Mo12Mn3(P4O25)2 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(12), one O(13), one O(2), one O(22), and one O(3) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O5 square pyramid, and  an edgeedge with one Mo(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 46°. The Mo(1)-O(12) bond length is 2.12 Å. The Mo(1)-O(13) bond length is 2.03 Å. The Mo(1)-O(2) bond length is 1.94 Å. The Mo(1)-O(22) bond length is 2.29 Å. The Mo(1)-O(3) bond length is 1.98 Å. In the second Mo site, Mo(2) is bonded to one O(18), one O(2), one O(21), one O(24), and one O(3) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(1)O5 square pyramid, and  an edgeedge with one Mo(5)O5 square pyramid. The corner-sharing octahedral tilt angles are 45°. The Mo(2)-O(18) bond length is 2.06 Å. The Mo(2)-O(2) bond length is 1.94 Å. The Mo(2)-O(21) bond length is 2.11 Å. The Mo(2)-O(24) bond length is 2.27 Å. The Mo(2)-O(3) bond length is 1.98 Å. In the third Mo site, Mo(3) is bonded to one O(14), one O(23), one O(25), one O(4), and one O(6) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(4)O5 square pyramid, and  an edgeedge with one Mo(6)O5 square pyramid. The corner-sharing octahedral tilt angles are 47°. The Mo(3)-O(14) bond length is 2.04 Å. The Mo(3)-O(23) bond length is 1.96 Å. The Mo(3)-O(25) bond length is 2.30 Å. The Mo(3)-O(4) bond length is 1.98 Å. The Mo(3)-O(6) bond length is 2.10 Å. In the fourth Mo site, Mo(4) is bonded to one O(11), one O(12), one O(22), one O(23), and one O(4) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(1)O5 square pyramid, and  an edgeedge with one Mo(3)O5 square pyramid. The corner-sharing octahedral tilt angles are 46°. The Mo(4)-O(11) bond length is 2.08 Å. The Mo(4)-O(12) bond length is 2.13 Å. The Mo(4)-O(22) bond length is 2.23 Å. The Mo(4)-O(23) bond length is 1.94 Å. The Mo(4)-O(4) bond length is 1.97 Å. In the fifth Mo site, Mo(5) is bonded to one O(15), one O(21), one O(24), one O(5), and one O(8) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O5 square pyramid, and  an edgeedge with one Mo(6)O5 square pyramid. The corner-sharing octahedral tilt angles are 45°. The Mo(5)-O(15) bond length is 2.07 Å. The Mo(5)-O(21) bond length is 2.12 Å. The Mo(5)-O(24) bond length is 2.29 Å. The Mo(5)-O(5) bond length is 1.97 Å. The Mo(5)-O(8) bond length is 1.94 Å. In the sixth Mo site, Mo(6) is bonded to one O(10), one O(25), one O(5), one O(6), and one O(8) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(3)O5 square pyramid, and  an edgeedge with one Mo(5)O5 square pyramid. The corner-sharing octahedral tilt angles are 47°. The Mo(6)-O(10) bond length is 2.02 Å. The Mo(6)-O(25) bond length is 2.30 Å. The Mo(6)-O(5) bond length is 1.99 Å. The Mo(6)-O(6) bond length is 2.12 Å. The Mo(6)-O(8) bond length is 1.95 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(16), one O(17), one O(19), one O(20), and one O(9) atom to form MnO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Mn(1)-O(16) bond length is 2.16 Å. The Mn(1)-O(17) bond length is 2.14 Å. The Mn(1)-O(19) bond length is 2.34 Å. The Mn(1)-O(20) bond length is 2.20 Å. The Mn(1)-O(9) bond length is 2.09 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mo(1)O5 square pyramids, corners with two equivalent Mo(2)O5 square pyramids, corners with two equivalent Mo(3)O5 square pyramids, corners with two equivalent Mo(4)O5 square pyramids, corners with two equivalent Mo(5)O5 square pyramids, and corners with two equivalent Mo(6)O5 square pyramids. Both Mn(2)-O(3) bond lengths are 2.16 Å. Both Mn(2)-O(4) bond lengths are 2.22 Å. Both Mn(2)-O(5) bond lengths are 2.20 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(15), one O(17), and one O(18) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O5 square pyramid,  a cornercorner with one Mo(5)O5 square pyramid, and  a cornercorner with one Mn(1)O5 square pyramid. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(15) bond length is 1.53 Å. The P(1)-O(17) bond length is 1.49 Å. The P(1)-O(18) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(11), one O(13), one O(19), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Mo(4)O5 square pyramid, and corners with two equivalent Mn(1)O5 square pyramids. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(19) bond length is 1.57 Å. The P(2)-O(9) bond length is 1.48 Å. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O5 square pyramid,  a cornercorner with one Mo(6)O5 square pyramid, and  a cornercorner with one Mn(1)O5 square pyramid. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(16) bond length is 1.51 Å. The P(3)-O(7) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(20), one O(22), one O(24), 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(2)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(5)O5 square pyramid,  a cornercorner with one Mo(6)O5 square pyramid, and  a cornercorner with one Mn(1)O5 square pyramid. The P(4)-O(20) bond length is 1.50 Å. The P(4)-O(22) bond length is 1.56 Å. The P(4)-O(24) bond length is 1.56 Å. The P(4)-O(25) bond length is 1.54 Å. There are twenty-five inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one P(1) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one Mo(1) and one Mo(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mo(3), one Mo(4), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mo(5), one Mo(6), and one Mn(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(6) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one P(3) atom. In the eighth O site, O(8) is bonded in an L-shaped geometry to one Mo(5) and one Mo(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Mo(6) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Mo(4) and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(4) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one Mo(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Mo(3) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one Mo(5) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the eighteenth O site, O(18) is bonded in a distorted single-bond geometry to one Mo(2) and one P(1) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the twentieth O site, O(20) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Mo(2) and one Mo(5) atom. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(4), and one P(4) atom. In the twenty-third O site, O(23) is bonded in an L-shaped geometry to one Mo(3) and one Mo(4) atom. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one Mo(2), one Mo(5), and one P(4) atom. In the twenty-fifth O site, O(25) is bonded in a distorted single-bond geometry to one Mo(3), one Mo(6), and one P(4) atom. Linkers: 16 [O]P([O])([O])=O. Metal clusters: 6 [Mn] ,24 [Mo]. The MOF has largest included sphere 5.63 A, density 2.33 g/cm3, surface area 1760.36 m2/g, accessible volume 0.21 cm3/g