Na2Mo12Zn2P8O51 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(22), one O(29), and one O(42) atom. The Na(1)-O(22) bond length is 2.61 Å. The Na(1)-O(29) bond length is 2.44 Å. The Na(1)-O(42) bond length is 2.41 Å. In the second Na site, Na(2) is bonded to two equivalent O(3), 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(10)O5 square pyramids, corners with two equivalent Mo(6)O5 square pyramids, and corners with two equivalent Mo(9)O5 square pyramids. Both Na(2)-O(3) bond lengths are 2.35 Å. Both Na(2)-O(5) bond lengths are 2.29 Å. Both Na(2)-O(8) bond lengths are 2.24 Å. In the third Na site, Na(3) is bonded to two equivalent O(10), two equivalent O(16), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Mo(12)O5 square pyramids, corners with two equivalent Mo(3)O5 square pyramids, and corners with two equivalent Mo(5)O5 square pyramids. Both Na(3)-O(10) bond lengths are 2.30 Å. Both Na(3)-O(16) bond lengths are 2.26 Å. Both Na(3)-O(2) bond lengths are 2.33 Å. There are twelve inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(12), one O(27), one O(3), and one O(38) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  an edgeedge with one Mo(9)O5 square pyramid. The corner-sharing octahedral tilt angles are 48°. The Mo(1)-O(1) bond length is 1.96 Å. The Mo(1)-O(12) bond length is 2.08 Å. The Mo(1)-O(27) bond length is 2.13 Å. The Mo(1)-O(3) bond length is 1.96 Å. The Mo(1)-O(38) bond length is 2.32 Å. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one O(2), one O(25), one O(39), one O(4), and one O(45) atom. The Mo(2)-O(2) bond length is 1.96 Å. The Mo(2)-O(25) bond length is 2.30 Å. The Mo(2)-O(39) bond length is 2.12 Å. The Mo(2)-O(4) bond length is 1.95 Å. The Mo(2)-O(45) bond length is 2.10 Å. In the third Mo site, Mo(3) is bonded to one O(15), one O(2), one O(35), one O(4), and one O(9) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  an edgeedge with one Mo(5)O5 square pyramid. The corner-sharing octahedral tilt angles are 49°. The Mo(3)-O(15) bond length is 2.29 Å. The Mo(3)-O(2) bond length is 1.96 Å. The Mo(3)-O(35) bond length is 2.12 Å. The Mo(3)-O(4) bond length is 1.96 Å. The Mo(3)-O(9) bond length is 2.08 Å. In the fourth Mo site, Mo(4) is bonded in a 5-coordinate geometry to one O(1), one O(20), one O(3), one O(32), and one O(43) atom. The Mo(4)-O(1) bond length is 1.96 Å. The Mo(4)-O(20) bond length is 2.12 Å. The Mo(4)-O(3) bond length is 1.95 Å. The Mo(4)-O(32) bond length is 2.08 Å. The Mo(4)-O(43) bond length is 2.29 Å. In the fifth Mo site, Mo(5) is bonded to one O(10), one O(14), one O(15), one O(35), and one O(6) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  an edgeedge with one Mo(3)O5 square pyramid. The corner-sharing octahedral tilt angles are 49°. The Mo(5)-O(10) bond length is 1.94 Å. The Mo(5)-O(14) bond length is 2.08 Å. The Mo(5)-O(15) bond length is 2.31 Å. The Mo(5)-O(35) bond length is 2.12 Å. The Mo(5)-O(6) bond length is 1.96 Å. In the sixth Mo site, Mo(6) is bonded to one O(17), one O(21), one O(42), one O(46), and one O(8) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one Mo(10)O5 square pyramid. The corner-sharing octahedral tilt angles are 47°. The Mo(6)-O(17) bond length is 2.11 Å. The Mo(6)-O(21) bond length is 1.96 Å. The Mo(6)-O(42) bond length is 2.06 Å. The Mo(6)-O(46) bond length is 2.30 Å. The Mo(6)-O(8) bond length is 1.95 Å. In the seventh Mo site, Mo(7) is bonded in a 5-coordinate geometry to one O(10), one O(31), one O(36), one O(40), and one O(6) atom. The Mo(7)-O(10) bond length is 1.95 Å. The Mo(7)-O(31) bond length is 2.06 Å. The Mo(7)-O(36) bond length is 2.30 Å. The Mo(7)-O(40) bond length is 2.14 Å. The Mo(7)-O(6) bond length is 1.96 Å. In the eighth Mo site, Mo(8) is bonded in a 5-coordinate geometry to one O(17), one O(28), one O(46), one O(5), and one O(7) atom. The Mo(8)-O(17) bond length is 2.14 Å. The Mo(8)-O(28) bond length is 2.05 Å. The Mo(8)-O(46) bond length is 2.31 Å. The Mo(8)-O(5) bond length is 1.95 Å. The Mo(8)-O(7) bond length is 1.96 Å. In the ninth Mo site, Mo(9) is bonded to one O(27), one O(30), one O(38), one O(5), and one O(7) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(2)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 48°. The Mo(9)-O(27) bond length is 2.11 Å. The Mo(9)-O(30) bond length is 2.08 Å. The Mo(9)-O(38) bond length is 2.32 Å. The Mo(9)-O(5) bond length is 1.96 Å. The Mo(9)-O(7) bond length is 1.97 Å. In the tenth Mo site, Mo(10) is bonded to one O(20), one O(21), one O(33), one O(43), and one O(8) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(2)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(10)-O(20) bond length is 2.10 Å. The Mo(10)-O(21) bond length is 