Mo6ZnP4O25 crystallizes in the tetragonal I4_1/acd space group. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(18), one O(3), and one O(4) atom. The Mo(1)-O(10) bond length is 1.94 Å. The Mo(1)-O(14) bond length is 1.99 Å. The Mo(1)-O(18) bond length is 2.10 Å. The Mo(1)-O(3) bond length is 2.28 Å. The Mo(1)-O(4) bond length is 2.05 Å. In the second Mo site, Mo(2) is bonded to one O(10), one O(13), one O(14), one O(2), and one O(21) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Zn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The Mo(2)-O(10) bond length is 1.93 Å. The Mo(2)-O(13) bond length is 2.27 Å. The Mo(2)-O(14) bond length is 1.98 Å. The Mo(2)-O(2) bond length is 2.11 Å. The Mo(2)-O(21) bond length is 2.07 Å. In the third Mo site, Mo(3) is bonded in a 5-coordinate geometry to one O(1), one O(19), one O(6), one O(8), and one O(9) atom. The Mo(3)-O(1) bond length is 2.24 Å. The Mo(3)-O(19) bond length is 2.08 Å. The Mo(3)-O(6) bond length is 1.97 Å. The Mo(3)-O(8) bond length is 1.92 Å. The Mo(3)-O(9) bond length is 2.15 Å. In the fourth Mo site, Mo(4) is bonded to one O(12), one O(18), one O(3), one O(5), and one O(7) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Zn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The Mo(4)-O(12) bond length is 1.94 Å. The Mo(4)-O(18) bond length is 2.10 Å. The Mo(4)-O(3) bond length is 2.28 Å. The Mo(4)-O(5) bond length is 1.99 Å. The Mo(4)-O(7) bond length is 2.04 Å. In the fifth Mo site, Mo(5) is bonded in a 5-coordinate geometry to one O(13), one O(17), one O(2), one O(6), and one O(8) atom. The Mo(5)-O(13) bond length is 2.29 Å. The Mo(5)-O(17) bond length is 2.05 Å. The Mo(5)-O(2) bond length is 2.09 Å. The Mo(5)-O(6) bond length is 1.98 Å. The Mo(5)-O(8) bond length is 1.94 Å. In the sixth Mo site, Mo(6) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(20), one O(5), and one O(9) atom. The Mo(6)-O(1) bond length is 2.27 Å. The Mo(6)-O(12) bond length is 1.93 Å. The Mo(6)-O(20) bond length is 2.08 Å. The Mo(6)-O(5) bond length is 1.97 Å. The Mo(6)-O(9) bond length is 2.12 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(16) and two equivalent O(23) atoms to form ZnO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(4)O4 tetrahedra. Both Zn(1)-O(16) bond lengths are 1.95 Å. Both Zn(1)-O(23) bond lengths are 1.91 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(14), two equivalent O(5), and two equivalent O(6) atoms to form ZnO6 octahedra that share corners with two equivalent Mo(2)O5 square pyramids and corners with two equivalent Mo(4)O5 square pyramids. Both Zn(2)-O(14) bond lengths are 2.19 Å. Both Zn(2)-O(5) bond lengths are 2.19 Å. Both Zn(2)-O(6) bond lengths are 2.14 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(19), one O(20), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O4 tetrahedra. The P(1)-O(16) bond length is 1.51 Å. The P(1)-O(19) bond length is 1.54 Å. The P(1)-O(20) bond length is 1.53 Å. The P(1)-O(24) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(13), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O5 square pyramid and  a cornercorner with one Mo(4)O5 square pyramid. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.50 Å. The P(2)-O(13) bond length is 1.55 Å. The P(2)-O(3) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(15), one O(22), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(4)O5 square pyramid. The P(3)-O(15) bond length is 1.51 Å. The P(3)-O(22) bond length is 1.58 Å. The P(3)-O(4) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(17), one O(21), one O(23), and one O(25) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O5 square pyramid and  a cornercorner with one Zn(1)O4 tetrahedra. The P(4)-O(17) bond length is 1.53 Å. The P(4)-O(21) bond length is 1.53 Å. The P(4)-O(23) bond length is 1.49 Å. The P(4)-O(25) bond length is 1.58 Å. There are twenty-five inequivalent O sites. In the first O site, O(24) is bonded in a single-bond geometry to one P(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Mo(3), one Mo(6), and one P(2) atom. In the third O site, O(5) is bonded in a 3-coordinate geometry to one Mo(4), one Mo(6), and one Zn(2) atom. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to one Mo(3), one Mo(5), and one Zn(2) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Mo(4) and one P(3) atom. In the sixth O site, O(2) is bonded in a bent 120 degrees geometry to one Mo(2) and one Mo(5) atom. In the seventh O site, O(3) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(4), and one P(2) atom. In the eighth O site, O(4) is bonded in a single-bond geometry to one Mo(1) and one P(3) atom. In the ninth O site, O(8) is bonded in an L-shaped geometry to one Mo(3) and one Mo(5) atom. In the tenth O site, O(9) is bonded in a water-like geometry to one Mo(3) and one Mo(6) atom. In the eleventh O site, O(10) is bonded in an L-shaped geometry to one Mo(1) and one Mo(2) atom. In the twelfth O site, O(11) is bonded in a single-bond geometry to one P(2) atom. In the thirteenth O site, O(12) is bonded in an L-shaped geometry to one Mo(4) and one Mo(6) atom. In the fourteenth O site, O(13) is bonded in a distorted single-bond geometry to one Mo(2), one Mo(5), and one P(2) atom. In the fifteenth O site, O(14) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Zn(2) atom. In the sixteenth O site, O(15) is bonded in a single-bond geometry to one P(3) atom. In the seventeenth O site, O(16) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the eighteenth O site, O(17) is bonded in a single-bond geometry to one Mo(5) and one P(4) atom. In the nineteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(4) atom. In the twentieth O site, O(19) is bonded in a single-bond geometry to one Mo(3) and one P(1) atom. In the twenty-first O site, O(20) is bonded in a single-bond geometry to one Mo(6) and one P(1) atom. In the twenty-second O site, O(21) is bonded in a distorted single-bond geometry to one Mo(2) and one P(4) atom. In the twenty-third O site, O(22) is bonded in a single-bond geometry to one P(3) atom. In the twenty-fourth O site, O(23) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(4) atom. In the twenty-fifth O site, O(25) is bonded in a single-bond geometry to one P(4) atom. Linkers: 128 [O]P([O])([O])=O. Metal clusters: 32 [Zn] ,192 [Mo]. The MOF has largest included sphere 7.87 A, density 1.77 g/cm3, surface area 1938.80 m2/g, accessible volume 0.36 cm3/g