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CeP is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ce3+ is bonded in a body-centered cubic geometry to eight equivalent P3- atoms. All Ce–P bond lengths are 3.03 Å. P3- is bonded in a body-centered cubic geometry to eight equivalent Ce3+ atoms.
CeP is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ce3+ is bonded to six equivalent P3- atoms to form a mixture of corner and edge-sharing CeP6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Ce–P bond lengths are 2.90 Å. P3- is bonded to six equivalent Ce3+ atoms to form a mixture of corner and edge-sharing PCe6 octahedra. The corner-sharing octahedral tilt angles are 0°.
CeP5 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. Ce3+ is bonded in a 10-coordinate geometry to ten P+0.60- atoms. There are a spread of Ce–P bond distances ranging from 2.86–3.25 Å. There are three inequivalent P+0.60- sites. In the first P+0.60- site, P+0.60- is bonded in a 5-coordinate geometry to three equivalent Ce3+ and two P+0.60- atoms. Both P–P bond lengths are 2.22 Å. In the second P+0.60- site, P+0.60- is bonded in a rectangular see-saw-like geometry to two equivalent Ce3+ and two equivalent P+0.60- atoms. Both P–P bond lengths are 2.22 Å. In the third P+0.60- site, P+0.60- is bonded to one Ce3+ and three P+0.60- atoms to form distorted edge-sharing PCeP3 tetrahedra. The P–P bond length is 2.24 Å.
CeP2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Ce4+ is bonded in a 9-coordinate geometry to nine P2- atoms. There are a spread of Ce–P bond distances ranging from 2.87–3.07 Å. There are two inequivalent P2- sites. In the first P2- site, P2- is bonded to five equivalent Ce4+ and one P2- atom to form a mixture of distorted edge and corner-sharing PCe5P pentagonal pyramids. The P–P bond length is 2.24 Å. In the second P2- site, P2- is bonded in a 6-coordinate geometry to four equivalent Ce4+ and two P2- atoms. The P–P bond length is 2.33 Å.
CeP3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Ce3+ is bonded to twelve equivalent P1- atoms to form a mixture of distorted corner and face-sharing CeP12 cuboctahedra. There are six shorter (2.81 Å) and six longer (3.18 Å) Ce–P bond lengths. P1- is bonded in a 6-coordinate geometry to four equivalent Ce3+ and two equivalent P1- atoms. Both P–P bond lengths are 2.54 Å.