Ce2Zr2O7 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms. In the second Ce site, Ce(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the third Ce site, Ce(3) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(1) atoms. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(4) and four equivalent O(3) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the third Zr site, Zr(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Ce(2), one Ce(3), one Zr(2), and one Zr(3) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(3)Ce2Zr2 tetrahedra, corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, corners with six equivalent O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. In the second O site, O(2) is bonded to one Ce(1), one Ce(3), and two equivalent Ce(2) atoms to form OCe4 tetrahedra that share corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(2)Ce4 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra. In the third O site, O(3) is bonded to one Ce(1), one Ce(2), one Zr(1), and one Zr(2) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(1)Ce2Zr2 tetrahedra, corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, corners with six equivalent O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Ce(2), one Zr(1), and one Zr(3) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(2)Ce4 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(2)Ce4 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra. In the fifth O site, O(5) is bonded to one Ce(1), one Ce(3), and two equivalent Zr(2) atoms to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(2)Ce4 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(5)Ce2Zr2 tetrahedra,  an edgeedge with one O(2)Ce4 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra.
Ce2Zr2O7 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms. Both Ce(1)-O(2) bond lengths are 2.33 Å. Both Ce(1)-O(5) bond lengths are 2.61 Å. All Ce(1)-O(3) bond lengths are 2.61 Å. In the second Ce site, Ce(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Ce(2)-O(1) bond lengths are 2.61 Å. Both Ce(2)-O(2) bond lengths are 2.33 Å. Both Ce(2)-O(3) bond lengths are 2.61 Å. Both Ce(2)-O(4) bond lengths are 2.61 Å. In the third Ce site, Ce(3) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(1) atoms. Both Ce(3)-O(2) bond lengths are 2.33 Å. Both Ce(3)-O(5) bond lengths are 2.61 Å. All Ce(3)-O(1) bond lengths are 2.61 Å. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(4) and four equivalent O(3) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Zr(1)-O(4) bond lengths are 2.10 Å. All Zr(1)-O(3) bond lengths are 2.10 Å. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Zr(2)-O(1) bond lengths are 2.10 Å. Both Zr(2)-O(3) bond lengths are 2.10 Å. Both Zr(2)-O(5) bond lengths are 2.10 Å. In the third Zr site, Zr(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form corner-sharing ZrO6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Zr(3)-O(4) bond lengths are 2.10 Å. All Zr(3)-O(1) bond lengths are 2.10 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Ce(2), one Ce(3), one Zr(2), and one Zr(3) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(3)Ce2Zr2 tetrahedra, corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, corners with six equivalent O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. In the second O site, O(2) is bonded to one Ce(1), one Ce(3), and two equivalent Ce(2) atoms to form OCe4 tetrahedra that share corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(2)Ce4 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra. In the third O site, O(3) is bonded to one Ce(1), one Ce(2), one Zr(1), and one Zr(2) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(1)Ce2Zr2 tetrahedra, corners with two equivalent O(4)Ce2Zr2 tetrahedra, corners with two equivalent O(5)Ce2Zr2 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, corners with six equivalent O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(1)Ce2Zr2 tetrahedra,  an edgeedge with one O(3)Ce2Zr2 tetrahedra,  an edgeedge with one O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(5)Ce2Zr2 tetrahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Ce(2), one Zr(1), and one Zr(3) atom to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(2)Ce4 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(4)Ce2Zr2 tetrahedra,  an edgeedge with one O(2)Ce4 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra. In the fifth O site, O(5) is bonded to one Ce(1), one Ce(3), and two equivalent Zr(2) atoms to form distorted OCe2Zr2 tetrahedra that share corners with two equivalent O(2)Ce4 tetrahedra, corners with four equivalent O(1)Ce2Zr2 tetrahedra, corners with four equivalent O(3)Ce2Zr2 tetrahedra, corners with four equivalent O(5)Ce2Zr2 tetrahedra,  an edgeedge with one O(2)Ce4 tetrahedra, edges with two equivalent O(1)Ce2Zr2 tetrahedra, and edges with two equivalent O(3)Ce2Zr2 tetrahedra.