Sm5(SO4)12 crystallizes in the monoclinic C2/c space group. There are three inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one O(10), one O(14), one O(15), one O(21), one O(22), one O(3), one O(5), and one O(7) atom. The Sm(1)-O(10) bond length is 2.53 Å. The Sm(1)-O(14) bond length is 2.49 Å. The Sm(1)-O(15) bond length is 2.42 Å. The Sm(1)-O(21) bond length is 2.31 Å. The Sm(1)-O(22) bond length is 2.30 Å. The Sm(1)-O(3) bond length is 2.46 Å. The Sm(1)-O(5) bond length is 2.53 Å. The Sm(1)-O(7) bond length is 2.52 Å. In the second Sm site, Sm(2) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(13), one O(16), one O(17), one O(4), one O(8), and two equivalent O(2) atoms. The Sm(2)-O(1) bond length is 2.42 Å. The Sm(2)-O(11) bond length is 2.52 Å. The Sm(2)-O(13) bond length is 2.49 Å. The Sm(2)-O(16) bond length is 2.40 Å. The Sm(2)-O(17) bond length is 2.46 Å. The Sm(2)-O(4) bond length is 2.44 Å. The Sm(2)-O(8) bond length is 2.64 Å. There is one shorter (2.35 Å) and one longer (2.63 Å) Sm(2)-O(2) bond length. In the third Sm site, Sm(3) is bonded to two equivalent O(18), two equivalent O(6), two equivalent O(8), and two equivalent O(9) atoms to form distorted SmO8 hexagonal bipyramids that share corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(4)O4 tetrahedra, and edges with two equivalent S(6)O4 tetrahedra. Both Sm(3)-O(18) bond lengths are 2.51 Å. Both Sm(3)-O(6) bond lengths are 2.38 Å. Both Sm(3)-O(8) bond lengths are 2.52 Å. Both Sm(3)-O(9) bond lengths are 2.34 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(12), one O(16), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Sm(3)O8 hexagonal bipyramid. The S(1)-O(1) bond length is 1.49 Å. The S(1)-O(12) bond length is 1.45 Å. The S(1)-O(16) bond length is 1.48 Å. The S(1)-O(6) bond length is 1.48 Å. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(11), one O(14), one O(17), and one O(5) atom. The S(2)-O(11) bond length is 1.48 Å. The S(2)-O(14) bond length is 1.48 Å. The S(2)-O(17) bond length is 1.47 Å. The S(2)-O(5) bond length is 1.49 Å. In the third S site, S(3) is bonded in a tetrahedral geometry to one O(10), one O(15), one O(3), and one O(7) atom. The S(3)-O(10) bond length is 1.48 Å. The S(3)-O(15) bond length is 1.48 Å. The S(3)-O(3) bond length is 1.48 Å. The S(3)-O(7) bond length is 1.48 Å. In the fourth S site, S(4) is bonded to one O(19), one O(2), one O(4), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Sm(3)O8 hexagonal bipyramid. The S(4)-O(19) bond length is 1.44 Å. The S(4)-O(2) bond length is 1.50 Å. The S(4)-O(4) bond length is 1.47 Å. The S(4)-O(9) bond length is 1.47 Å. In the fifth S site, S(5) is bonded in a tetrahedral geometry to one O(21), one O(22), one O(23), and one O(24) atom. The S(5)-O(21) bond length is 1.48 Å. The S(5)-O(22) bond length is 1.46 Å. The S(5)-O(23) bond length is 1.43 Å. The S(5)-O(24) bond length is 1.46 Å. In the sixth S site, S(6) is bonded to one O(13), one O(18), one O(20), and one O(8) atom to form SO4 tetrahedra that share  an edgeedge with one Sm(3)O8 hexagonal bipyramid. The S(6)-O(13) bond length is 1.47 Å. The S(6)-O(18) bond length is 1.47 Å. The S(6)-O(20) bond length is 1.45 Å. The S(6)-O(8) bond length is 1.51 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Sm(2) and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Sm(2) and one S(4) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Sm(1) and one S(3) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Sm(2) and one S(4) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Sm(1) and one S(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Sm(3) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted water-like geometry to one Sm(1) and one S(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Sm(2), one Sm(3), and one S(6) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Sm(3) and one S(4) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Sm(1) and one S(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Sm(2) and one S(2) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one S(1) atom. In the thirteenth O site, O(13) is bonded in a distorted water-like geometry to one Sm(2) and one S(6) atom. In the fourteenth O site, O(14) is bonded in a distorted water-like geometry to one Sm(1) and one S(2) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one S(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Sm(2) and one S(1) atom. In the seventeenth O site, O(17) is bonded in a distorted water-like geometry to one Sm(2) and one S(2) atom. In the eighteenth O site, O(18) is bonded in a distorted water-like geometry to one Sm(3) and one S(6) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one S(4) atom. In the twentieth O site, O(20) is bonded in a single-bond geometry to one S(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Sm(1) and one S(5) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one S(5) atom. In the twenty-third O site, O(23) is bonded in a single-bond geometry to one S(5) atom. In the twenty-fourth O site, O(24) is bonded in a single-bond geometry to one S(5) atom. Linkers: 48 [O]S([O])(=O)=O. Metal clusters: 20 [Sm]. The MOF has largest included sphere 6.20 A, density 1.89 g/cm3, surface area 2277.07 m2/g, accessible volume 0.27 cm3/g