1.96 Å. The Mo(10)-O(33) bond length is 2.06 Å. The Mo(10)-O(43) bond length is 2.30 Å. The Mo(10)-O(8) bond length is 1.95 Å. In the eleventh Mo site, Mo(11) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(22), one O(29), one O(36), and one O(40) atom. The Mo(11)-O(16) bond length is 1.95 Å. The Mo(11)-O(18) bond length is 1.96 Å. The Mo(11)-O(22) bond length is 1.68 Å. The Mo(11)-O(29) bond length is 2.06 Å. The Mo(11)-O(36) bond length is 2.29 Å. The Mo(11)-O(40) bond length is 2.13 Å. In the twelfth Mo site, Mo(12) is bonded to one O(13), one O(16), one O(18), one O(25), and one O(39) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The Mo(12)-O(13) bond length is 2.08 Å. The Mo(12)-O(16) bond length is 1.95 Å. The Mo(12)-O(18) bond length is 1.96 Å. The Mo(12)-O(25) bond length is 2.28 Å. The Mo(12)-O(39) bond length is 2.12 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(19), one O(24), one O(26), and one O(44) atom to form ZnO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. The Zn(1)-O(19) bond length is 1.97 Å. The Zn(1)-O(24) bond length is 1.95 Å. The Zn(1)-O(26) bond length is 1.95 Å. The Zn(1)-O(44) bond length is 1.89 Å. In the second Zn site, Zn(2) is bonded to one O(23), one O(41), one O(47), and one O(50) atom to form ZnO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. The Zn(2)-O(23) bond length is 1.96 Å. The Zn(2)-O(41) bond length is 1.88 Å. The Zn(2)-O(47) bond length is 1.95 Å. The Zn(2)-O(50) bond length is 1.95 Å. There are eight inequivalent P sites. In the first P site, P(1) is bonded to one O(23), one O(38), one O(43), and one O(46) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Mo(10)O5 square pyramid,  a cornercorner with one Mo(6)O5 square pyramid,  a cornercorner with one Mo(9)O5 square pyramid, and  a cornercorner with one Zn(2)O4 tetrahedra. The P(1)-O(23) bond length is 1.55 Å. The P(1)-O(38) bond length is 1.53 Å. The P(1)-O(43) bond length is 1.54 Å. The P(1)-O(46) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(19), one O(32), one O(33), and one O(51) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(10)O5 square pyramid and  a cornercorner with one Zn(1)O4 tetrahedra. The P(2)-O(19) bond length is 1.51 Å. The P(2)-O(32) bond length is 1.52 Å. The P(2)-O(33) bond length is 1.53 Å. The P(2)-O(51) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(28), one O(41), one O(42), and one O(49) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(6)O5 square pyramid and  a cornercorner with one Zn(2)O4 tetrahedra. The P(3)-O(28) bond length is 1.55 Å. The P(3)-O(41) bond length is 1.53 Å. The P(3)-O(42) bond length is 1.55 Å. The P(3)-O(49) bond length is 1.52 Å. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(26), and one O(30) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Mo(9)O5 square pyramid, and  a cornercorner with one Zn(1)O4 tetrahedra. The P(4)-O(11) bond length is 1.53 Å. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(26) bond length is 1.52 Å. The P(4)-O(30) bond length is 1.55 Å. In the fifth P site, P(5) is bonded to one O(15), one O(24), one O(25), and one O(36) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(12)O5 square pyramid,  a cornercorner with one Mo(3)O5 square pyramid,  a cornercorner with one Mo(5)O5 square pyramid, and  a cornercorner with one Zn(1)O4 tetrahedra. The P(5)-O(15) bond length is 1.54 Å. The P(5)-O(24) bond length is 1.52 Å. The P(5)-O(25) bond length is 1.54 Å. The P(5)-O(36) bond length is 1.54 Å. In the sixth P site, P(6) is bonded to one O(13), one O(45), one O(47), and one O(48) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(12)O5 square pyramid and  a cornercorner with one Zn(2)O4 tetrahedra. The P(6)-O(13) bond length is 1.53 Å. The P(6)-O(45) bond length is 1.53 Å. The P(6)-O(47) bond length is 1.52 Å. The P(6)-O(48) bond length is 1.55 Å. In the seventh P site, P(7) is bonded to one O(14), one O(34), one O(50), 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(5)O5 square pyramid, and  a cornercorner with one Zn(2)O4 tetrahedra. The P(7)-O(14) bond length is 1.53 Å. The P(7)-O(34) bond length is 1.54 Å. The P(7)-O(50) bond length is 1.52 Å. The P(7)-O(9) bond length is 1.54 Å. In the eighth P site, P(8) is bonded to one O(29), one O(31), one O(37), and one O(44) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O4 tetrahedra. The P(8)-O(29) bond length is 1.54 Å. The P(8)-O(31) bond length is 1.55 Å. The P(8)-O(37) bond length is 1.52 Å. The P(8)-O(44) bond length is 1.53 Å. There are fifty-one inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to one Mo(1) and one Mo(4) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(3), one Mo(2), and one