NaC2H2O3 crystallizes in the orthorhombic Pbca space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.54 Å. The Na(1)-O(2) bond length is 2.47 Å. The Na(1)-O(3) bond length is 2.35 Å. The Na(1)-O(6) bond length is 2.31 Å. Both Na(1)-O(4) bond lengths are 2.38 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms to form distorted edge-sharing NaO6 pentagonal pyramids. The Na(2)-O(1) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.32 Å. The Na(2)-O(3) bond length is 2.47 Å. The Na(2)-O(6) bond length is 2.41 Å. There is one shorter (2.38 Å) and one longer (2.52 Å) Na(2)-O(5) bond length. There are four inequivalent C sites. In the first C site, C(3) is bonded in a distorted water-like geometry to one H(2) and one O(4) atom. The C(3)-H(2) bond length is 1.10 Å. The C(3)-O(4) bond length is 1.43 Å. In the second C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(4)-O(5) bond length is 1.28 Å. The C(4)-O(6) bond length is 1.26 Å. In the third C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(1)-O(1) bond length is 1.28 Å. The C(1)-O(2) bond length is 1.26 Å. In the fourth C site, C(2) is bonded in a distorted water-like geometry to one H(1) and one O(3) atom. The C(2)-H(1) bond length is 1.10 Å. The C(2)-O(3) bond length is 1.43 Å. There are four inequivalent H sites. In the first H site, H(3) is bonded in a linear geometry to one O(1) and one O(3) atom. The H(3)-O(1) bond length is 1.59 Å. The H(3)-O(3) bond length is 1.01 Å. In the second H site, H(4) is bonded in a distorted linear geometry to one O(4) and one O(5) atom. The H(4)-O(4) bond length is 1.00 Å. The H(4)-O(5) bond length is 1.60 Å. In the third H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(2) is bonded in a single-bond geometry to one C(3) atom. There are six inequivalent O sites. In the first O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one C(2), and one H(3) atom. In the second O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one C(3), and one H(4) atom. In the third O site, O(1) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(2), one C(1), and one H(3) atom. In the fourth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one C(4), and one H(4) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(4) atom. Linkers: 4 [O]C(=O)[C@@H](O)[C@H](O)C([O])=O ,4 [O]C(=O)[C@H](O)[C@@H](O)C([O])=O. Metal clusters: 16 [Na]. The MOF has largest included sphere 1.89 A, density 1.96 g/cm3, surface area 1817.46 m2/g, accessible volume 0.05 cm3/g