Sm32O21 crystallizes in the trigonal R3m space group. There are ten inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(5) atom. In the second Sm site, Sm(2) is bonded in a bent 120 degrees geometry to two equivalent O(2) atoms. In the third Sm site, Sm(3) is bonded in a trigonal non-coplanar geometry to three equivalent O(5) atoms. In the fourth Sm site, Sm(4) is bonded in a bent 120 degrees geometry to one Sm(6) and two equivalent O(3) atoms. In the fifth Sm site, Sm(5) is bonded in a trigonal non-coplanar geometry to one Sm(6), one O(1), one O(2), and one O(4) atom. In the sixth Sm site, Sm(6) is bonded to three equivalent Sm(4), three equivalent Sm(9), and six equivalent Sm(5) atoms to form SmSm12 cuboctahedra that share corners with six equivalent O(2)Sm4 tetrahedra, edges with three equivalent O(3)Sm4 tetrahedra, edges with three equivalent O(4)Sm4 tetrahedra, and edges with six equivalent O(1)Sm4 tetrahedra. In the seventh Sm site, Sm(7) is bonded in a tetrahedral geometry to one O(3), one O(4), and two equivalent O(1) atoms. In the eighth Sm site, Sm(8) is bonded in a water-like geometry to one O(4) and one O(5) atom. In the ninth Sm site, Sm(9) is bonded in a bent 120 degrees geometry to one Sm(6) and two equivalent O(1) atoms. In the tenth Sm site, Sm(10) is bonded in a trigonal non-coplanar geometry to one O(3) and two equivalent O(2) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Sm(1), one Sm(5), one Sm(7), and one Sm(9) atom to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent O(4)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the second O site, O(2) is bonded to one Sm(1), one Sm(10), one Sm(2), and one Sm(5) atom to form OSm4 tetrahedra that share  a cornercorner with one Sm(6)Sm12 cuboctahedra,  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(4)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, and corners with two equivalent O(2)Sm4 tetrahedra. In the third O site, O(3) is bonded to one Sm(10), one Sm(7), and two equivalent Sm(4) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(4)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the fourth O site, O(4) is bonded to one Sm(7), one Sm(8), and two equivalent Sm(5) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with four equivalent O(1)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the fifth O site, O(5) is bonded to one Sm(3), one Sm(8), and two equivalent Sm(1) atoms to form corner-sharing OSm4 tetrahedra.
Sm32O21 crystallizes in the trigonal R3m space group. There are ten inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(5) atom. The Sm(1)-O(1) bond length is 2.33 Å. The Sm(1)-O(2) bond length is 2.34 Å. The Sm(1)-O(5) bond length is 2.31 Å. In the second Sm site, Sm(2) is bonded in a bent 120 degrees geometry to two equivalent O(2) atoms. Both Sm(2)-O(2) bond lengths are 2.31 Å. In the third Sm site, Sm(3) is bonded in a trigonal non-coplanar geometry to three equivalent O(5) atoms. All Sm(3)-O(5) bond lengths are 2.39 Å. In the fourth Sm site, Sm(4) is bonded in a bent 120 degrees geometry to one Sm(6) and two equivalent O(3) atoms. The Sm(4)-Sm(6) bond length is 3.72 Å. Both Sm(4)-O(3) bond lengths are 2.33 Å. In the fifth Sm site, Sm(5) is bonded in a trigonal non-coplanar geometry to one Sm(6), one O(1), one O(2), and one O(4) atom. The Sm(5)-Sm(6) bond length is 3.93 Å. The Sm(5)-O(1) bond length is 2.35 Å. The Sm(5)-O(2) bond length is 2.28 Å. The Sm(5)-O(4) bond length is 2.35 Å. In the sixth Sm site, Sm(6) is bonded to three equivalent Sm(4), three equivalent Sm(9), and six equivalent Sm(5) atoms to form SmSm12 cuboctahedra that share corners with six equivalent O(2)Sm4 tetrahedra, edges with three equivalent O(3)Sm4 tetrahedra, edges with three equivalent O(4)Sm4 tetrahedra, and edges with six equivalent O(1)Sm4 tetrahedra. All Sm(6)-Sm(9) bond lengths are 3.92 Å. In the seventh Sm site, Sm(7) is bonded in a tetrahedral geometry to one O(3), one O(4), and two equivalent O(1) atoms. The Sm(7)-O(3) bond length is 2.32 Å. The Sm(7)-O(4) bond length is 2.39 Å. Both Sm(7)-O(1) bond lengths are 2.37 Å. In the eighth Sm site, Sm(8) is bonded in a water-like geometry to one O(4) and one O(5) atom. The Sm(8)-O(4) bond length is 2.29 Å. The Sm(8)-O(5) bond length is 2.28 Å. In the ninth Sm site, Sm(9) is bonded in a bent 120 degrees geometry to one Sm(6) and two equivalent O(1) atoms. Both Sm(9)-O(1) bond lengths are 2.32 Å. In the tenth Sm site, Sm(10) is bonded in a trigonal non-coplanar geometry to one O(3) and two equivalent O(2) atoms. The Sm(10)-O(3) bond length is 2.30 Å. Both Sm(10)-O(2) bond lengths are 2.34 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Sm(1), one Sm(5), one Sm(7), and one Sm(9) atom to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent O(4)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the second O site, O(2) is bonded to one Sm(1), one Sm(10), one Sm(2), and one Sm(5) atom to form OSm4 tetrahedra that share  a cornercorner with one Sm(6)Sm12 cuboctahedra,  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(4)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, and corners with two equivalent O(2)Sm4 tetrahedra. In the third O site, O(3) is bonded to one Sm(10), one Sm(7), and two equivalent Sm(4) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(4)Sm4 tetrahedra, corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the fourth O site, O(4) is bonded to one Sm(7), one Sm(8), and two equivalent Sm(5) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one O(5)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra, corners with four equivalent O(1)Sm4 tetrahedra, and  an edgeedge with one Sm(6)Sm12 cuboctahedra. In the fifth O site, O(5) is bonded to one Sm(3), one Sm(8), and two equivalent Sm(1) atoms to form corner-sharing OSm4 tetrahedra.