Na2Mo6C5P3NH6O23 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(1), one O(7), one O(9), and two equivalent O(10) atoms to form distorted NaO5 square pyramids that share  a cornercorner with one P(1)CO3 tetrahedra and  an edgeedge with one Na(1)O5 square pyramid. The Na(1)-O(1) bond length is 2.44 Å. The Na(1)-O(7) bond length is 2.38 Å. The Na(1)-O(9) bond length is 2.37 Å. There is one shorter (2.37 Å) and one longer (2.44 Å) Na(1)-O(10) bond length. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(2), one O(3), and one O(4) atom. The Mo(1)-O(1) bond length is 1.70 Å. The Mo(1)-O(11) bond length is 1.93 Å. The Mo(1)-O(2) bond length is 1.94 Å. The Mo(1)-O(3) bond length is 2.36 Å. The Mo(1)-O(4) bond length is 2.18 Å. In the second Mo site, Mo(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one O(6) atom. The Mo(2)-O(2) bond length is 1.94 Å. The Mo(2)-O(3) bond length is 2.30 Å. The Mo(2)-O(5) bond length is 1.92 Å. The Mo(2)-O(6) bond length is 2.30 Å. In the third Mo site, Mo(3) is bonded in a 5-coordinate geometry to one O(12), one O(13), one O(5), one O(7), and one O(8) atom. The Mo(3)-O(12) bond length is 1.94 Å. The Mo(3)-O(13) bond length is 2.33 Å. The Mo(3)-O(5) bond length is 1.90 Å. The Mo(3)-O(7) bond length is 1.72 Å. The Mo(3)-O(8) bond length is 2.29 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded to one P(1); one N(1); and two equivalent H(1,2) atoms to form distorted corner-sharing CPH2N tetrahedra. The C(1)-P(1) bond length is 1.83 Å. The C(1)-N(1) bond length is 1.51 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. In the second C site, C(2) is bonded to one P(2), one N(1), and two equivalent H(3) atoms to form distorted corner-sharing CPH2N tetrahedra. The C(2)-P(2) bond length is 1.81 Å. The C(2)-N(1) bond length is 1.53 Å. Both C(2)-H(3) bond lengths are 1.08 Å. In the third C site, C(3) is bonded in a bent 120 degrees geometry to one C(4) and two equivalent O(8) atoms. The C(3)-C(4) bond length is 1.49 Å. Both C(3)-O(8) bond lengths are 1.28 Å. In the fourth C site, C(4) is bonded in a single-bond geometry to one C(3) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one C(1), one O(4), one O(6), and one O(9) atom to form PCO3 tetrahedra that share  a cornercorner with one Na(1)O5 square pyramid. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.52 Å. The P(1)-O(9) bond length is 1.51 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one C(2), one O(13), and two equivalent O(3) atoms. The P(2)-O(13) bond length is 1.54 Å. Both P(2)-O(3) bond lengths are 1.52 Å. N(1) is bonded in a trigonal non-coplanar geometry to one C(2) and two equivalent C(1) atoms. There are two 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 C(2) atom. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one Mo(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Mo(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mo(2) and one Mo(3) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one Mo(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Na(1) and one Mo(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Mo(3) and one C(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one P(1) atom. In the tenth O site, O(10) is bonded in an L-shaped geometry to two equivalent Na(1) atoms. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to two equivalent Mo(1) atoms. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to two equivalent Mo(3) atoms. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to two equivalent Mo(3) and one P(2) atom. Linkers: 2 [O]P([O])(=O)CN(CP([O])([O])=O)CP([O])([O])=O. Metal clusters: 4 [Na] ,12 [Mo]. The MOF has largest included sphere 4.44 A, density 1.97 g/cm3, surface area 2435.87 m2/g, accessible volume 0.19 cm3/g