NaC3N7H6O2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form face-sharing NaN2O4 octahedra. Both Na(1)-N(1) bond lengths are 2.68 Å. Both Na(1)-O(1) bond lengths are 2.40 Å. Both Na(1)-O(2) bond lengths are 2.37 Å. In the second Na site, Na(2) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form face-sharing NaN2O4 octahedra. Both Na(2)-N(1) bond lengths are 2.68 Å. Both Na(2)-O(1) bond lengths are 2.36 Å. Both Na(2)-O(2) bond lengths are 2.40 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(2), one N(3), and one H(5) atom. The C(1)-N(2) bond length is 1.31 Å. The C(1)-N(3) bond length is 1.38 Å. The C(1)-H(5) bond length is 1.08 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(3), and one H(6) atom. The C(2)-N(1) bond length is 1.32 Å. The C(2)-N(3) bond length is 1.37 Å. The C(2)-H(6) bond length is 1.09 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(3), one N(4), and one N(7) atom. The C(3)-N(3) bond length is 1.40 Å. The C(3)-N(4) bond length is 1.34 Å. The C(3)-N(7) bond length is 1.34 Å. There are seven inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one C(2), and one N(2) atom. The N(1)-N(2) bond length is 1.40 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one C(1) and one N(1) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one C(1), one C(2), and one C(3) atom. In the fourth N site, N(4) is bonded in a distorted single-bond geometry to one C(3), one N(5), and one H(3) atom. The N(4)-N(5) bond length is 1.34 Å. The N(4)-H(3) bond length is 1.78 Å. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one N(4), one N(6), and one H(4) atom. The N(5)-N(6) bond length is 1.32 Å. The N(5)-H(4) bond length is 1.77 Å. In the sixth N site, N(6) is bonded in a water-like geometry to one N(5) and one N(7) atom. The N(6)-N(7) bond length is 1.35 Å. In the seventh N site, N(7) is bonded in a distorted single-bond geometry to one C(3) and one N(6) atom. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.99 Å. 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 0.99 Å. In the third H site, H(3) is bonded in a single-bond geometry to one N(4) and one O(2) atom. The H(3)-O(2) bond length is 0.99 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(5) and one O(2) atom. The H(4)-O(2) bond length is 1.00 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(1) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(2) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(3), and one H(4) atom. Linkers: 8 O ,4 c1nncn1C1=NN=N[N]1. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.87 A, density 1.66 g/cm3, surface area 3866.54 m2/g, accessible volume 0.07 cm3/g