NaC4N4H8O3 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one N(3), one O(1), one O(4), one O(5), and two equivalent O(3) atoms. The Na(1)-N(3) bond length is 2.51 Å. The Na(1)-O(1) bond length is 2.36 Å. The Na(1)-O(4) bond length is 2.40 Å. The Na(1)-O(5) bond length is 2.65 Å. There is one shorter (2.37 Å) and one longer (2.45 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to one N(5), one O(1), one O(2), one O(4), and two equivalent O(6) atoms to form distorted edge-sharing NaNO5 octahedra. The Na(2)-N(5) bond length is 2.49 Å. The Na(2)-O(1) bond length is 2.34 Å. The Na(2)-O(2) bond length is 2.51 Å. The Na(2)-O(4) bond length is 2.47 Å. There is one shorter (2.33 Å) and one longer (2.38 Å) Na(2)-O(6) bond length. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted water-like geometry to one C(2), one N(1), and one N(4) atom. The C(1)-C(2) bond length is 1.46 Å. The C(1)-N(1) bond length is 1.35 Å. The C(1)-N(4) bond length is 1.35 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(7) atom. The C(2)-C(3) bond length is 1.41 Å. The C(2)-C(7) bond length is 1.41 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2) and one H(13) atom. The C(3)-H(13) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(5) and one H(14) atom. The C(4)-C(5) bond length is 1.41 Å. The C(4)-H(14) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(4), one C(6), and one C(8) atom. The C(5)-C(6) bond length is 1.40 Å. The C(5)-C(8) bond length is 1.46 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(5), one C(7), and one H(15) atom. The C(6)-C(7) bond length is 1.40 Å. The C(6)-H(15) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(2), one C(6), and one H(16) atom. The C(7)-H(16) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(5), one N(5), and one N(8) atom. The C(8)-N(5) bond length is 1.35 Å. The C(8)-N(8) bond length is 1.35 Å. There are eight inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one C(1) and one N(2) atom. The N(1)-N(2) bond length is 1.35 Å. In the second N site, N(2) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one N(3), and one H(3) atom. The N(2)-N(3) bond length is 1.33 Å. The N(2)-H(3) bond length is 1.77 Å. In the third N site, N(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one N(2), and one N(4) atom. The N(3)-N(4) bond length is 1.34 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 1.77 Å. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Na(2), one C(8), and one N(6) atom. The N(5)-N(6) bond length is 1.34 Å. In the sixth N site, N(6) is bonded in a distorted trigonal planar geometry to one N(5), one N(7), and one H(5) atom. The N(6)-N(7) bond length is 1.32 Å. The N(6)-H(5) bond length is 1.70 Å. In the seventh N site, N(7) is bonded in a distorted trigonal planar geometry to one N(6), one N(8), and one H(10) atom. The N(7)-N(8) bond length is 1.34 Å. The N(7)-H(10) bond length is 1.77 Å. In the eighth N site, N(8) is bonded in a distorted single-bond geometry to one C(8) and one N(7) atom. There are sixteen 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 N(4) and one O(1) atom. The H(2)-O(1) bond length is 1.00 Å. In the third H site, H(3) is bonded in a single-bond geometry to one N(2) and one O(2) atom. The H(3)-O(2) bond length is 1.01 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(2) atom. The H(4)-O(2) bond length is 0.97 Å. In the fifth H site, H(5) is bonded in a distorted single-bond geometry to one N(6) and one O(3) atom. The H(5)-O(3) bond length is 1.01 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(3) atom. The H(6)-O(3) bond length is 0.98 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(4) atom. The H(7)-O(4) bond length is 0.98 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(4) atom. The H(8)-O(4) bond length is 0.99 Å. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(5) atom. The H(9)-O(5) bond length is 0.98 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one N(7) and one O(5) atom. The H(10)-O(5) bond length is 1.01 Å. In the eleventh H site, H(11) is bonded in a single-bond geometry to one O(6) atom. The H(11)-O(6) bond length is 0.98 Å. In the twelfth H site, H(12) is bonded in a single-bond geometry to one O(6) atom. The H(12)-O(6) bond length is 0.99 Å. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(3) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(4) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(6) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(7) atom. There are six 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 water-like geometry to one Na(2), one H(3), and one H(4) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(5), and one H(6) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Na(1), one Na(2), one H(7), and one H(8) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one Na(1), one H(10), and one H(9) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to two equivalent Na(2), one H(11), and one H(12) atom. Linkers: 2 c1cc(C2=NN=N[N]2)ccc1C1=NN=N[N]1. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.88 A, density 1.58 g/cm3, surface area 3791.52 m2/g, accessible volume 0.11 cm3/g