U5(SO4)9 crystallizes in the orthorhombic P2_12_12_1 space group. There are five inequivalent U sites. In the first U site, U(1) is bonded in a distorted pentagonal planar geometry to one O(1), one O(12), one O(14), one O(2), and one O(6) atom. The U(1)-O(1) bond length is 2.32 Å. The U(1)-O(12) bond length is 2.49 Å. The U(1)-O(14) bond length is 2.42 Å. The U(1)-O(2) bond length is 2.30 Å. The U(1)-O(6) bond length is 2.48 Å. In the second U site, U(2) is bonded in a distorted pentagonal planar geometry to one O(21), one O(26), one O(3), one O(30), and one O(4) atom. The U(2)-O(21) bond length is 2.48 Å. The U(2)-O(26) bond length is 2.28 Å. The U(2)-O(3) bond length is 2.36 Å. The U(2)-O(30) bond length is 2.41 Å. The U(2)-O(4) bond length is 2.50 Å. In the third U site, U(3) is bonded in a distorted pentagonal planar geometry to one O(17), one O(19), one O(35), one O(5), and one O(9) atom. The U(3)-O(17) bond length is 2.48 Å. The U(3)-O(19) bond length is 2.33 Å. The U(3)-O(35) bond length is 2.48 Å. The U(3)-O(5) bond length is 2.34 Å. The U(3)-O(9) bond length is 2.35 Å. In the fourth U site, U(4) is bonded in a pentagonal planar geometry to one O(15), one O(22), one O(27), one O(29), and one O(8) atom. The U(4)-O(15) bond length is 2.45 Å. The U(4)-O(22) bond length is 2.48 Å. The U(4)-O(27) bond length is 2.33 Å. The U(4)-O(29) bond length is 2.33 Å. The U(4)-O(8) bond length is 2.39 Å. In the fifth U site, U(5) is bonded in a pentagonal planar geometry to one O(10), one O(13), one O(16), one O(20), and one O(24) atom. The U(5)-O(10) bond length is 2.33 Å. The U(5)-O(13) bond length is 2.32 Å. The U(5)-O(16) bond length is 2.46 Å. The U(5)-O(20) bond length is 2.47 Å. The U(5)-O(24) bond length is 2.31 Å. There are nine inequivalent S sites. In the first S site, S(1) is bonded in a tetrahedral geometry to one O(2), one O(24), one O(25), and one O(34) atom. The S(1)-O(2) bond length is 1.49 Å. The S(1)-O(24) bond length is 1.49 Å. The S(1)-O(25) bond length is 1.44 Å. The S(1)-O(34) bond length is 1.42 Å. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(1), one O(16), one O(18), and one O(20) atom. The S(2)-O(1) bond length is 1.49 Å. The S(2)-O(16) bond length is 1.52 Å. The S(2)-O(18) bond length is 1.47 Å. The S(2)-O(20) bond length is 1.50 Å. In the third S site, S(3) is bonded in a tetrahedral geometry to one O(10), one O(36), one O(5), and one O(8) atom. The S(3)-O(10) bond length is 1.48 Å. The S(3)-O(36) bond length is 1.44 Å. The S(3)-O(5) bond length is 1.53 Å. The S(3)-O(8) bond length is 1.46 Å. In the fourth S site, S(4) is bonded in a tetrahedral geometry to one O(13), one O(27), one O(7), and one O(9) atom. The S(4)-O(13) bond length is 1.50 Å. The S(4)-O(27) bond length is 1.48 Å. The S(4)-O(7) bond length is 1.44 Å. The S(4)-O(9) bond length is 1.46 Å. In the fifth S site, S(5) is bonded in a tetrahedral geometry to one O(12), one O(23), one O(30), and one O(6) atom. The S(5)-O(12) bond length is 1.51 Å. The S(5)-O(23) bond length is 1.44 Å. The S(5)-O(30) bond length is 1.50 Å. The S(5)-O(6) bond length is 1.49 Å. In the sixth S site, S(6) is bonded in a tetrahedral geometry to one O(17), one O(28), one O(3), and one O(35) atom. The S(6)-O(17) bond length is 1.49 Å. The S(6)-O(28) bond length is 1.44 Å. The S(6)-O(3) bond length is 1.48 Å. The S(6)-O(35) bond length is 1.48 Å. In the seventh S site, S(7) is bonded in a tetrahedral geometry to one O(11), one O(14), one O(21), and one O(4) atom. The S(7)-O(11) bond length is 1.43 Å. The S(7)-O(14) bond length is 1.48 Å. The S(7)-O(21) bond length is 1.49 Å. The S(7)-O(4) bond length is 1.47 Å. In the eighth S site, S(8) is bonded in a tetrahedral geometry to one O(15), one O(22), one O(29), and one O(33) atom. The S(8)-O(15) bond length is 1.49 Å. The S(8)-O(22) bond length is 1.46 Å. The S(8)-O(29) bond length is 1.50 Å. The S(8)-O(33) bond length is 1.43 Å. In the ninth S site, S(9) is bonded in a tetrahedral geometry to one O(19), one O(26), one O(31), and one O(32) atom. The S(9)-O(19) bond length is 1.47 Å. The S(9)-O(26) bond length is 1.53 Å. The S(9)-O(31) bond length is 1.47 Å. The S(9)-O(32) bond length is 1.44 Å. There are thirty-six inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one U(1) and one S(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one U(1) and one S(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one U(2) and one S(6) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one U(2) and one S(7) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one U(3) and one S(3) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one U(1) and one S(5) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one S(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one U(4) and one S(3) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one U(3) and one S(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one U(5) and one S(3) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one S(7) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one U(1) and one S(5) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one U(5) and one S(4) atom. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one U(1) and one S(7) atom. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one U(4) and one S(8) atom. In the sixteenth O site, O(16) is bonded in a distorted single-bond geometry to one U(5) and one S(2) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one U(3) and one S(6) atom. In the eighteenth O site, O(18) is bonded in a single-bond geometry to one S(2) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one U(3) and one S(9) atom. In the twentieth O site, O(20) is bonded in a distorted single-bond geometry to one U(5) and one S(2) atom. In the twenty-first O site, O(21) is bonded in a distorted single-bond geometry to one U(2) and one S(7) atom. In the twenty-second O site, O(22) is bonded in a single-bond geometry to one U(4) and one S(8) 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 distorted single-bond geometry to one U(5) and one S(1) atom. In the twenty-fifth O site, O(25) is bonded in a single-bond geometry to one S(1) atom. In the twenty-sixth O site, O(26) is bonded in a distorted single-bond geometry to one U(2) and one S(9) atom. In the twenty-seventh O site, O(27) is bonded in a distorted single-bond geometry to one U(4) and one S(4) atom. In the twenty-eighth O site, O(28) is bonded in a single-bond geometry to one S(6) atom. In the twenty-ninth O site, O(29) is bonded in a single-bond geometry to one U(4) and one S(8) atom. In the thirtieth O site, O(30) is bonded in a single-bond geometry to one U(2) and one S(5) atom. In the thirty-first O site, O(31) is bonded in a single-bond geometry to one S(9) atom. In the thirty-second O site, O(32) is bonded in a single-bond geometry to one S(9) atom. In the thirty-third O site, O(33) is bonded in a single-bond geometry to one S(8) atom. In the thirty-fourth O site, O(34) is bonded in a single-bond geometry to one S(1) atom. In the thirty-fifth O site, O(35) is bonded in a single-bond geometry to one U(3) and one S(6) atom. In the thirty-sixth O site, O(36) is bonded in a single-bond geometry to one S(3) atom. Linkers: 36 [O]S([O])(=O)=O. Metal clusters: 20 [U]. The MOF has largest included sphere 10.79 A, density 1.66 g/cm3, surface area 1982.36 m2/g, accessible volume 0.40 cm3/g