Sm3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Sm sites. In the first Sm site, Sm(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 Sm site, Sm(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 Sm(1), one Sm(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnSm2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Sm2Zn10 cuboctahedra, corners with two equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with two equivalent Zn(5)Sm2Zn10 cuboctahedra, edges with two equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with three equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Sm3Zn9 cuboctahedra. In the second Zn site, Zn(1) is bonded to one Sm(2), two equivalent Sm(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 ZnSm3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Sm3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Sm2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Sm2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Sm2Zn10 cuboctahedra, edges with five equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Sm3Zn9 cuboctahedra. In the third Zn site, Zn(4) is bonded to one Sm(1), one Sm(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnSm2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with five equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with two equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with three equivalent Zn(4)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(3)Sm2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Sm3Zn9 cuboctahedra. In the fourth Zn site, Zn(5) is bonded to two equivalent Sm(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnSm2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with four equivalent Zn(3)Sm2Zn10 cuboctahedra, edges with four equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with four equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with four equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Sm3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Sm(1), one Zn(4), two equivalent Zn(2), two equivalent Zn(3), and four equivalent Zn(1) atoms.
Sm3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Sm sites. In the first Sm site, Sm(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 Sm(1)-Zn(3) bond lengths are 3.13 Å. Both Sm(1)-Zn(4) bond lengths are 3.05 Å. There are a spread of Sm(1)-Zn(2) bond distances ranging from 3.18-3.59 Å. There are four shorter (3.24 Å) and four longer (3.38 Å) Sm(1)-Zn(1) bond lengths. In the second Sm site, Sm(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 Sm(2)-Zn(3) bond lengths are 3.09 Å. All Sm(2)-Zn(4) bond lengths are 3.18 Å. All Sm(2)-Zn(5) bond lengths are 3.41 Å. All Sm(2)-Zn(1) bond lengths are 3.32 Å. There are five inequivalent Zn sites. In the first Zn site, Zn(3) is bonded to one Sm(1), one Sm(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnSm2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Sm2Zn10 cuboctahedra, corners with two equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with two equivalent Zn(5)Sm2Zn10 cuboctahedra, edges with two equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with three equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Sm3Zn9 cuboctahedra. The Zn(3)-Zn(3) bond length is 2.57 Å. The Zn(3)-Zn(5) bond length is 2.61 Å. Both Zn(3)-Zn(2) bond lengths are 2.75 Å. Both Zn(3)-Zn(4) bond lengths are 2.86 Å. There are two shorter (2.66 Å) and two longer (2.75 Å) Zn(3)-Zn(1) bond lengths. In the second Zn site, Zn(1) is bonded to one Sm(2), two equivalent Sm(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 ZnSm3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Sm3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Sm2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Sm2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Sm2Zn10 cuboctahedra, edges with five equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Sm3Zn9 cuboctahedra. The Zn(1)-Zn(5) bond length is 2.60 Å. There is one shorter (2.58 Å) and one longer (2.69 Å) Zn(1)-Zn(1) bond length. There is one shorter (2.52 Å) and one longer (2.72 Å) Zn(1)-Zn(2) bond length. There is one shorter (2.71 Å) and one longer (2.72 Å) Zn(1)-Zn(4) bond length. In the third Zn site, Zn(4) is bonded to one Sm(1), one Sm(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnSm2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with five equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with two equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with three equivalent Zn(4)Sm2Zn10 cuboctahedra, faces with five equivalent Zn(3)Sm2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Sm3Zn9 cuboctahedra. The Zn(4)-Zn(2) bond length is 2.62 Å. The Zn(4)-Zn(4) bond length is 2.66 Å. Both Zn(4)-Zn(5) bond lengths are 2.57 Å. In the fourth Zn site, Zn(5) is bonded to two equivalent Sm(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnSm2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(4)Sm2Zn10 cuboctahedra, corners with four equivalent Zn(5)Sm2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Sm3Zn9 cuboctahedra, edges with four equivalent Zn(3)Sm2Zn10 cuboctahedra, edges with four equivalent Zn(1)Sm3Zn9 cuboctahedra, faces with two equivalent Zn(5)Sm2Zn10 cuboctahedra, faces with four equivalent Zn(3)Sm2Zn10 cuboctahedra, faces with four equivalent Zn(4)Sm2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Sm3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Sm(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 2.76 Å.