Ce4CNI6 crystallizes in the tetragonal P4_2/mnm space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 2-coordinate geometry to two equivalent N(1), one I(1), and four equivalent I(3) atoms. In the second Ce site, Ce(2) is bonded in a distorted single-bond geometry to two equivalent C(1), one N(1), one I(1), one I(2), and two equivalent I(3) atoms. In the third Ce site, Ce(3) is bonded in a distorted octahedral geometry to one C(1), one I(2), and four equivalent I(3) atoms. C(1) is bonded in a 6-coordinate geometry to one Ce(3), four equivalent Ce(2), and one C(1) atom. N(1) is bonded to two equivalent Ce(1) and two equivalent Ce(2) atoms to form edge-sharing NCe4 tetrahedra. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Ce(1) and two equivalent Ce(2) atoms. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to one Ce(3) and two equivalent Ce(2) atoms. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Ce(1), one Ce(2), and one Ce(3) atom.
Ce4CNI6 crystallizes in the tetragonal P4_2/mnm space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 2-coordinate geometry to two equivalent N(1), one I(1), and four equivalent I(3) atoms. Both Ce(1)-N(1) bond lengths are 2.31 Å. The Ce(1)-I(1) bond length is 3.79 Å. All Ce(1)-I(3) bond lengths are 3.49 Å. In the second Ce site, Ce(2) is bonded in a distorted single-bond geometry to two equivalent C(1), one N(1), one I(1), one I(2), and two equivalent I(3) atoms. Both Ce(2)-C(1) bond lengths are 2.62 Å. The Ce(2)-N(1) bond length is 2.30 Å. The Ce(2)-I(1) bond length is 3.22 Å. The Ce(2)-I(2) bond length is 3.41 Å. Both Ce(2)-I(3) bond lengths are 3.20 Å. In the third Ce site, Ce(3) is bonded in a distorted octahedral geometry to one C(1), one I(2), and four equivalent I(3) atoms. The Ce(3)-C(1) bond length is 2.32 Å. The Ce(3)-I(2) bond length is 3.52 Å. All Ce(3)-I(3) bond lengths are 3.21 Å. C(1) is bonded in a 6-coordinate geometry to one Ce(3), four equivalent Ce(2), and one C(1) atom. The C(1)-C(1) bond length is 1.43 Å. N(1) is bonded to two equivalent Ce(1) and two equivalent Ce(2) atoms to form edge-sharing NCe4 tetrahedra. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Ce(1) and two equivalent Ce(2) atoms. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to one Ce(3) and two equivalent Ce(2) atoms. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Ce(1), one Ce(2), and one Ce(3) atom.