Gd4C2H2S5O24 crystallizes in the monoclinic C2/c space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(3), one O(4), one O(6), one O(7), and two equivalent O(2) atoms. The Gd(1)-O(11) bond length is 2.38 Å. The Gd(1)-O(12) bond length is 2.33 Å. The Gd(1)-O(3) bond length is 2.46 Å. The Gd(1)-O(4) bond length is 2.36 Å. The Gd(1)-O(6) bond length is 2.58 Å. The Gd(1)-O(7) bond length is 2.48 Å. There is one shorter (2.41 Å) and one longer (2.59 Å) Gd(1)-O(2) bond length. In the second Gd site, Gd(2) is bonded to one O(1), one O(10), one O(5), one O(6), one O(8), and one O(9) atom to form distorted GdO6 pentagonal pyramids that share  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. The Gd(2)-O(1) bond length is 2.39 Å. The Gd(2)-O(10) bond length is 2.41 Å. The Gd(2)-O(5) bond length is 2.37 Å. The Gd(2)-O(6) bond length is 2.45 Å. The Gd(2)-O(8) bond length is 2.30 Å. The Gd(2)-O(9) bond length is 2.38 Å. C(1) is bonded in a trigonal planar geometry to one H(1), one O(2), and one O(6) atom. The C(1)-H(1) bond length is 0.91 Å. The C(1)-O(2) bond length is 1.25 Å. The C(1)-O(6) bond length is 1.27 Å. H(1) is bonded in a single-bond geometry to one C(1) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded to one O(4), one O(5), one O(7), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Gd(2)O6 pentagonal pyramids. The S(1)-O(4) bond length is 1.47 Å. The S(1)-O(5) bond length is 1.48 Å. The S(1)-O(7) bond length is 1.48 Å. The S(1)-O(8) bond length is 1.48 Å. In the second S site, S(2) is bonded to one O(1), one O(10), one O(12), and one O(3) atom to form SO4 tetrahedra that share corners with two equivalent Gd(2)O6 pentagonal pyramids. The S(2)-O(1) bond length is 1.48 Å. The S(2)-O(10) bond length is 1.49 Å. The S(2)-O(12) bond length is 1.46 Å. The S(2)-O(3) bond length is 1.48 Å. In the third S site, S(3) is bonded to two equivalent O(11) and two equivalent O(9) atoms to form SO4 tetrahedra that share corners with two equivalent Gd(2)O6 pentagonal pyramids. Both S(3)-O(11) bond lengths are 1.48 Å. Both S(3)-O(9) bond lengths are 1.48 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Gd(2) and one S(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Gd(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Gd(1) and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Gd(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Gd(2) and one S(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Gd(1), one Gd(2), and one C(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Gd(1) and one S(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Gd(2) and one S(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Gd(2) and one S(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Gd(2) and one S(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Gd(1) and one S(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Gd(1) and one S(2) atom. Linkers: 20 [O]S([O])(=O)=O ,8 [O]C=O. Metal clusters: 16 [Gd]. The MOF has largest included sphere 4.58 A, density 3.25 g/cm3, surface area 1568.18 m2/g, accessible volume 0.11 cm3/g