Na4Ni2C15H3(N3O7)2 crystallizes in the orthorhombic I222 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted square co-planar geometry to one O(12), one O(2), one O(4), and one O(8) atom. The Na(1)-O(12) bond length is 2.35 Å. The Na(1)-O(2) bond length is 2.38 Å. The Na(1)-O(4) bond length is 2.38 Å. The Na(1)-O(8) bond length is 2.32 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(13), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.49 Å. The Na(2)-O(11) bond length is 2.41 Å. The Na(2)-O(13) bond length is 2.41 Å. The Na(2)-O(7) bond length is 2.76 Å. The Na(2)-O(8) bond length is 2.31 Å. The Na(2)-O(9) bond length is 2.42 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(12), one O(13), one O(14), and one O(8) atom. The Na(3)-O(12) bond length is 2.88 Å. The Na(3)-O(13) bond length is 2.60 Å. The Na(3)-O(14) bond length is 2.58 Å. The Na(3)-O(8) bond length is 2.80 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(3), one O(5), and one O(7) atom. The Na(4)-O(11) bond length is 2.83 Å. The Na(4)-O(12) bond length is 2.29 Å. The Na(4)-O(14) bond length is 2.59 Å. The Na(4)-O(3) bond length is 2.52 Å. The Na(4)-O(5) bond length is 2.35 Å. The Na(4)-O(7) bond length is 2.47 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in an octahedral geometry to one N(2), one N(3), one N(4), one O(3), one O(5), and one O(7) atom. The Ni(1)-N(2) bond length is 2.02 Å. The Ni(1)-N(3) bond length is 2.02 Å. The Ni(1)-N(4) bond length is 2.02 Å. The Ni(1)-O(3) bond length is 2.11 Å. The Ni(1)-O(5) bond length is 2.11 Å. The Ni(1)-O(7) bond length is 2.13 Å. In the second Ni site, Ni(2) is bonded in an octahedral geometry to one N(1), one N(5), one N(6), one O(1), one O(11), and one O(9) atom. The Ni(2)-N(1) bond length is 2.01 Å. The Ni(2)-N(5) bond length is 2.02 Å. The Ni(2)-N(6) bond length is 2.03 Å. The Ni(2)-O(1) bond length is 2.12 Å. The Ni(2)-O(11) bond length is 2.13 Å. The Ni(2)-O(9) bond length is 2.10 Å. There are fifteen inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one N(1) atom. The C(1)-N(1) bond length is 1.36 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one N(2) atom. The C(2)-N(2) bond length is 1.37 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(1) atom. The C(3)-N(1) bond length is 1.36 Å. The C(3)-N(2) bond length is 1.32 Å. The C(3)-H(1) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(4)-O(1) bond length is 1.28 Å. The C(4)-O(2) bond length is 1.21 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(5)-O(3) bond length is 1.27 Å. The C(5)-O(4) bond length is 1.27 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one N(3) atom. The C(6)-N(3) bond length is 1.36 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one N(3), one N(6), and one H(2) atom. The C(7)-N(3) bond length is 1.37 Å. The C(7)-N(6) bond length is 1.31 Å. The C(7)-H(2) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(8)-O(5) bond length is 1.27 Å. The C(8)-O(6) bond length is 1.23 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one N(4) atom. The C(9)-N(4) bond length is 1.38 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one N(5) atom. The C(10)-N(5) bond length is 1.36 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one N(4), one N(5), and one H(3) atom. The C(11)-N(4) bond length is 1.33 Å. The C(11)-N(5) bond length is 1.31 Å. The C(11)-H(3) bond length is 0.93 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one O(7) and one O(8) atom. The C(12)-O(7) bond length is 1.24 Å. The C(12)-O(8) bond length is 1.26 Å. In the thirteenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(12) atom. The C(13)-O(11) bond length is 1.27 Å. The C(13)-O(12) bond length is 1.24 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one N(6) atom. The C(14)-N(6) bond length is 1.38 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(15)-O(10) bond length is 1.20 Å. The C(15)-O(9) bond length is 1.26 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Ni(2), one C(1), and one C(3) atom. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Ni(1), one C(2), and one C(3) atom. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Ni(1), one C(6), and one C(7) atom. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Ni(1), one C(11), and one C(9) atom. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Ni(2), one C(10), and one C(11) atom. In the sixth N site, N(6) is bonded in a distorted trigonal planar geometry to one Ni(2), one C(14), and one C(7) atom. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(7) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(11) atom. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Ni(2), and one C(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Na(1) and one C(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(4), one Ni(1), and one C(5) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Na(1) and one C(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Ni(1), and one C(8) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one C(8) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ni(1), and one C(12) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one C(12) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Ni(2), and one C(15) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one C(15) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ni(2), and one C(13) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Na(4), and one C(13) atom. In the thirteenth O site, O(13) is bonded in a water-like geometry to one Na(2) and one Na(3) atom. In the fourteenth O site, O(14) is bonded in a water-like geometry to one Na(3) and one Na(4) atom. Linkers: 5 [O]C(=O)C1=C(C([O])=O)N=C[N]1 ,6 [O]C(=O)[C]1N=CN=C1C([O])=O. Metal clusters: 16 [Na] ,8 [Ni]. The MOF has largest included sphere 5.79 A, density 1.33 g/cm3, surface area 3286.73 m2/g, accessible volume 0.27 cm3/g