate geometry to two equivalent Si(2) and three equivalent Si(1) atoms. Ce(1) is bonded in a 9-coordinate geometry to four equivalent Si(1) and five 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 three equivalent Li(1), four equivalent Ce(1), and two equivalent Si(2) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), five equivalent Ce(1), and two equivalent Si(1) atoms.
LiCeSi2 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 5-coordinate geometry to two equivalent Si(2) and three equivalent Si(1) atoms. There is one shorter (2.59 Å) and one longer (2.66 Å) Li(1)-Si(2) bond length. There are two shorter (2.64 Å) and one longer (2.65 Å) Li(1)-Si(1) bond length. Ce(1) is bonded in a 9-coordinate geometry to four equivalent Si(1) and five equivalent Si(2) atoms. There are a spread of Ce(1)-Si(1) bond distances ranging from 3.10-3.23 Å. There are a spread of Ce(1)-Si(2) bond distances ranging from 3.09-3.31 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to three equivalent Li(1), four equivalent Ce(1), and two equivalent Si(2) atoms. Both Si(1)-Si(2) bond lengths are 2.39 Å. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), five equivalent Ce(1), and two equivalent Si(1) atoms.