Yb2C21NH15S3O14 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(14), one O(7), one O(9), and two equivalent O(2) atoms. The Yb(1)-O(1) bond length is 2.39 Å. The Yb(1)-O(10) bond length is 2.25 Å. The Yb(1)-O(11) bond length is 2.21 Å. The Yb(1)-O(14) bond length is 2.32 Å. The Yb(1)-O(7) bond length is 2.20 Å. The Yb(1)-O(9) bond length is 2.34 Å. There is one shorter (2.34 Å) and one longer (2.50 Å) Yb(1)-O(2) bond length. In the second Yb site, Yb(2) is bonded in a distorted pentagonal bipyramidal geometry to one O(12), one O(13), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The Yb(2)-O(12) bond length is 2.18 Å. The Yb(2)-O(13) bond length is 2.41 Å. The Yb(2)-O(3) bond length is 2.25 Å. The Yb(2)-O(4) bond length is 2.28 Å. The Yb(2)-O(5) bond length is 2.31 Å. The Yb(2)-O(6) bond length is 2.21 Å. The Yb(2)-O(8) bond length is 2.24 Å. There are twenty-one inequivalent C sites. In the first C site, C(16) is bonded in a distorted single-bond geometry to one C(17) and one H(8) atom. The C(16)-C(17) bond length is 1.39 Å. The C(16)-H(8) bond length is 1.09 Å. In the second C site, C(17) is bonded in a trigonal planar geometry to one C(16), one C(18), and one S(3) atom. The C(17)-C(18) bond length is 1.48 Å. The C(17)-S(3) bond length is 1.72 Å. In the third C site, C(18) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(11), and one O(12) atom. The C(18)-O(11) bond length is 1.26 Å. The C(18)-O(12) bond length is 1.28 Å. In the fourth C site, C(19) is bonded to one N(1), one H(10), one H(11), and one H(9) atom to form corner-sharing CH3N tetrahedra. The C(19)-N(1) bond length is 1.46 Å. The C(19)-H(10) bond length is 1.10 Å. The C(19)-H(11) bond length is 1.10 Å. The C(19)-H(9) bond length is 1.10 Å. In the fifth C site, C(20) is bonded to one N(1), one H(12), one H(13), and one H(14) atom to form corner-sharing CH3N tetrahedra. The C(20)-N(1) bond length is 1.46 Å. The C(20)-H(12) bond length is 1.09 Å. The C(20)-H(13) bond length is 1.10 Å. The C(20)-H(14) bond length is 1.10 Å. In the sixth C site, C(21) is bonded in a trigonal planar geometry to one N(1), one H(15), and one O(14) atom. The C(21)-N(1) bond length is 1.34 Å. The C(21)-H(15) bond length is 1.10 Å. The C(21)-O(14) bond length is 1.25 Å. In the seventh C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.47 Å. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.29 Å. In the eighth C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one S(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-S(1) bond length is 1.73 Å. In the ninth C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(1) atom. The C(3)-C(4) bond length is 1.41 Å. The C(3)-H(1) bond length is 1.09 Å. In the tenth 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 1.09 Å. In the eleventh C site, C(5) is bonded in a trigonal planar geometry to one C(4), one C(6), and one S(1) atom. The C(5)-C(6) bond length is 1.49 Å. The C(5)-S(1) bond length is 1.72 Å. In the twelfth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(3), and one O(4) atom. The C(6)-O(3) bond length is 1.27 Å. The C(6)-O(4) bond length is 1.27 Å. In the thirteenth C site, C(7) is bonded in a distorted bent 120 degrees geometry to one C(8), one O(5), and one O(6) atom. The C(7)-C(8) bond length is 1.48 Å. The C(7)-O(5) bond length is 1.27 Å. The C(7)-O(6) bond length is 1.28 Å. In the fourteenth C site, C(8) is bonded in a trigonal planar geometry to one C(7), one C(9), and one S(2) atom. The C(8)-C(9) bond length is 1.39 Å. The C(8)-S(2) bond length is 1.72 Å. In the fifteenth C site, C(9) is bonded in a distorted trigonal planar geometry to one C(10), one C(8), and one H(3) atom. The C(9)-C(10) bond length is 1.41 Å. The C(9)-H(3) bond length is 1.09 Å. In the sixteenth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(4) atom. The C(10)-C(11) bond length is 1.39 Å. The C(10)-H(4) bond length is 1.09 Å. In the seventeenth C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one S(2) atom. The C(11)-C(12) bond length is 1.48 Å. The C(11)-S(2) bond length is 1.72 Å. In the eighteenth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(7), and one O(8) atom. The C(12)-O(7) bond length is 1.28 Å. The C(12)-O(8) bond length is 1.26 Å. In the nineteenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one C(14), one O(10), and one O(9) atom. The C(13)-C(14) bond length is 1.47 Å. The C(13)-O(10) bond length is 1.27 Å. The C(13)-O(9) bond length is 1.29 Å. In the twentieth C site, C(14) is bonded in a trigonal planar geometry to one C(13), one C(15), and one S(3) atom. The C(14)-C(15) bond length is 1.39 Å. The C(14)-S(3) bond length is 1.72 Å. In the twenty-first C site, C(15) is bonded in a distorted single-bond geometry to one C(14) and one H(7) atom. The C(15)-H(7) bond length is 1.09 Å. N(1) is bonded in a trigonal planar geometry to one C(19), one C(20), and one C(21) atom. There are fifteen inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) 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(9) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(10) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(13) atom. The H(5)-O(13) bond length is 1.00 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(13) atom. The H(6)-O(13) bond length is 0.97 Å. 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(16) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(19) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(19) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(19) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(20) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(20) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(20) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(21) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one C(2) and one C(5) atom. In the second S site, S(2) is bonded in an L-shaped geometry to one C(11) and one C(8) atom. In the third S site, S(3) is bonded in an L-shaped geometry to one C(14) and one C(17) atom. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Yb(1) and one C(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Yb(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Yb(2) and one C(6) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Yb(2) and one C(6) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Yb(2) and one C(7) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Yb(2) and one C(7) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Yb(1) and one C(12) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Yb(2) and one C(12) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Yb(1) and one C(13) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Yb(1) and one C(13) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one Yb(1) and one C(18) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Yb(2) and one C(18) atom. In the thirteenth O site, O(13) is bonded in a distorted water-like geometry to one Yb(2), one H(5), and one H(6) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Yb(1) and one C(21) atom. Linkers: 12 [O]C(=O)c1ccc(C([O])=O)s1. Metal clusters: 8 [Yb]. The MOF has largest included sphere 4.81 A, density 1.94 g/cm3, surface area 2810.97 m2/g, accessible volume 0.21 cm3/g