Ce2Si7 crystallizes in the orthorhombic Cmmm space group. Ce(1) is bonded in a 14-coordinate geometry to two equivalent Si(1), four equivalent Si(3), and eight equivalent Si(2) atoms. There are three inequivalent Si sites. In the first Si site, Si(3) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(3), and four equivalent Si(2) atoms. In the second Si site, Si(1) is bonded in a body-centered cubic geometry to four equivalent Ce(1) and four equivalent Si(2) atoms. In the third Si site, Si(2) is bonded in a 10-coordinate geometry to four equivalent Ce(1), one Si(1), two equivalent Si(3), and three equivalent Si(2) atoms.
Ce2Si7 crystallizes in the orthorhombic Cmmm space group. Ce(1) is bonded in a 14-coordinate geometry to two equivalent Si(1), four equivalent Si(3), and eight equivalent Si(2) atoms. Both Ce(1)-Si(1) bond lengths are 3.02 Å. There are two shorter (3.05 Å) and two longer (3.21 Å) Ce(1)-Si(3) bond lengths. There are four shorter (3.06 Å) and four longer (3.20 Å) Ce(1)-Si(2) bond lengths. There are three inequivalent Si sites. In the first Si site, Si(3) is bonded in a 9-coordinate geometry to four equivalent Ce(1), one Si(3), and four equivalent Si(2) atoms. The Si(3)-Si(3) bond length is 2.53 Å. All Si(3)-Si(2) bond lengths are 2.59 Å. In the second Si site, Si(1) is bonded in a body-centered cubic geometry to four equivalent Ce(1) and four equivalent Si(2) atoms. All Si(1)-Si(2) bond lengths are 2.56 Å. In the third Si site, Si(2) is bonded in a 10-coordinate geometry to four equivalent Ce(1), one Si(1), two equivalent Si(3), and three equivalent Si(2) atoms. There are a spread of Si(2)-Si(2) bond distances ranging from 2.50-2.66 Å.