Mo12Zn4C9PH3O34 crystallizes in the orthorhombic Pnnm space group. There are seven inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 5-coordinate geometry to one O(1), one O(15), one O(18), one O(3), and one O(8) atom. The Mo(1)-O(1) bond length is 1.96 Å. The Mo(1)-O(15) bond length is 2.00 Å. The Mo(1)-O(18) bond length is 2.56 Å. The Mo(1)-O(3) bond length is 1.99 Å. The Mo(1)-O(8) bond length is 2.02 Å. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(3), one O(6), and one O(9) atom. The Mo(2)-O(1) bond length is 1.94 Å. The Mo(2)-O(10) bond length is 2.12 Å. The Mo(2)-O(3) bond length is 1.94 Å. The Mo(2)-O(6) bond length is 2.60 Å. The Mo(2)-O(9) bond length is 1.97 Å. In the third Mo site, Mo(3) is bonded to one O(11), one O(16), one O(20), one O(6), and one O(9) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Zn(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one Zn(3)O5 trigonal bipyramid,  an edgeedge with one Mo(3)O5 square pyramid, and  an edgeedge with one Mo(4)O5 square pyramid. The Mo(3)-O(11) bond length is 1.81 Å. The Mo(3)-O(16) bond length is 2.03 Å. The Mo(3)-O(20) bond length is 1.98 Å. The Mo(3)-O(6) bond length is 2.63 Å. The Mo(3)-O(9) bond length is 1.84 Å. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(11), one O(5), one O(6), and one O(7) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one Zn(3)O5 trigonal bipyramid, and  an edgeedge with one Mo(3)O5 square pyramid. The Mo(4)-O(10) bond length is 2.10 Å. The Mo(4)-O(11) bond length is 2.01 Å. The Mo(4)-O(5) bond length is 1.95 Å. The Mo(4)-O(6) bond length is 2.49 Å. The Mo(4)-O(7) bond length is 1.94 Å. In the fifth Mo site, Mo(5) is bonded in a 3-coordinate geometry to one O(12), one O(17), one O(19), one O(5), and one O(7) atom. The Mo(5)-O(12) bond length is 1.99 Å. The Mo(5)-O(17) bond length is 2.49 Å. The Mo(5)-O(19) bond length is 2.06 Å. The Mo(5)-O(5) bond length is 1.99 Å. The Mo(5)-O(7) bond length is 2.01 Å. In the sixth Mo site, Mo(6) is bonded in a 5-coordinate geometry to one O(18), two equivalent O(4), and two equivalent O(8) atoms. The Mo(6)-O(18) bond length is 2.56 Å. Both Mo(6)-O(4) bond lengths are 2.01 Å. Both Mo(6)-O(8) bond lengths are 1.81 Å. In the seventh Mo site, Mo(7) is bonded to one O(17), two equivalent O(12), and two equivalent O(4) atoms to form distorted MoO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent Zn(1)O4 tetrahedra. The Mo(7)-O(17) bond length is 2.59 Å. Both Mo(7)-O(12) bond lengths are 1.83 Å. Both Mo(7)-O(4) bond lengths are 2.02 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form ZnO4 tetrahedra that share  a cornercorner with one Mo(4)O5 square pyramid and  a cornercorner with one Mo(7)O5 square pyramid. The Zn(1)-O(2) bond length is 1.93 Å. The Zn(1)-O(3) bond length is 1.97 Å. The Zn(1)-O(4) bond length is 1.96 Å. The Zn(1)-O(5) bond length is 1.97 Å. In the second Zn site, Zn(2) is bonded to one O(15), one O(16), and two equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with two equivalent Mo(3)O5 square pyramids. The Zn(2)-O(15) bond length is 1.97 Å. The Zn(2)-O(16) bond length is 1.94 Å. Both Zn(2)-O(1) bond lengths are 1.98 Å. In the third Zn site, Zn(3) is bonded to one O(20), two equivalent O(14), and two equivalent O(7) atoms to form distorted ZnO5 trigonal bipyramids that share corners with two equivalent Mo(3)O5 square pyramids and corners with two equivalent Mo(4)O5 square pyramids. The Zn(3)-O(20) bond length is 2.02 Å. Both Zn(3)-O(14) bond lengths are 2.12 Å. Both Zn(3)-O(7) bond lengths are 1.99 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(5), and one H(1) atom. The C(1)-C(2) bond length is 1.36 Å. The C(1)-C(5) bond length is 1.41 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(4) atom. The C(2)-C(3) bond length is 1.45 Å. The C(2)-C(4) bond length is 1.40 Å. In the third C site, C(3) is bonded in a bent 120 degrees geometry to one C(2), one O(13), and one O(2) atom. The