NaMo6ZnP4O25 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(14), two equivalent O(5), and two equivalent O(8) atoms to form NaO6 octahedra that share corners with two equivalent Mo(1)O5 square pyramids, corners with two equivalent Mo(3)O5 square pyramids, corners with two equivalent Mo(4)O5 square pyramids, and corners with two equivalent Mo(6)O5 square pyramids. Both Na(1)-O(14) bond lengths are 2.30 Å. Both Na(1)-O(5) bond lengths are 2.26 Å. Both Na(1)-O(8) bond lengths are 2.35 Å. In the second Na site, Na(2) is bonded in a linear geometry to two equivalent O(18) atoms. Both Na(2)-O(18) bond lengths are 2.42 Å. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one Mo(6)O5 square pyramid. The corner-sharing octahedral tilt angles are 47°. The Mo(1)-O(1) bond length is 2.06 Å. The Mo(1)-O(2) bond length is 2.28 Å. The Mo(1)-O(3) bond length is 1.94 Å. The Mo(1)-O(4) bond length is 2.11 Å. The Mo(1)-O(5) bond length is 1.94 Å. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Mo(2)-O(2) bond length is 2.28 Å. The Mo(2)-O(4) bond length is 2.12 Å. The Mo(2)-O(6) bond length is 2.08 Å. The Mo(2)-O(7) bond length is 1.94 Å. The Mo(2)-O(8) bond length is 1.95 Å. In the third Mo site, Mo(3) is bonded to one O(10), one O(11), one O(7), one O(8), and one O(9) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one Mo(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 48°. The Mo(3)-O(10) bond length is 2.31 Å. The Mo(3)-O(11) bond length is 2.12 Å. The Mo(3)-O(7) bond length is 1.93 Å. The Mo(3)-O(8) bond length is 1.95 Å. The Mo(3)-O(9) bond length is 2.07 Å. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(11), one O(12), one O(13), and one O(14) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one Mo(3)O5 square pyramid. The corner-sharing octahedral tilt angles are 48°. The Mo(4)-O(10) bond length is 2.31 Å. The Mo(4)-O(11) bond length is 2.12 Å. The Mo(4)-O(12) bond length is 2.08 Å. The Mo(4)-O(13) bond length is 1.94 Å. The Mo(4)-O(14) bond length is 1.95 Å. In the fifth Mo site, Mo(5) is bonded in a 5-coordinate geometry to one O(13), one O(14), one O(15), one O(16), and one O(17) atom. The Mo(5)-O(13) bond length is 1.94 Å. The Mo(5)-O(14) bond length is 1.94 Å. The Mo(5)-O(15) bond length is 2.13 Å. The Mo(5)-O(16) bond length is 2.06 Å. The Mo(5)-O(17) bond length is 2.31 Å. In the sixth Mo site, Mo(6) is bonded to one O(15), one O(17), one O(18), one O(3), and one O(5) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  an edgeedge with one Mo(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 47°. The Mo(6)-O(15) bond length is 2.13 Å. The Mo(6)-O(17) bond length is 2.30 Å. The Mo(6)-O(18) bond length is 2.06 Å. The Mo(6)-O(3) bond length is 1.94 Å. The Mo(6)-O(5) bond length is 1.94 Å. Zn(1) is bonded to one O(21), one O(23), one O(24), and one O(25) atom to form ZnO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Zn(1)-O(21) bond length is 1.89 Å. The Zn(1)-O(23) bond length is 1.94 Å. The Zn(1)-O(24) bond length is 1.95 Å. The Zn(1)-O(25) bond length is 1.96 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(17), one O(2), and one O(25) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Mo(3)O5 square pyramid,  a cornercorner with one Mo(4)O5 square pyramid,  a cornercorner with one Mo(6)O5 square pyramid, and  a cornercorner with one Zn(1)O4 tetrahedra. The P(1)-O(10) bond length is 1.54 Å. The P(1)-O(17) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(25) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(19), one O(24), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O5 square pyramid and  a cornercorner with one Zn(1)O4 tetrahedra. The P(2)-O(1) bond length is 1.52 Å. The P(2)-O(19) bond length is 1.54 Å. The P(2)-O(24) bond length is 1.51 Å. The P(2)-O(6) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(12), one O(20), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O5 square pyramid,  a cornercorner with one Mo(4)O5 square pyramid, and  a cornercorner with one Zn(1)O4 tetrahedra. The P(3)-O(12) bond length is 1.54 Å. The P(3)-O(20) bond length is 1.54 Å. The P(3)-O(23) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(16), one O(18), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(6)O5 square pyramid and  a cornercorner with one Zn(1)O4 tetrahedra. The P(4)-O(16) bond length is 1.53 Å. The P(4)-O(18) bond length is 1.55 Å. The P(4)-O(21) bond length is 1.52 Å. The P(4)-O(22) bond length is 1.52 Å. There are twenty-five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Mo(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(2), and one P(1) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one Mo(1) and one Mo(6) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1), one Mo(1), and one Mo(6) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Mo(2) and one P(2) atom. In the seventh O site, O(7) is bonded in an L-shaped geometry to one Mo(2) and one Mo(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Na(1), one Mo(2), and one Mo(3) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Mo(3) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Mo(3), one Mo(4), and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(4) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Mo(4) and one P(3) atom. In the thirteenth O site, O(13) is bonded in an L-shaped geometry to one Mo(4) and one Mo(5) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Na(1), one Mo(4), and one Mo(5) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Mo(5) and one Mo(6) atom. In the sixteenth O site, O(16) is bonded in a single-bond geometry to one Mo(5) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one Mo(5), one Mo(6), and one P(1) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Na(2), one Mo(6), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one P(2) atom. In the twentieth O site, O(20) is bonded in a single-bond geometry to one P(3) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(4) atom. In the twenty-second O site, O(22) is bonded in a single-bond geometry to one P(4) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one P(2) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(1) atom. Linkers: 8 [O]P([O])([O])=O. Metal clusters: 2 [Na] ,2 [Zn] ,12 [Mo]. The MOF has largest included sphere 5.96 A, density 2.02 g/cm3, surface area 1893.71 m2/g, accessible volume 0.27 cm3/g