NaCN5H6O3 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one N(2), one N(5), one O(2), one O(3), and two equivalent O(1) atoms to form distorted edge-sharing NaN2O4 octahedra. The Na(1)-N(2) bond length is 2.49 Å. The Na(1)-N(5) bond length is 2.59 Å. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.40 Å. There is one shorter (2.42 Å) and one longer (2.54 Å) Na(1)-O(1) bond length. C(1) is bonded in a trigonal planar geometry to one N(1), one N(4), and one O(1) atom. The C(1)-N(1) bond length is 1.38 Å. The C(1)-N(4) bond length is 1.36 Å. The C(1)-O(1) bond length is 1.27 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one C(1), one N(2), and one N(5) atom. The N(1)-N(2) bond length is 1.36 Å. The N(1)-N(5) bond length is 1.39 Å. In the second N site, N(2) is bonded in a trigonal planar geometry to one Na(1), one N(1), and one N(3) atom. The N(2)-N(3) bond length is 1.29 Å. In the third N site, N(3) is bonded in a 3-coordinate geometry to one N(2), one N(4), and one H(3) atom. The N(3)-N(4) bond length is 1.36 Å. The N(3)-H(3) bond length is 1.80 Å. In the fourth N site, N(4) is bonded in a distorted single-bond geometry to one C(1), one N(3), and one H(2) atom. The N(4)-H(2) bond length is 1.78 Å. In the fifth N site, N(5) is bonded in a distorted water-like geometry to one Na(1), one N(1), one H(5), and one H(6) atom. The N(5)-H(5) bond length is 1.04 Å. The N(5)-H(6) bond length is 1.03 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) atom. The H(1)-O(2) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one N(4) and one O(2) atom. The H(2)-O(2) bond length is 1.00 Å. In the third H site, H(3) is bonded in a single-bond geometry to one N(3) and one O(3) atom. The H(3)-O(3) bond length is 1.00 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(3) atom. The H(4)-O(3) bond length is 0.99 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one N(5) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one N(5) atom. There are three inequivalent O sites. In the first O site, O(3) is bonded in a distorted water-like geometry to one Na(1), one H(3), and one H(4) atom. In the second O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Na(1) and one C(1) atom. In the third O site, O(2) is bonded in a distorted water-like geometry to one Na(1), one H(1), and one H(2) atom. Linkers: 4 NN1N=N[N]C1=O. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.36 A, density 1.77 g/cm3, surface area 3486.67 m2/g, accessible volume 0.10 cm3/g