CeAgSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Ag(1), four equivalent Si(2), and six equivalent Si(1) atoms. Ag(1) is bonded to four equivalent Ce(1), four equivalent Ag(1), and four equivalent Si(2) atoms to form a mixture of distorted face and corner-sharing AgCe4Si4Ag4 cuboctahedra. 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 Si(2), and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to four equivalent Ce(1), four equivalent Ag(1), and one Si(1) atom.
CeAgSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Ag(1), four equivalent Si(2), and six equivalent Si(1) atoms. There are two shorter (3.40 Å) and two longer (3.45 Å) Ce(1)-Ag(1) bond lengths. All Ce(1)-Si(2) bond lengths are 3.21 Å. There are two shorter (3.09 Å) and four longer (3.19 Å) Ce(1)-Si(1) bond lengths. Ag(1) is bonded to four equivalent Ce(1), four equivalent Ag(1), and four equivalent Si(2) atoms to form a mixture of distorted face and corner-sharing AgCe4Si4Ag4 cuboctahedra. All Ag(1)-Ag(1) bond lengths are 2.99 Å. There are two shorter (2.58 Å) and two longer (2.61 Å) Ag(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 Si(2), and two equivalent Si(1) atoms. The Si(1)-Si(2) bond length is 2.31 Å. Both Si(1)-Si(1) bond lengths are 2.39 Å. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to four equivalent Ce(1), four equivalent Ag(1), and one Si(1) atom.