C(3)-O(13) bond length is 1.25 Å. The C(3)-O(2) bond length is 1.27 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to two equivalent C(2) and one H(2) atom. The C(4)-H(2) bond length is 0.93 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(6) and two equivalent C(1) atoms. The C(5)-C(6) bond length is 1.54 Å. In the sixth C site, C(6) is bonded in a bent 120 degrees geometry to one C(5) and two equivalent O(14) atoms. Both C(6)-O(14) bond lengths are 1.21 Å. P(1) is bonded to one O(17), one O(18), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one Mo(7)O5 square pyramid, corners with two equivalent Mo(3)O5 square pyramids, and corners with two equivalent Mo(4)O5 square pyramids. The P(1)-O(17) bond length is 1.57 Å. The P(1)-O(18) bond length is 1.55 Å. Both P(1)-O(6) bond lengths are 1.53 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. There are twenty inequivalent O sites. In the first O site, O(13) is bonded in a single-bond geometry to one C(3) atom. In the second O site, O(14) is bonded in an L-shaped geometry to one Zn(3) and one C(6) atom. In the third O site, O(20) is bonded in a distorted single-bond geometry to two equivalent Mo(3) and one Zn(3) atom. In the fourth O site, O(15) is bonded in a trigonal planar geometry to two equivalent Mo(1) and one Zn(2) atom. In the fifth O site, O(16) is bonded in a single-bond geometry to two equivalent Mo(3) and one Zn(2) atom. In the sixth O site, O(17) is bonded in a distorted single-bond geometry to one Mo(7), two equivalent Mo(5), and one P(1) atom. In the seventh O site, O(18) is bonded in a single-bond geometry to one Mo(6), two equivalent Mo(1), and one P(1) atom. In the eighth O site, O(19) is bonded in a bent 120 degrees geometry to two equivalent Mo(5) atoms. In the ninth O site, O(1) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Zn(2) atom. In the tenth O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(3) atom. In the eleventh O site, O(3) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Zn(1) atom. In the twelfth O site, O(4) is bonded in a single-bond geometry to one Mo(6), one Mo(7), and one Zn(1) atom. In the thirteenth O site, O(5) is bonded in a 3-coordinate geometry to one Mo(4), one Mo(5), and one Zn(1) atom. In the fourteenth O site, O(6) is bonded in a single-bond geometry to one Mo(2), one Mo(3), one Mo(4), and one P(1) atom. In the fifteenth O site, O(7) is bonded in a 3-coordinate geometry to one Mo(4), one Mo(5), and one Zn(3) atom. In the sixteenth O site, O(8) is bonded in a distorted single-bond geometry to one Mo(1) and one Mo(6) atom. In the seventeenth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Mo(2) and one Mo(3) atom. In the eighteenth O site, O(10) is bonded in a bent 120 degrees geometry to one Mo(2) and one Mo(4) atom. In the nineteenth O site, O(11) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(4) atom. In the twentieth O site, O(12) is bonded in a bent 120 degrees geometry to one Mo(5) and one Mo(7) atom. Linkers: 4 [O]C(=O)c1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 1 O=[C]O[Zn@]12O[Mo@]34O[Mo]5O[Mo]56(O[Mo]5O[Mo@@]78O[Zn]O[Mo@@]9%10O[Mo@@]%11%12O[Mo]%13O[Mo]%13%14%15O[Zn@@](O[C]=O)(O%11)O[Mo]%11%13(O[Zn]%16(O[C]O%16)O[Mo]%16%17(O[Mo](O[Mo@@](O[Zn]O[Mo@]%18(O3)O[Mo]%183(O[Zn@](O[C]=O)(O4)O[Mo]4(O[Zn]%18(O[C]O%18)O[Mo](O5)(O1)(O6)[Mo]1O[Mo]O[Mo]4O1)(O7)O3)O8)(O%14)O%11)O[Mo]9(O[Zn@](O[C]=O)(O%12)O%16)(O%10)O%17)[Mo]1O[Mo]O[Mo]%13O1)O%15)O2 ,1 O=[C]O[Zn@]12O[Mo@@]34O[Mo]5O[Mo]56(O[Mo]5O[Mo@@]78O[Zn]O[Mo@@]9%10O[Mo@]%11%12O[Mo]%13O[Mo]%13%14%15O[Mo]%13O[Mo@@]%16(O[Zn]O[Mo@]%17(O3)O[Mo]%173(O[Zn@](O[C]=O)(O4)O[Mo]4(O[Zn]%17(O[C]O%17)O[Mo](O5)(O1)(O6)[Mo]1O[Mo]O[Mo]4O1)(O7)O3)O8)O[Mo]13(O[Zn]4(O[C]O4)O[Mo](O%13)(O[Zn@](O[C]=O)(O%11)O%14)(O%15)[Mo]4O[Mo]O[Mo]1O4)O[Zn@@](O[C]=O)(O%12)O[Mo]9(O%16)(O%10)O3)O2. RCSR code: rtl. The MOF has largest included sphere 9.73 A, density 1.42 g/cm3, surface area 1639.24 m2/g, accessible volume 0.45 cm3/g