NaCH3(N2O)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one N(2), two equivalent O(2), and three equivalent O(1) atoms to form edge-sharing NaNO5 octahedra. The Na(1)-N(2) bond length is 2.53 Å. There is one shorter (2.37 Å) and one longer (2.46 Å) Na(1)-O(2) bond length. There are a spread of Na(1)-O(1) bond distances ranging from 2.42-2.47 Å. 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 1.37 Å. The C(1)-N(4) bond length is 1.37 Å. The C(1)-O(1) bond length is 1.27 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a distorted single-bond geometry to one C(1) and one N(3) atom. The N(4)-N(3) bond length is 1.35 Å. In the second N site, N(1) is bonded in a 3-coordinate geometry to one C(1), one N(2), and one H(1) atom. The N(1)-N(2) bond length is 1.34 Å. The N(1)-H(1) bond length is 1.06 Å. In the third 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 1.30 Å. In the fourth N site, N(3) is bonded in a distorted trigonal planar geometry to one N(2), one N(4), and one H(1) atom. The N(3)-H(1) bond length is 1.71 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one N(1) and one N(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) atom. The H(2)-O(2) bond length is 0.98 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(2) atom. The H(3)-O(2) bond length is 1.00 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Na(1) and one C(1) atom. In the second O site, O(2) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(2), and one H(3) atom. Linkers: 4 O ,4 O=C1[N]N=NN1. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.46 A, density 1.89 g/cm3, surface area 2603.98 m2/g, accessible volume 0.04 cm3/g