CeNiSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Ni(1), four equivalent Si(1), and six equivalent Si(2) atoms. Ni(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(2), and four equivalent Si(1) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to four equivalent Ce(1) and four equivalent Ni(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to six equivalent Ce(1), one Ni(1), and two equivalent Si(2) atoms.
CeNiSi2 crystallizes in the orthorhombic Cmcm space group. Ce(1) is bonded in a 14-coordinate geometry to four equivalent Ni(1), four equivalent Si(1), and six equivalent Si(2) atoms. All Ce(1)-Ni(1) bond lengths are 3.12 Å. There are two shorter (3.08 Å) and two longer (3.12 Å) Ce(1)-Si(1) bond lengths. There are four shorter (3.08 Å) and two longer (3.16 Å) Ce(1)-Si(2) bond lengths. Ni(1) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(2), and four equivalent Si(1) atoms. The Ni(1)-Si(2) bond length is 2.29 Å. There are two shorter (2.32 Å) and two longer (2.34 Å) Ni(1)-Si(1) bond lengths. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to four equivalent Ce(1) and four equivalent Ni(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to six equivalent Ce(1), one Ni(1), and two equivalent Si(2) atoms. Both Si(2)-Si(2) bond lengths are 2.41 Å.