Na3C6N7H12O9 crystallizes in the trigonal R3c space group. Na(1) is bonded in a 7-coordinate geometry to one N(1), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-N(1) bond length is 2.52 Å. There is one shorter (2.60 Å) and one longer (2.61 Å) Na(1)-O(1) bond length. There is one shorter (2.42 Å) and one longer (2.49 Å) Na(1)-O(2) bond length. There is one shorter (2.38 Å) and one longer (2.42 Å) Na(1)-O(3) bond length. There are two inequivalent C sites. In the first C site, C(2) is bonded to one N(1), one N(2), one H(3), and one H(4) atom to form corner-sharing CH2N2 tetrahedra. The C(2)-N(1) bond length is 1.48 Å. The C(2)-N(2) bond length is 1.47 Å. The C(2)-H(3) bond length is 1.10 Å. The C(2)-H(4) bond length is 1.10 Å. In the second C site, C(1) is bonded to two equivalent N(1), one H(1), and one H(2) atom to form corner-sharing CH2N2 tetrahedra. Both C(1)-N(1) bond lengths are 1.48 Å. The C(1)-H(1) bond length is 1.10 Å. The C(1)-H(2) bond length is 1.10 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Na(1), one C(2), and two equivalent C(1) atoms to form corner-sharing NNaC3 tetrahedra. In the second N site, N(2) is bonded in a trigonal non-coplanar geometry to three equivalent C(2) atoms. In the third N site, N(3) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The N(3)-O(1) bond length is 1.26 Å. The N(3)-O(2) bond length is 1.27 Å. The N(3)-O(3) bond length is 1.28 Å. There are four inequivalent H sites. In the first H site, H(4) is bonded in a single-bond geometry to one C(2) atom. 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 C(2) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one N(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one N(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one N(3) atom. Linkers: 2 C1N2CN3CN1CN(C2)C3. Metal clusters: 6 [Na]. The MOF has largest included sphere 1.64 A, density 1.74 g/cm3, surface area 3321.02 m2/g, accessible volume 0.07 cm3/g