NaH3(C3O)2 crystallizes in the hexagonal P6_5 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(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. The Na(1)-O(2) bond length is 2.55 Å. The Na(1)-O(4) bond length is 2.64 Å. There is one shorter (2.28 Å) and one longer (2.51 Å) Na(1)-O(1) bond length. There is one shorter (2.26 Å) and one longer (2.44 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(2)-O(1) bond length is 2.38 Å. The Na(2)-O(2) bond length is 2.34 Å. The Na(2)-O(3) bond length is 2.39 Å. The Na(2)-O(4) bond length is 2.30 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-O(1) bond length is 1.26 Å. The C(1)-O(2) bond length is 1.24 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(4), and one C(5) atom. The C(2)-C(4) bond length is 1.42 Å. The C(2)-C(5) bond length is 1.37 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(11), one C(4), and one C(6) atom. The C(3)-C(11) bond length is 1.43 Å. The C(3)-C(4) bond length is 1.43 Å. The C(3)-C(6) bond length is 1.42 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(7) atom. The C(4)-C(7) bond length is 1.42 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(2) and one H(1) atom. The C(5)-H(1) bond length is 0.93 Å. In the sixth C site, C(6) is bonded in a single-bond geometry to one C(3) and one H(2) atom. The C(6)-H(2) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(4), one C(9), and one H(3) atom. The C(7)-C(9) bond length is 1.34 Å. The C(7)-H(3) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(9) and one H(4) atom. The C(8)-C(9) bond length is 1.39 Å. The C(8)-H(4) bond length is 0.93 Å. In the ninth C site, C(9) is bonded in a distorted trigonal planar geometry to one C(7), 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 single-bond geometry to one C(11) and one H(6) atom. The C(10)-C(11) bond length is 1.37 Å. The C(10)-H(6) bond length is 0.93 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(3) atom. The C(11)-C(12) bond length is 1.51 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.26 Å. The C(12)-O(4) bond length is 1.24 Å. There are six inequivalent H sites. In the first H site, H(1) 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 C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(8) 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 four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), and one C(1) atom to form a mixture of distorted edge and corner-sharing ONa3C trigonal pyramids. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one C(1) atom. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), and one C(12) atom to form a mixture of distorted edge and corner-sharing ONa3C trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(12) atom. Linkers: 6 [O]C(=O)c1ccc(C([O])=O)c2ccccc12. Metal clusters: 12 [Na]. The MOF has largest included sphere 7.09 A, density 1.04 g/cm3, surface area 4118.73 m2/g, accessible volume 0.47 cm3/g