Ce3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 18-coordinate geometry to two equivalent Zn(3), two equivalent Zn(4), six equivalent Zn(2), and eight equivalent Zn(1) atoms. In the second Ce site, Ce(2) is bonded in a 20-coordinate geometry to four equivalent Zn(3), four equivalent Zn(4), four equivalent Zn(5), and eight equivalent Zn(1) atoms. There are five inequivalent Zn sites. In the first Zn site, Zn(3) is bonded to one Ce(1), one Ce(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnCe2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Ce2Zn10 cuboctahedra, corners with two equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with two equivalent Zn(5)Ce2Zn10 cuboctahedra, edges with two equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with three equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Ce3Zn9 cuboctahedra. In the second Zn site, Zn(1) is bonded to one Ce(2), two equivalent Ce(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted ZnCe3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Ce3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Ce2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Ce2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Ce2Zn10 cuboctahedra, edges with five equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Ce3Zn9 cuboctahedra. In the third Zn site, Zn(4) is bonded to one Ce(1), one Ce(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnCe2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with five equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with two equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with three equivalent Zn(4)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(3)Ce2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Ce3Zn9 cuboctahedra. In the fourth Zn site, Zn(5) is bonded to two equivalent Ce(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnCe2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with four equivalent Zn(3)Ce2Zn10 cuboctahedra, edges with four equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with four equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with four equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Ce3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Ce(1), one Zn(4), two equivalent Zn(2), two equivalent Zn(3), and four equivalent Zn(1) atoms.
Ce3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 18-coordinate geometry to two equivalent Zn(3), two equivalent Zn(4), six equivalent Zn(2), and eight equivalent Zn(1) atoms. Both Ce(1)-Zn(3) bond lengths are 3.18 Å. Both Ce(1)-Zn(4) bond lengths are 3.10 Å. There are a spread of Ce(1)-Zn(2) bond distances ranging from 3.21-3.66 Å. There are four shorter (3.28 Å) and four longer (3.44 Å) Ce(1)-Zn(1) bond lengths. In the second Ce site, Ce(2) is bonded in a 20-coordinate geometry to four equivalent Zn(3), four equivalent Zn(4), four equivalent Zn(5), and eight equivalent Zn(1) atoms. All Ce(2)-Zn(3) bond lengths are 3.14 Å. All Ce(2)-Zn(4) bond lengths are 3.22 Å. All Ce(2)-Zn(5) bond lengths are 3.46 Å. All Ce(2)-Zn(1) bond lengths are 3.37 Å. There are five inequivalent Zn sites. In the first Zn site, Zn(3) is bonded to one Ce(1), one Ce(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnCe2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Ce2Zn10 cuboctahedra, corners with two equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with two equivalent Zn(5)Ce2Zn10 cuboctahedra, edges with two equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with three equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Ce3Zn9 cuboctahedra. The Zn(3)-Zn(3) bond length is 2.63 Å. The Zn(3)-Zn(5) bond length is 2.65 Å. Both Zn(3)-Zn(2) bond lengths are 2.80 Å. Both Zn(3)-Zn(4) bond lengths are 2.91 Å. There are two shorter (2.69 Å) and two longer (2.80 Å) Zn(3)-Zn(1) bond lengths. In the second Zn site, Zn(1) is bonded to one Ce(2), two equivalent Ce(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted ZnCe3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Ce3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Ce2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Ce2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Ce2Zn10 cuboctahedra, edges with five equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Ce3Zn9 cuboctahedra. The Zn(1)-Zn(5) bond length is 2.64 Å. There is one shorter (2.61 Å) and one longer (2.73 Å) Zn(1)-Zn(1) bond length. There is one shorter (2.56 Å) and one longer (2.77 Å) Zn(1)-Zn(2) bond length. There is one shorter (2.75 Å) and one longer (2.77 Å) Zn(1)-Zn(4) bond length. In the third Zn site, Zn(4) is bonded to one Ce(1), one Ce(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnCe2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with five equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with two equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with three equivalent Zn(4)Ce2Zn10 cuboctahedra, faces with five equivalent Zn(3)Ce2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Ce3Zn9 cuboctahedra. The Zn(4)-Zn(2) bond length is 2.66 Å. The Zn(4)-Zn(4) bond length is 2.70 Å. Both Zn(4)-Zn(5) bond lengths are 2.62 Å. In the fourth Zn site, Zn(5) is bonded to two equivalent Ce(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnCe2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(4)Ce2Zn10 cuboctahedra, corners with four equivalent Zn(5)Ce2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Ce3Zn9 cuboctahedra, edges with four equivalent Zn(3)Ce2Zn10 cuboctahedra, edges with four equivalent Zn(1)Ce3Zn9 cuboctahedra, faces with two equivalent Zn(5)Ce2Zn10 cuboctahedra, faces with four equivalent Zn(3)Ce2Zn10 cuboctahedra, faces with four equivalent Zn(4)Ce2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Ce3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Ce(1), one Zn(4), two equivalent Zn(2), two equivalent Zn(3), and four equivalent Zn(1) atoms. Both Zn(2)-Zn(2) bond lengths are 2.80 Å.