CeP5 crystallizes in the monoclinic P2_1/m space group. Ce(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Ce(1), one P(2), and one P(3) atom to form PCe2P2 tetrahedra that share corners with four equivalent P(3)Ce2P2 tetrahedra, corners with five equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(2)CeP3 tetrahedra, and  an edgeedge with one P(3)Ce2P2 tetrahedra. In the second P site, P(1) is bonded to two equivalent Ce(1) and two equivalent P(2) atoms to form distorted PCe2P2 tetrahedra that share corners with two equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(2)CeP3 tetrahedra, and corners with ten equivalent P(3)Ce2P2 tetrahedra. In the third P site, P(2) is bonded to one Ce(1), one P(1), one P(2), and one P(3) atom to form PCeP3 tetrahedra that share corners with three equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(3)Ce2P2 tetrahedra, and  an edgeedge with one P(2)CeP3 tetrahedra.
CeP5 crystallizes in the monoclinic P2_1/m space group. Ce(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There is one shorter (3.04 Å) and one longer (3.06 Å) Ce(1)-P(1) bond length. Both Ce(1)-P(2) bond lengths are 3.06 Å. There are two shorter (3.06 Å) and two longer (3.10 Å) Ce(1)-P(3) bond lengths. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Ce(1), one P(2), and one P(3) atom to form PCe2P2 tetrahedra that share corners with four equivalent P(3)Ce2P2 tetrahedra, corners with five equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(2)CeP3 tetrahedra, and  an edgeedge with one P(3)Ce2P2 tetrahedra. The P(3)-P(2) bond length is 2.16 Å. The P(3)-P(3) bond length is 2.20 Å. In the second P site, P(1) is bonded to two equivalent Ce(1) and two equivalent P(2) atoms to form distorted PCe2P2 tetrahedra that share corners with two equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(2)CeP3 tetrahedra, and corners with ten equivalent P(3)Ce2P2 tetrahedra. Both P(1)-P(2) bond lengths are 2.20 Å. In the third P site, P(2) is bonded to one Ce(1), one P(1), one P(2), and one P(3) atom to form PCeP3 tetrahedra that share corners with three equivalent P(1)Ce2P2 tetrahedra, corners with six equivalent P(3)Ce2P2 tetrahedra, and  an edgeedge with one P(2)CeP3 tetrahedra. The P(2)-P(2) bond length is 2.20 Å.