Na5GdC12H24O29Cl2 crystallizes in the trigonal R32 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form edge-sharing NaO6 octahedra. All Na(1)-O(3) bond lengths are 2.37 Å. All Na(1)-O(4) bond lengths are 2.45 Å. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted NaO6 octahedra that share corners with two equivalent Cl(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. Both Na(2)-O(3) bond lengths are 2.47 Å. Both Na(2)-O(4) bond lengths are 2.30 Å. Both Na(2)-O(6) bond lengths are 2.47 Å. Gd(1) is bonded in a 9-coordinate geometry to three equivalent O(1) and six equivalent O(2) atoms. All Gd(1)-O(1) bond lengths are 2.48 Å. All Gd(1)-O(2) bond lengths are 2.39 Å. There are two inequivalent C sites. In the first C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(2) and one O(3) atom. The C(2)-O(2) bond length is 1.29 Å. The C(2)-O(3) bond length is 1.25 Å. In the second C site, C(1) is bonded in a distorted trigonal non-coplanar geometry to one H(1), one H(2), and one O(1) atom. The C(1)-H(1) bond length is 1.10 Å. The C(1)-H(2) bond length is 1.10 Å. The C(1)-O(1) bond length is 1.43 Å. There are four inequivalent H sites. In the first H site, H(4) is bonded in a single-bond geometry to one O(4) atom. The H(4)-O(4) bond length is 0.97 Å. In the second H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(2) is bonded in a single-bond geometry to one C(1) atom. In the fourth H site, H(3) is bonded in a single-bond geometry to one O(2) and one O(4) atom. The H(3)-O(2) bond length is 1.69 Å. The H(3)-O(4) bond length is 1.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Gd(1) and two equivalent C(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Gd(1), one C(2), and one H(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(2) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(3), and one H(4) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one Cl(1) atom. The O(5)-Cl(1) bond length is 1.45 Å. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Na(2) and one Cl(1) atom. The O(6)-Cl(1) bond length is 1.46 Å. Cl(1) is bonded to one O(5) and three equivalent O(6) atoms to form ClO4 tetrahedra that share corners with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Linkers: 3 [O]C(=O)COCC([O])=O ,6 O ,2 [O].[O].[O].[O]Cl. Metal clusters: 5 [Na] ,1 [Gd]. The MOF has largest included sphere 2.16 A, density 2.15 g/cm3, surface area 2386.34 m2/g, accessible volume 0.05 cm3/g