Na6GdC40N8H24S8O36Cl crystallizes in the tetragonal P-4 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(6), one O(8), one O(9), two equivalent O(4), and one Cl(1) atom to form distorted NaClO5 pentagonal pyramids that share  a cornercorner with one Na(1)ClO5 pentagonal pyramid,  an edgeedge with one Na(2)O6 octahedra, and edges with two equivalent Na(1)ClO5 pentagonal pyramids. The Na(1)-O(6) bond length is 2.55 Å. The Na(1)-O(8) bond length is 2.72 Å. The Na(1)-O(9) bond length is 2.48 Å. There is one shorter (2.39 Å) and one longer (2.40 Å) Na(1)-O(4) bond length. The Na(1)-Cl(1) bond length is 2.74 Å. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms to form edge-sharing NaO6 octahedra. Both Na(2)-O(3) bond lengths are 2.32 Å. Both Na(2)-O(6) bond lengths are 2.49 Å. Both Na(2)-O(9) bond lengths are 2.38 Å. Gd(1) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. All Gd(1)-O(1) bond lengths are 2.36 Å. All Gd(1)-O(2) bond lengths are 2.38 Å. There are ten inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(1) atom. The C(1)-N(1) bond length is 1.36 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(3) and one H(2) atom. The C(2)-C(3) bond length is 1.41 Å. The C(2)-H(2) bond length is 0.93 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one S(1) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-S(1) bond length is 1.78 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(3) atom. The C(4)-C(5) bond length is 1.38 Å. The C(4)-H(3) bond length is 0.93 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(4), one C(6), and one N(1) atom. The C(5)-C(6) bond length is 1.48 Å. The C(5)-N(1) bond length is 1.36 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(5), one C(7), and one N(2) atom. The C(6)-C(7) bond length is 1.37 Å. The C(6)-N(2) bond length is 1.37 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(6), one C(8), and one H(4) atom. The C(7)-C(8) bond length is 1.39 Å. The C(7)-H(4) bond length is 0.93 Å. In the eighth 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 1.41 Å. The C(8)-S(2) bond length is 1.77 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(8) and one H(5) atom. The C(9)-H(5) bond length is 0.93 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(6) atom. The C(10)-N(2) bond length is 1.33 Å. The C(10)-H(6) bond length is 0.93 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(1), one C(5), and one O(1) atom. The N(1)-O(1) bond length is 1.32 Å. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(10), one C(6), and one O(2) atom. The N(2)-O(2) bond length is 1.31 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(9) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(10) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(3), one O(3), one O(4), and one O(5) atom. The S(1)-O(3) bond length is 1.44 Å. The S(1)-O(4) bond length is 1.47 Å. The S(1)-O(5) bond length is 1.44 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one C(8), one O(6), one O(7), and one O(8) atom. The S(2)-O(6) bond length is 1.44 Å. The S(2)-O(7) bond length is 1.44 Å. The S(2)-O(8) bond length is 1.47 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Gd(1) and one N(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Gd(1) and one N(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Na(2) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one S(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one S(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Na(1) and one S(2) atom. In the ninth O site, O(9) is bonded in an L-shaped geometry to one Na(1) and one Na(2) atom. Cl(1) is bonded in a rectangular see-saw-like geometry to four equivalent Na(1) atoms. Linkers: 4 [O]S([O])([O])c1cc[n+]([O-])c(-c2cc(S([O])([O])[O])cc[n+]2[O-])c1. Metal clusters: 6 [Na] ,1 [O].[O].[O][Gd]([O])([O])([O])([O])[O]. The MOF has largest included sphere 4.94 A, density 1.60 g/cm3, surface area 3324.57 m2/g, accessible volume 0.16 cm3/g