NaH10(CO2)2NaC8H10(O4Br)2 is Indium-like structured and crystallizes in the orthorhombic C222_1 space group. The structure is zero-dimensional and consists of four NaC8H10(O4Br)2 clusters and four NaH10(CO2)2 clusters. In each NaC8H10(O4Br)2 cluster, Na(1) is bonded in an octahedral geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Both Na(1)-O(3) bond lengths are 2.41 Å. Both Na(1)-O(4) bond lengths are 2.42 Å. Both Na(1)-O(5) bond lengths are 2.36 Å. There are four inequivalent C sites. In the first C site, C(3) is bonded in a distorted water-like geometry to one H(8) and one O(5) atom. The C(3)-H(8) bond length is 1.10 Å. The C(3)-O(5) bond length is 1.43 Å. In the second C site, C(4) is bonded in a distorted water-like geometry to one H(1) and one O(6) atom. The C(4)-H(1) bond length is 1.10 Å. The C(4)-O(6) bond length is 1.48 Å. In the third C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(6) atom. The C(1)-O(3) bond length is 1.23 Å. The C(1)-O(6) bond length is 1.34 Å. In the fourth C site, C(2) is bonded in a distorted water-like geometry to one H(7) and one O(4) atom. The C(2)-H(7) bond length is 1.11 Å. The C(2)-O(4) bond length is 1.41 Å. There are five inequivalent H sites. In the first H site, H(7) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(8) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(1) 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 O(4) and one Br(1) atom. The H(4)-O(4) bond length is 1.00 Å. The H(4)-Br(1) bond length is 2.15 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(5) atom. The H(5)-O(5) bond length is 0.98 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one C(1) atom. In the second O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one C(2), and one H(4) atom. In the third O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one C(3), and one H(5) atom. In the fourth O site, O(6) is bonded in a water-like geometry to one C(1) and one C(4) atom. Br(1) is bonded in a 1-coordinate geometry to one H(4) atom. In each NaH10(CO2)2 cluster, Na(2) is bonded in a distorted square co-planar geometry to one O(1), one O(2), and two equivalent O(7) atoms. The Na(2)-O(1) bond length is 2.32 Å. The Na(2)-O(2) bond length is 2.28 Å. Both Na(2)-O(7) bond lengths are 2.40 Å. C(5) is bonded in a distorted trigonal non-coplanar geometry to one H(10), one H(9), and one O(7) atom. The C(5)-H(10) bond length is 1.10 Å. The C(5)-H(9) bond length is 1.10 Å. The C(5)-O(7) bond length is 1.43 Å. There are five inequivalent H sites. In the first H site, H(9) is bonded in a single-bond geometry to one C(5) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.98 Å. In the third H site, H(10) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(3) is bonded in a single-bond geometry to one O(2) atom. The H(3)-O(2) bond length is 0.98 Å. In the fifth H site, H(6) is bonded in a single-bond geometry to one O(7) atom. The H(6)-O(7) bond length is 0.99 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Na(2) and two equivalent H(2) atoms. In the second O site, O(2) is bonded in a distorted water-like geometry to one Na(2) and two equivalent H(3) atoms. In the third O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one C(5), and one H(6) atom. Linkers: 4 O=C1O[C@H](CO)[C@@H](O)[C@H]1O. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.47 A, density 1.98 g/cm3, surface area 3250.16 m2/g, accessible volume 0.09 cm3/g