Pr4CeO10 is Fluorite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. In the second Pr site, Pr(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. Ce(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form OPr4 tetrahedra that share corners with four equivalent O(1)Pr4 tetrahedra, corners with six equivalent O(2)Ce2Pr2 tetrahedra, corners with six equivalent O(3)Pr4 tetrahedra,  an edgeedge with one O(2)Ce2Pr2 tetrahedra,  an edgeedge with one O(3)Pr4 tetrahedra, and edges with four equivalent O(1)Pr4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Pr(1) and two equivalent Ce(1) atoms to form OCe2Pr2 tetrahedra that share corners with six equivalent O(1)Pr4 tetrahedra, corners with ten equivalent O(2)Ce2Pr2 tetrahedra,  an edgeedge with one O(1)Pr4 tetrahedra, and edges with five equivalent O(2)Ce2Pr2 tetrahedra. In the third O site, O(3) is bonded to four equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra.
Pr4CeO10 is Fluorite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. All Pr(1)-O(1) bond lengths are 2.51 Å. All Pr(1)-O(2) bond lengths are 2.44 Å. In the second Pr site, Pr(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Pr(2)-O(1) bond lengths are 2.48 Å. All Pr(2)-O(3) bond lengths are 2.48 Å. Ce(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. All Ce(1)-O(2) bond lengths are 2.38 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form OPr4 tetrahedra that share corners with four equivalent O(1)Pr4 tetrahedra, corners with six equivalent O(2)Ce2Pr2 tetrahedra, corners with six equivalent O(3)Pr4 tetrahedra,  an edgeedge with one O(2)Ce2Pr2 tetrahedra,  an edgeedge with one O(3)Pr4 tetrahedra, and edges with four equivalent O(1)Pr4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Pr(1) and two equivalent Ce(1) atoms to form OCe2Pr2 tetrahedra that share corners with six equivalent O(1)Pr4 tetrahedra, corners with ten equivalent O(2)Ce2Pr2 tetrahedra,  an edgeedge with one O(1)Pr4 tetrahedra, and edges with five equivalent O(2)Ce2Pr2 tetrahedra. In the third O site, O(3) is bonded to four equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra.