CeC21H9(SO2)3 crystallizes in the monoclinic Cc space group. Ce(1) is bonded in a 9-coordinate geometry to one O(2), one O(3), one O(5), two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms. The Ce(1)-O(2) bond length is 2.52 Å. The Ce(1)-O(3) bond length is 2.53 Å. The Ce(1)-O(5) bond length is 2.57 Å. There is one shorter (2.46 Å) and one longer (2.74 Å) Ce(1)-O(1) bond length. There is one shorter (2.56 Å) and one longer (2.76 Å) Ce(1)-O(4) bond length. There is one shorter (2.58 Å) and one longer (2.72 Å) Ce(1)-O(6) bond length. There are twenty-one inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one C(7) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-C(6) bond length is 1.40 Å. The C(1)-C(7) bond length is 1.48 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(1) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-H(1) bond length is 0.95 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(12), one C(2), and one C(4) atom. The C(3)-C(12) bond length is 1.46 Å. The C(3)-C(4) bond length is 1.39 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(2) atom. The C(4)-C(5) bond length is 1.39 Å. The C(4)-H(2) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(17), one C(4), and one C(6) atom. The C(5)-C(17) bond length is 1.49 Å. The C(5)-C(6) bond length is 1.40 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(1), one C(5), and one H(3) atom. The C(6)-H(3) bond length is 0.95 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(1), one C(10), and one S(1) atom. The C(7)-C(10) bond length is 1.35 Å. The C(7)-S(1) bond length is 1.73 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(11), one C(9), and one S(1) atom. The C(8)-C(11) bond length is 1.51 Å. The C(8)-C(9) bond length is 1.36 Å. The C(8)-S(1) bond length is 1.71 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(10), one C(8), and one H(4) atom. The C(9)-C(10) bond length is 1.41 Å. The C(9)-H(4) bond length is 0.95 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(7), one C(9), and one H(5) atom. The C(10)-H(5) bond length is 0.95 Å. In the eleventh C site, C(11) is bonded in a bent 120 degrees geometry to one C(8), one O(1), and one O(2) atom. The C(11)-O(1) bond length is 1.27 Å. The C(11)-O(2) bond length is 1.26 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(15), one C(3), and one S(2) atom. The C(12)-C(15) bond length is 1.39 Å. The C(12)-S(2) bond length is 1.72 Å. In the thirteenth C site, C(13) is bonded in a trigonal planar geometry to one C(14), one C(16), and one S(2) atom. The C(13)-C(14) bond length is 1.39 Å. The C(13)-C(16) bond length is 1.45 Å. The C(13)-S(2) bond length is 1.73 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13) and one H(6) atom. The C(14)-H(6) bond length is 0.95 Å. In the fifteenth C site, C(15) is bonded in a distorted single-bond geometry to one C(12) and one H(7) atom. The C(15)-H(7) bond length is 0.95 Å. In the sixteenth C site, C(16) is bonded in a distorted bent 120 degrees geometry to one C(13), one O(3), and one O(4) atom. The C(16)-O(3) bond length is 1.26 Å. The C(16)-O(4) bond length is 1.30 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(20), one C(5), and one S(3) atom. The C(17)-C(20) bond length is 1.37 Å. The C(17)-S(3) bond length is 1.72 Å. In the eighteenth C site, C(18) is bonded in a trigonal planar geometry to one C(19), one C(21), and one S(3) atom. The C(18)-C(19) bond length is 1.37 Å. The C(18)-C(21) bond length is 1.48 Å. The C(18)-S(3) bond length is 1.70 Å. In the nineteenth C site, C(19) is bonded in a distorted single-bond geometry to one C(18) and one H(8) atom. The C(19)-H(8) bond length is 0.95 Å. In the twentieth C site, C(20) is bonded in a distorted single-bond geometry to one C(17) and one H(9) atom. The C(20)-H(9) bond length is 0.95 Å. In the twenty-first C site, C(21) is bonded in a bent 120 degrees geometry to one C(18), one O(5), and one O(6) atom. The C(21)-O(5) bond length is 1.26 Å. The C(21)-O(6) bond length is 1.29 Å. There are nine inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(9) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(10) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(14) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(15) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(19) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(20) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one C(7) and one C(8) atom. In the second S site, S(2) is bonded in an L-shaped geometry to one C(12) and one C(13) atom. In the third S site, S(3) is bonded in an L-shaped geometry to one C(17) and one C(18) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Ce(1) and one C(11) atom. In the second O site, O(2) is bonded in a distorted water-like geometry to one Ce(1) and one C(11) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ce(1) and one C(16) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one C(16) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ce(1) and one C(21) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one C(21) atom. Linkers: 2 [O]C(=O)c1ccc(-c2cc(-c3ccc(C([O])=O)s3)cc(-c3ccc(C([O])=O)s3)c2)s1. Metal clusters: 2 [Ce]. RCSR code: acs. The MOF has largest included sphere 8.29 A, density 1.28 g/cm3, surface area 3223.68 m2/g, accessible volume 0.34 cm3/g