K2CeCl5 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms. Ce(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and four equivalent Cl(4) atoms to form distorted edge-sharing CeCl7 pentagonal bipyramids. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent K(1) and one Ce(1) atom to form distorted ClK4Ce trigonal bipyramids that share  a cornercorner with one Cl(2)K4Ce trigonal bipyramid, corners with four equivalent Cl(1)K4Ce trigonal bipyramids, corners with four equivalent Cl(3)K4Ce trigonal bipyramids, corners with four equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(3)K4Ce trigonal bipyramid, edges with four equivalent Cl(2)K4Ce trigonal bipyramids, edges with four equivalent Cl(4)K2Ce2 trigonal pyramids, and  a faceface with one Cl(3)K4Ce trigonal bipyramid. In the second Cl site, Cl(2) is bonded to four equivalent K(1) and one Ce(1) atom to form distorted ClK4Ce trigonal bipyramids that share  a cornercorner with one Cl(1)K4Ce trigonal bipyramid, corners with four equivalent Cl(2)K4Ce trigonal bipyramids, corners with five equivalent Cl(3)K4Ce trigonal bipyramids, corners with four equivalent Cl(4)K2Ce2 trigonal pyramids, edges with two equivalent Cl(3)K4Ce trigonal bipyramids, edges with four equivalent Cl(1)K4Ce trigonal bipyramids, and edges with four equivalent Cl(4)K2Ce2 trigonal pyramids. In the third Cl site, Cl(3) is bonded to four equivalent K(1) and one Ce(1) atom to form ClK4Ce trigonal bipyramids that share corners with four equivalent Cl(1)K4Ce trigonal bipyramids, corners with five equivalent Cl(2)K4Ce trigonal bipyramids, corners with eight equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(1)K4Ce trigonal bipyramid, edges with two equivalent Cl(2)K4Ce trigonal bipyramids, edges with two equivalent Cl(3)K4Ce trigonal bipyramids, edges with two equivalent Cl(4)K2Ce2 trigonal pyramids, and  a faceface with one Cl(1)K4Ce trigonal bipyramid. In the fourth Cl site, Cl(4) is bonded to two equivalent K(1) and two equivalent Ce(1) atoms to form distorted ClK2Ce2 trigonal pyramids that share corners with two equivalent Cl(1)K4Ce trigonal bipyramids, corners with two equivalent Cl(2)K4Ce trigonal bipyramids, corners with four equivalent Cl(3)K4Ce trigonal bipyramids, corners with six equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(3)K4Ce trigonal bipyramid, edges with two equivalent Cl(1)K4Ce trigonal bipyramids, edges with two equivalent Cl(2)K4Ce trigonal bipyramids, and  an edgeedge with one Cl(4)K2Ce2 trigonal pyramid.
K2CeCl5 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms. There is one shorter (3.18 Å) and one longer (3.22 Å) K(1)-Cl(1) bond length. There is one shorter (3.26 Å) and one longer (3.38 Å) K(1)-Cl(2) bond length. There is one shorter (3.15 Å) and one longer (3.22 Å) K(1)-Cl(3) bond length. There is one shorter (3.28 Å) and one longer (3.30 Å) K(1)-Cl(4) bond length. Ce(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and four equivalent Cl(4) atoms to form distorted edge-sharing CeCl7 pentagonal bipyramids. The Ce(1)-Cl(1) bond length is 2.81 Å. The Ce(1)-Cl(2) bond length is 2.79 Å. The Ce(1)-Cl(3) bond length is 2.81 Å. There are two shorter (2.84 Å) and two longer (2.88 Å) Ce(1)-Cl(4) bond lengths. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent K(1) and one Ce(1) atom to form distorted ClK4Ce trigonal bipyramids that share  a cornercorner with one Cl(2)K4Ce trigonal bipyramid, corners with four equivalent Cl(1)K4Ce trigonal bipyramids, corners with four equivalent Cl(3)K4Ce trigonal bipyramids, corners with four equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(3)K4Ce trigonal bipyramid, edges with four equivalent Cl(2)K4Ce trigonal bipyramids, edges with four equivalent Cl(4)K2Ce2 trigonal pyramids, and  a faceface with one Cl(3)K4Ce trigonal bipyramid. In the second Cl site, Cl(2) is bonded to four equivalent K(1) and one Ce(1) atom to form distorted ClK4Ce trigonal bipyramids that share  a cornercorner with one Cl(1)K4Ce trigonal bipyramid, corners with four equivalent Cl(2)K4Ce trigonal bipyramids, corners with five equivalent Cl(3)K4Ce trigonal bipyramids, corners with four equivalent Cl(4)K2Ce2 trigonal pyramids, edges with two equivalent Cl(3)K4Ce trigonal bipyramids, edges with four equivalent Cl(1)K4Ce trigonal bipyramids, and edges with four equivalent Cl(4)K2Ce2 trigonal pyramids. In the third Cl site, Cl(3) is bonded to four equivalent K(1) and one Ce(1) atom to form ClK4Ce trigonal bipyramids that share corners with four equivalent Cl(1)K4Ce trigonal bipyramids, corners with five equivalent Cl(2)K4Ce trigonal bipyramids, corners with eight equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(1)K4Ce trigonal bipyramid, edges with two equivalent Cl(2)K4Ce trigonal bipyramids, edges with two equivalent Cl(3)K4Ce trigonal bipyramids, edges with two equivalent Cl(4)K2Ce2 trigonal pyramids, and  a faceface with one Cl(1)K4Ce trigonal bipyramid. In the fourth Cl site, Cl(4) is bonded to two equivalent K(1) and two equivalent Ce(1) atoms to form distorted ClK2Ce2 trigonal pyramids that share corners with two equivalent Cl(1)K4Ce trigonal bipyramids, corners with two equivalent Cl(2)K4Ce trigonal bipyramids, corners with four equivalent Cl(3)K4Ce trigonal bipyramids, corners with six equivalent Cl(4)K2Ce2 trigonal pyramids,  an edgeedge with one Cl(3)K4Ce trigonal bipyramid, edges with two equivalent Cl(1)K4Ce trigonal bipyramids, edges with two equivalent Cl(2)K4Ce trigonal bipyramids, and  an edgeedge with one Cl(4)K2Ce2 trigonal pyramid.