Na4Mo5C5NH6O22 crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(18), one O(19), one O(20), one O(3), and one O(8) atom to form a mixture of edge and corner-sharing NaO5 square pyramids. The Na(1)-O(18) bond length is 2.29 Å. The Na(1)-O(19) bond length is 2.33 Å. The Na(1)-O(20) bond length is 2.41 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(8) bond length is 2.46 Å. In the second Na site, Na(2) is bonded to one O(13), one O(18), one O(19), one O(20), and one O(21) atom to form a mixture of edge and corner-sharing NaO5 square pyramids. The Na(2)-O(13) bond length is 2.45 Å. The Na(2)-O(18) bond length is 2.50 Å. The Na(2)-O(19) bond length is 2.29 Å. The Na(2)-O(20) bond length is 2.20 Å. The Na(2)-O(21) bond length is 2.44 Å. In the third Na site, Na(3) is bonded in a rectangular see-saw-like geometry to one O(21), one O(22), one O(5), and one O(9) atom. The Na(3)-O(21) bond length is 2.53 Å. The Na(3)-O(22) bond length is 2.29 Å. The Na(3)-O(5) bond length is 2.53 Å. The Na(3)-O(9) bond length is 2.48 Å. In the fourth Na site, Na(4) is bonded in a T-shaped geometry to one O(1), one O(15), and one O(22) atom. The Na(4)-O(1) bond length is 2.73 Å. The Na(4)-O(15) bond length is 2.58 Å. The Na(4)-O(22) bond length is 2.43 Å. There are five inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(3), one O(6), and two equivalent O(7) atoms. The Mo(1)-O(10) bond length is 2.14 Å. The Mo(1)-O(2) bond length is 1.75 Å. The Mo(1)-O(3) bond length is 1.70 Å. The Mo(1)-O(6) bond length is 1.89 Å. There is one shorter (1.94 Å) and one longer (2.43 Å) Mo(1)-O(7) bond length. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one N(1), one O(11), one O(17), one O(4), and one O(8) atom. The Mo(2)-N(1) bond length is 2.37 Å. The Mo(2)-O(11) bond length is 2.11 Å. The Mo(2)-O(17) bond length is 2.17 Å. The Mo(2)-O(4) bond length is 1.81 Å. The Mo(2)-O(8) bond length is 1.69 Å. In the third Mo site, Mo(3) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(15), one O(2), and one O(7) atom. The Mo(3)-O(10) bond length is 1.89 Å. The Mo(3)-O(14) bond length is 1.94 Å. The Mo(3)-O(15) bond length is 1.72 Å. The Mo(3)-O(2) bond length is 2.34 Å. The Mo(3)-O(7) bond length is 2.24 Å. In the fourth Mo site, Mo(4) is bonded in a distorted square pyramidal geometry to one O(10), one O(12), one O(4), one O(5), and one O(6) atom. The Mo(4)-O(10) bond length is 2.18 Å. The Mo(4)-O(12) bond length is 1.93 Å. The Mo(4)-O(4) bond length is 1.98 Å. The Mo(4)-O(5) bond length is 1.71 Å. The Mo(4)-O(6) bond length is 2.24 Å. In the fifth Mo site, Mo(5) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(14), one O(6), one O(7), and one O(9) atom. The Mo(5)-O(12) bond length is 1.93 Å. The Mo(5)-O(13) bond length is 1.70 Å. The Mo(5)-O(14) bond length is 1.94 Å. The Mo(5)-O(6) bond length is 2.29 Å. The Mo(5)-O(7) bond length is 2.22 Å. The Mo(5)-O(9) bond length is 1.72 Å. There are five inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(17) atom. The C(1)-O(1) bond length is 1.23 Å. The C(1)-O(17) bond length is 1.28 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one N(1) and two equivalent H(1,2) atoms. The C(2)-N(1) bond length is 1.48 Å. Both C(2)-H(1,2) bond lengths are 0.97 Å. In the third C site, C(3) is bonded in a 3-coordinate geometry to one N(1) and two equivalent H(3,4) atoms. The C(3)-N(1) bond length is 1.50 Å. Both C(3)-H(3,4) bond lengths are 0.97 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(16) atom. The C(4)-O(11) bond length is 1.30 Å. The C(4)-O(16) bond length is 1.22 Å. In the fifth C site, C(5) is bonded in a 3-coordinate geometry to one N(1) and two equivalent H(5,6) atoms. The C(5)-N(1) bond length is 1.49 Å. Both C(5)-H(5,6) bond lengths are 0.97 Å. N(1) is bonded in a distorted trigonal non-coplanar geometry to one Mo(2), one C(2), one C(3), and one C(5) atom. There are three inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(3,4) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(5,6) is bonded in a single-bond geometry to one C(5) atom. There are twenty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Na(4) and one C(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one Mo(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Na(1) and one Mo(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mo(2) and one Mo(4) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Na(3) and one Mo(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mo(1), one Mo(4), and one Mo(5) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Mo(3), one Mo(5), and two equivalent Mo(1) atoms. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(1) and one Mo(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one Mo(5) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(3), and one Mo(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Mo(2) and one C(4) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Mo(4) and one Mo(5) atom. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Na(2) and one Mo(5) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Na(4) and one Mo(3) atom. In the sixteenth O site, O(16) is bonded in a single-bond geometry to one C(4) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 120 degrees geometry to one Mo(2) and one C(1) atom. In the eighteenth O site, O(18) is bonded in an L-shaped geometry to one Na(1) and one Na(2) atom. In the nineteenth O site, O(19) is bonded in an L-shaped geometry to one Na(1) and one Na(2) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Na(1) and one Na(2) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Na(2) and one Na(3) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one Na(3) and one Na(4) atom. Linkers: 4 [O]C(=O)CN(CCN(CC([O])=O)CC([O])=O)CC([O])=O. Metal clusters: 32 [Na] ,40 [Mo]. The MOF has largest included sphere 6.42 A, density 1.69 g/cm3, surface area 2765.45 m2/g, accessible volume 0.26 cm3/g