Na6W12Cu3C4H8(NO22)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(2), and one O(7) atom. The Na(1)-O(1) bond length is 2.29 Å. The Na(1)-O(10) bond length is 2.36 Å. The Na(1)-O(2) bond length is 2.48 Å. The Na(1)-O(7) bond length is 2.41 Å. In the second Na site, Na(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(18), one O(2), and one O(22) atom. The Na(2)-O(1) bond length is 2.52 Å. The Na(2)-O(18) bond length is 2.27 Å. The Na(2)-O(2) bond length is 2.53 Å. The Na(2)-O(22) bond length is 2.34 Å. In the third Na site, Na(3) is bonded in a bent 150 degrees geometry to one O(19) and one O(7) atom. The Na(3)-O(19) bond length is 2.23 Å. The Na(3)-O(7) bond length is 2.33 Å. There are six inequivalent W sites. In the first W site, W(1) is bonded to one O(12), one O(13), one O(15), one O(4), and one O(5) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(5)O5 square pyramid and  an edgeedge with one W(3)O6 octahedra. The W(1)-O(12) bond length is 1.91 Å. The W(1)-O(13) bond length is 1.90 Å. The W(1)-O(15) bond length is 2.16 Å. The W(1)-O(4) bond length is 1.79 Å. The W(1)-O(5) bond length is 2.31 Å. In the second W site, W(2) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(14), one O(5), and one O(6) atom. The W(2)-O(12) bond length is 1.94 Å. The W(2)-O(14) bond length is 2.17 Å. The W(2)-O(5) bond length is 2.26 Å. The W(2)-O(6) bond length is 1.88 Å. In the third W site, W(3) is bonded to one O(10), one O(13), one O(15), one O(3), one O(8), and one O(9) atom to form a mixture of distorted edge and corner-sharing WO6 octahedra. The W(3)-O(10) bond length is 1.72 Å. The W(3)-O(13) bond length is 1.96 Å. The W(3)-O(15) bond length is 2.22 Å. The W(3)-O(3) bond length is 2.08 Å. The W(3)-O(8) bond length is 1.86 Å. The W(3)-O(9) bond length is 1.76 Å. In the fourth W site, W(4) is bonded in a 6-coordinate geometry to one O(11), one O(17), one O(19), one O(20), one O(6), and one O(8) atom. The W(4)-O(11) bond length is 1.90 Å. The W(4)-O(17) bond length is 2.24 Å. The W(4)-O(19) bond length is 1.76 Å. The W(4)-O(20) bond length is 1.88 Å. The W(4)-O(6) bond length is 1.93 Å. The W(4)-O(8) bond length is 1.94 Å. In the fifth W site, W(5) is bonded to one O(17), one O(20), one O(21), one O(3), and one O(5) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(3)O6 octahedra and  a cornercorner with one W(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 37°. The W(5)-O(17) bond length is 2.22 Å. The W(5)-O(20) bond length is 2.06 Å. The W(5)-O(21) bond length is 1.95 Å. The W(5)-O(3) bond length is 1.81 Å. The W(5)-O(5) bond length is 1.88 Å. In the sixth W site, W(6) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(15), one O(17), one O(18), and one O(21) atom. The W(6)-O(11) bond length is 2.06 Å. The W(6)-O(14) bond length is 1.81 Å. The W(6)-O(15) bond length is 1.94 Å. The W(6)-O(17) bond length is 2.27 Å. The W(6)-O(18) bond length is 1.71 Å. The W(6)-O(21) bond length is 1.95 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a T-shaped geometry to one N(1), one O(16), and one O(4) atom. The Cu(1)-N(1) bond length is 1.97 Å. The Cu(1)-O(16) bond length is 1.93 Å. The Cu(1)-O(4) bond length is 1.96 Å. In the second Cu site, Cu(2) is bonded in a linear geometry to two equivalent O(9) atoms. Both Cu(2)-O(9) bond lengths are 1.95 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 3-coordinate geometry to one N(1) and two equivalent H(1,2) atoms. The C(1)-N(1) bond length is 1.49 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(16) and one O(22) atom. The C(2)-O(16) bond length is 1.27 Å. The C(2)-O(22) bond length is 1.21 Å. N(1) is bonded in a distorted tetrahedral geometry to one Cu(1), one C(1), one H(3), and one H(4) atom. The N(1)-H(3) bond length is 0.90 Å. The N(1)-H(4) bond length is 0.90 Å. There are three inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3) is bonded in a single-bond geometry to one N(1) atom. In the third H site, H(4) is bonded in a single-bond geometry to one N(1) atom. There are twenty-two inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to one Na(1) and one Na(2) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one Na(1) and one Na(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one W(3) and one W(5) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(1) and one Cu(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one W(1), one W(2), and one W(5) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one W(2) and one W(4) atom. In the seventh O site, O(7) is bonded in a water-like geometry to one Na(1) and one Na(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one W(3) and one W(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one W(3) and one Cu(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Na(1) and one W(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one W(4) and one W(6) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one W(1) and one W(2) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one W(1) and one W(3) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one W(2) and one W(6) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one W(1), one W(3), and one W(6) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(2) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one W(4), one W(5), and one W(6) atom. In the eighteenth O site, O(18) is bonded in a distorted linear geometry to one Na(2) and one W(6) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Na(3) and one W(4) atom. In the twentieth O site, O(20) is bonded in a bent 120 degrees geometry to one W(4) and one W(5) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one W(5) and one W(6) atom. In the twenty-second O site, O(22) is bonded in a distorted water-like geometry to one Na(2) and one C(2) atom. Linkers: 2 NCC([O])=O. Metal clusters: 6 [Na] ,3 [Cu] ,12 [W]. The MOF has largest included sphere 4.37 A, density 3.35 g/cm3, surface area 1559.01 m2/g, accessible volume 0.10 cm3/g