Mo(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Na(2), one Mo(1), and one Mo(4) atom. In the fourth O site, O(4) is bonded in an L-shaped geometry to one Mo(2) and one Mo(3) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(2), one Mo(8), and one Mo(9) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one Mo(5) and one Mo(7) atom. In the seventh O site, O(7) is bonded in an L-shaped geometry to one Mo(8) and one Mo(9) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Na(2), one Mo(10), and one Mo(6) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Mo(3) and one P(7) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Na(3), one Mo(5), and one Mo(7) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Mo(1) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one Mo(12) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a distorted single-bond geometry to one Mo(5) and one P(7) atom. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one Mo(3), one Mo(5), and one P(5) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Na(3), one Mo(11), and one Mo(12) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Mo(6) and one Mo(8) atom. In the eighteenth O site, O(18) is bonded in an L-shaped geometry to one Mo(11) and one Mo(12) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(2) atom. In the twentieth O site, O(20) is bonded in a bent 120 degrees geometry to one Mo(10) and one Mo(4) atom. In the twenty-first O site, O(21) is bonded in an L-shaped geometry to one Mo(10) and one Mo(6) atom. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to one Na(1) and one Mo(11) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one Zn(2) and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one Zn(1) and one P(5) atom. In the twenty-fifth O site, O(25) is bonded in a distorted single-bond geometry to one Mo(12), one Mo(2), and one P(5) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(4) atom. In the twenty-seventh O site, O(27) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(9) atom. In the twenty-eighth O site, O(28) is bonded in a single-bond geometry to one Mo(8) and one P(3) atom. In the twenty-ninth O site, O(29) is bonded in a 3-coordinate geometry to one Na(1), one Mo(11), and one P(8) atom. In the thirtieth O site, O(30) is bonded in a distorted single-bond geometry to one Mo(9) and one P(4) atom. In the thirty-first O site, O(31) is bonded in a single-bond geometry to one Mo(7) and one P(8) atom. In the thirty-second O site, O(32) is bonded in a distorted single-bond geometry to one Mo(4) and one P(2) atom. In the thirty-third O site, O(33) is bonded in a distorted single-bond geometry to one Mo(10) and one P(2) atom. In the thirty-fourth O site, O(34) is bonded in a single-bond geometry to one P(7) atom. In the thirty-fifth O site, O(35) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(5) atom. In the thirty-sixth O site, O(36) is bonded in a distorted single-bond geometry to one Mo(11), one Mo(7), and one P(5) atom. In the thirty-seventh O site, O(37) is bonded in a single-bond geometry to one P(8) atom. In the thirty-eighth O site, O(38) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(9), and one P(1) atom. In the thirty-ninth O site, O(39) is bonded in a bent 120 degrees geometry to one Mo(12) and one Mo(2) atom. In the fortieth O site, O(40) is bonded in a bent 120 degrees geometry to one Mo(11) and one Mo(7) atom. In the forty-first O site, O(41) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(3) atom. In the forty-second O site, O(42) is bonded in a 3-coordinate geometry to one Na(1), one Mo(6), and one P(3) atom. In the forty-third O site, O(43) is bonded in a distorted single-bond geometry to one Mo(10), one Mo(4), and one P(1) atom. In the forty-fourth O site, O(44) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(8) atom. In the forty-fifth O site, O(45) is bonded in a distorted single-bond geometry to one Mo(2) and one P(6) atom. In the forty-sixth O site, O(46) is bonded in a distorted single-bond geometry to one Mo(6), one Mo(8), and one P(1) atom. In the forty-seventh O site, O(47) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(6) atom. In the forty-eighth O site, O(48) is bonded in a single-bond geometry to one P(6) atom. In the forty-ninth O site, O(49) is bonded in a single-bond geometry to one P(3) atom. In the fiftieth O site, O(50) is bonded in a distorted bent 120 degrees geometry to one Zn(2) and one P(7) atom. In the fifty-first O site, O(51) is bonded in a single-bond geometry to one P(2) atom. Linkers: 16 [O]P([O])([O])=O. Metal clusters: 4 [Na] ,4 [Zn] ,24 [Mo]. The MOF has largest included sphere 6.01 A, density 2.03 g/cm3, surface area 1874.72 m2/g, accessible volume 0.23 cm3/g