NaC3H4(NO)3 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to one N(1), one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form a mixture of edge and corner-sharing NaNO5 octahedra. The corner-sharing octahedral tilt angles range from 47-68°. The Na(1)-N(1) bond length is 2.48 Å. The Na(1)-O(1) bond length is 2.37 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.44 Å. There is one shorter (2.37 Å) and one longer (2.44 Å) Na(1)-O(2) bond length. There are three inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(3), and one O(1) atom. The C(1)-C(2) bond length is 1.47 Å. The C(1)-C(3) bond length is 1.47 Å. The C(1)-O(1) bond length is 1.24 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one N(3) atom. The C(2)-C(3) bond length is 1.41 Å. The C(2)-N(3) bond length is 1.35 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(2), and one N(1) atom. The C(3)-N(1) bond length is 1.35 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Na(1), one C(3), and one N(2) atom. The N(1)-N(2) bond length is 1.34 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one N(1) and one N(3) atom. The N(2)-N(3) bond length is 1.35 Å. In the third N site, N(3) is bonded in a 1-coordinate geometry to one C(2) and one N(2) atom. There are four 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 1.00 Å. 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(3) atom. The H(3)-O(3) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(4) atom. The H(4)-O(4) bond length is 0.99 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted water-like geometry to two equivalent Na(1) and two equivalent H(3) atoms. In the second O site, O(4) is bonded in a distorted water-like geometry to two equivalent Na(1) and two equivalent H(4) atoms. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one C(1) atom. In the fourth O site, O(2) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(2) atom. Linkers: 2 O=C1[C]2N=NN=C2C(=O)C2=N[N]N=C12. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.31 A, density 1.86 g/cm3, surface area 2695.31 m2/g, accessible volume 0.03 cm3/g