Mo12Zn4C9PH3O34 crystallizes in the orthorhombic Pbca space group. There are twelve inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(12), one O(15), and one O(24) atom. The Mo(1)-O(1) bond length is 1.96 Å. The Mo(1)-O(11) bond length is 2.01 Å. The Mo(1)-O(12) bond length is 2.47 Å. The Mo(1)-O(15) bond length is 2.02 Å. The Mo(1)-O(24) bond length is 1.96 Å. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one O(1), one O(14), one O(24), one O(30), and one O(34) atom. The Mo(2)-O(1) bond length is 1.95 Å. The Mo(2)-O(14) bond length is 2.07 Å. The Mo(2)-O(24) bond length is 1.95 Å. The Mo(2)-O(30) bond length is 2.02 Å. The Mo(2)-O(34) bond length is 2.49 Å. In the third Mo site, Mo(3) is bonded in a 3-coordinate geometry to one O(20), one O(22), one O(26), one O(27), and one O(32) atom. The Mo(3)-O(20) bond length is 2.02 Å. The Mo(3)-O(22) bond length is 2.58 Å. The Mo(3)-O(26) bond length is 1.82 Å. The Mo(3)-O(27) bond length is 2.01 Å. The Mo(3)-O(32) bond length is 1.81 Å. In the fourth Mo site, Mo(4) is bonded in a 5-coordinate geometry to one O(17), one O(22), one O(28), one O(32), and one O(9) atom. The Mo(4)-O(17) bond length is 1.96 Å. The Mo(4)-O(22) bond length is 2.60 Å. The Mo(4)-O(28) bond length is 1.96 Å. The Mo(4)-O(32) bond length is 2.04 Å. The Mo(4)-O(9) bond length is 1.96 Å. In the fifth Mo site, Mo(5) is bonded in a 3-coordinate geometry to one O(16), one O(18), one O(22), one O(26), and one O(9) atom. The Mo(5)-O(16) bond length is 1.95 Å. The Mo(5)-O(18) bond length is 1.97 Å. The Mo(5)-O(22) bond length is 2.57 Å. The Mo(5)-O(26) bond length is 2.02 Å. The Mo(5)-O(9) bond length is 1.93 Å. In the sixth Mo site, Mo(6) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(19), and one O(8) atom. The Mo(6)-O(10) bond length is 1.95 Å. The Mo(6)-O(11) bond length is 2.02 Å. The Mo(6)-O(12) bond length is 2.51 Å. The Mo(6)-O(19) bond length is 2.03 Å. The Mo(6)-O(8) bond length is 1.96 Å. In the seventh Mo site, Mo(7) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(19), one O(20), and one O(27) atom. The Mo(7)-O(12) bond length is 2.62 Å. The Mo(7)-O(15) bond length is 1.84 Å. The Mo(7)-O(19) bond length is 1.82 Å. The Mo(7)-O(20) bond length is 2.00 Å. The Mo(7)-O(27) bond length is 2.01 Å. In the eighth Mo site, Mo(8) is bonded in a 5-coordinate geometry to one O(13), one O(16), one O(18), one O(21), and one O(33) atom. The Mo(8)-O(13) bond length is 2.59 Å. The Mo(8)-O(16) bond length is 1.97 Å. The Mo(8)-O(18) bond length is 1.97 Å. The Mo(8)-O(21) bond length is 2.07 Å. The Mo(8)-O(33) bond length is 2.02 Å. In the ninth Mo site, Mo(9) is bonded in a 5-coordinate geometry to one O(14), one O(17), one O(28), one O(31), and one O(34) atom. The Mo(9)-O(14) bond length is 2.09 Å. The Mo(9)-O(17) bond length is 1.95 Å. The Mo(9)-O(28) bond length is 1.96 Å. The Mo(9)-O(31) bond length is 2.02 Å. The Mo(9)-O(34) bond length is 2.56 Å. In the tenth Mo site, Mo(10) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(21), one O(29), and one O(8) atom. The Mo(10)-O(10) bond length is 1.96 Å. The Mo(10)-O(13) bond length is 2.50 Å. The Mo(10)-O(21) bond length is 2.07 Å. The Mo(10)-O(29) bond length is 2.01 Å. The Mo(10)-O(8) bond length is 1.96 Å. In the eleventh Mo site, Mo(11) is bonded in a 5-coordinate geometry to one O(13), one O(23), one O(25), one O(29), and one O(33) atom. The Mo(11)-O(13) bond length is 2.57 Å. The Mo(11)-O(23) bond length is 1.99 Å. The Mo(11)-O(25) bond length is 2.03 Å. The Mo(11)-O(29) bond length is 1.83 Å. The Mo(11)-O(33) bond length is 1.80 Å. In the twelfth Mo site, Mo(12) is bonded in a 4-coordinate geometry to one O(23), one O(25), one O(30), one O(31), and one O(34) atom. The Mo(12)-O(23) bond length is 2.01 Å. The Mo(12)-O(25) bond length is 2.00 Å. The Mo(12)-O(30) bond length is 1.83 Å. The Mo(12)-O(31) bond length is 1.82 Å. The Mo(12)-O(34) bond length is 2.57 Å. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a tetrahedral geometry to one O(11), one O(24), one O(25), and one O(8) atom. The Zn(1)-O(11) bond length is 1.95 Å. The Zn(1)-O(24) bond length is 1.97 Å. The Zn(1)-O(25) bond length is 1.94 Å. The Zn(1)-O(8) bond length is 1.97 Å. In the second Zn site, Zn(2) is bonded in a tetrahedral geometry to one O(10), one O(18), one O(20), and one O(3) atom. The Zn(2)-O(10) bond length is 1.98 Å. The Zn(2)-O(18) bond length is 1.96 Å. The Zn(2)-O(20) bond length is 1.95 Å. The Zn(2)-O(3) bond length is 1.94 Å. In the third Zn site, Zn(3) is bonded in a distorted tetrahedral geometry to one O(16), one O(17), one O(23), and one O(5) atom. The Zn(3)-O(16) bond length is 1.97 Å. The Zn(3)-O(17) bond length is 2.01 Å. The Zn(3)-O(23) bond length is 1.96 Å. The Zn(3)-O(5) bond length is 1.97 Å. In the fourth Zn site, Zn(4) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(27), and one O(28) atom. The Zn(4)-O(1) bond length is 1.97 Å. The Zn(4)-O(2) bond length is 1.93 Å. The Zn(4)-O(27) bond length is 1.94 Å. The Zn(4)-O(28) bond length is 1.95 Å. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a bent 120 degrees geometry to one C(5), one O(2), and one O(4) atom. The C(1)-C(5) bond length is 1.50 Å. The C(1)-O(2) bond length is 1.29 Å. The C(1)-O(4) bond length is 1.22 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(3), one C(6), and one C(8) atom. The C(2)-C(3) bond length is 1.48 Å. The C(2)-C(6) bond length is 1.38 Å. The C(2)-C(8) bond length is 1.41 Å. In the third C site, C(6) is bonded in a distorted single-bond geometry to one C(2), one C(7), and one H(1) atom. The C(6)-C(7) bond length is 1.40 Å. The C(6)-H(1) bond length is 0.95 Å. In the fourth C site, C(7) is bonded in a trigonal planar geometry to one C(4), one C(6), and one C(9) atom. The C(7)-C(4) bond length is 1.40 Å. The C(7)-C(9) bond length is 1.51 Å. In the fifth C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(3), and one O(6) atom. The C(3)-O(3) bond length is 1.29 Å. The C(3)-O(6) bond length is 1.23 Å. In the sixth C site, C(9) is bonded in a bent 120 degrees geometry to one C(7), one O(5), and one O(7) atom. The C(9)-O(5) bond length is 1.32 Å. The C(9)-O(7) bond length is 1.21 Å. In the seventh C site, C(4) is bonded in a distorted single-bond geometry to one C(5), one C(7), and one H(3) atom. The C(4)-C(5) bond length is 1.43 Å. The C(4)-H(3) bond length is 1.11 Å. In the eighth C site, C(5) is bonded in a trigonal planar geometry to one C(1), one C(4), and one C(8) atom. The C(5)-C(8) bond length is 1.36 Å. In the ninth C site, C(8) is bonded in a distorted single-bond geometry to one C(2), one C(5), and one H(2) atom. The C(8)-H(2) bond length is 0.95 Å. P(1) is bonded in a tetrahedral geometry to one O(12), one O(13), one O(22), and one O(34) atom. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(13) bond length is 1.56 Å. The P(1)-O(22) bond length is 1.53 Å. The P(1)-O(34) bond length is 1.56 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(6) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(8) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. There are thirty-four inequivalent O sites. In the first O site, O(25) is bonded in a single-bond geometry to one Mo(11), one Mo(12), and one Zn(1) atom. In the second O site, O(26) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(5) atom. In the third O site, O(27) is bonded in a single-bond geometry to one Mo(3), one Mo(7), and one Zn(4) atom. In the fourth O site, O(28) is bonded in a 3-coordinate geometry to one Mo(4), one Mo(9), and one Zn(4) atom. In the fifth O site, O(29) is bonded in a distorted bent 120 degrees geometry to one Mo(10) and one Mo(11) atom. In the sixth O site, O(30) is bonded in a distorted bent 120 degrees geometry to one Mo(12) and one Mo(2) atom. In the seventh O site, O(31) is bonded in a bent 120 degrees geometry to one Mo(12) and one Mo(9) atom. In the eighth O site, O(32) is bonded in a bent 120 degrees geometry to one Mo(3) and one Mo(4) atom. In the ninth O site, O(33) is bonded in a bent 120 degrees geometry to one Mo(11) and one Mo(8) atom. In the tenth O site, O(34) is bonded in a single-bond geometry to one Mo(12), one Mo(2), one Mo(9), and one P(1) atom. In the eleventh O site, O(1) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Zn(4) atom. In the twelfth O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(4) and one C(1) atom. In the thirteenth O site, O(3) is bonded in a bent 120 degrees geometry to one Zn(2) and one C(3) atom. In the fourteenth O site, O(4) is bonded in a single-bond geometry to one C(1) atom. In the fifteenth O site, O(5) is bonded in a water-like geometry to one Zn(3) and one C(9) atom. In the sixteenth O site, O(6) is bonded in a single-bond geometry to one C(3) atom. In the seventeenth O site, O(7) is bonded in a distorted single-bond geometry to one C(9) atom. In the eighteenth O site, O(8) is bonded in a 3-coordinate geometry to one Mo(10), one Mo(6), and one Zn(1) atom. In the nineteenth O site, O(9) is bonded in a bent 120 degrees geometry to one Mo(4) and one Mo(5) atom. In the twentieth O site, O(10) is bonded in a 3-coordinate geometry to one Mo(10), one Mo(6), and one Zn(2) atom. In the twenty-first O site, O(11) is bonded in a trigonal planar geometry to one Mo(1), one Mo(6), and one Zn(1) atom. In the twenty-second O site, O(12) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(6), one Mo(7), and one P(1) atom. In the twenty-third O site, O(13) is bonded in a single-bond geometry to one Mo(10), one Mo(11), one Mo(8), and one P(1) atom. In the twenty-fourth O site, O(14) is bonded in a bent 120 degrees geometry to one Mo(2) and one Mo(9) atom. In the twenty-fifth O site, O(15) is bonded in a single-bond geometry to one Mo(1) and one Mo(7) atom. In the twenty-sixth O site, O(16) is bonded in a distorted single-bond geometry to one Mo(5), one Mo(8), and one Zn(3) atom. In the twenty-seventh O site, O(17) is bonded in a distorted single-bond geometry to one Mo(4), one Mo(9), and one Zn(3) atom. In the twenty-eighth O site, O(18) is bonded in a 3-coordinate geometry to one Mo(5), one Mo(8), and one Zn(2) atom. In the twenty-ninth O site, O(19) is bonded in a distorted bent 120 degrees geometry to one Mo(6) and one Mo(7) atom. In the thirtieth O site, O(20) is bonded in a single-bond geometry to one Mo(3), one Mo(7), and one Zn(2) atom. In the thirty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Mo(10) and one Mo(8) atom. In the thirty-second O site, O(22) is bonded in a single-bond geometry to one Mo(3), one Mo(4), one Mo(5), and one P(1) atom. In the thirty-third O site, O(23) is bonded in a distorted single-bond geometry to one Mo(11), one Mo(12), and one Zn(3) atom. In the thirty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Zn(1) atom. Linkers: 8 [O]C(=O)c1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 4 O=[C]O[Zn]1O[Mo]2O[Mo@@]34O[Zn](O[C]=O)O[Mo@]5(O[Zn](O[C]=O)O[Mo]67(O[Mo]O[Mo@]3(O1)O6)O[Mo@@]71O[Mo]3O[Zn]O[Mo]678O[Mo@]9%10O[Zn](O[C]=O)O[Mo@@]%11%12O[Mo](O[Zn](O[C]=O)O[Mo@@]%11%13O[Mo]O[Mo]%11(O[Zn](O[C]=O)O9)(O%13)O[Mo@]%119O[Mo](O[Zn]O[Mo]%11%13(O5)O[Mo]%11(O3)(O1)O%13)O[Mo]6(O9)(O7)O8)O[Mo]13(O%12)O[Mo@]1(O%10)O3)O[Mo@]13O[Mo]1(O2)(O4)O3. RCSR code: pyr. The MOF has largest included sphere 10.41 A, density 1.36 g/cm3, surface area 1662.63 m2/g, accessible volume 0.49 cm3/g