K4V10P7O40 crystallizes in the tetragonal P4_3 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(13), one O(14), one O(19), one O(22), one O(23), one O(3), and one O(8) atom. The K(1)-O(13) bond length is 2.86 Å. The K(1)-O(14) bond length is 2.69 Å. The K(1)-O(19) bond length is 2.88 Å. The K(1)-O(22) bond length is 2.99 Å. The K(1)-O(23) bond length is 3.00 Å. The K(1)-O(3) bond length is 2.92 Å. The K(1)-O(8) bond length is 2.79 Å. In the second K site, K(2) is bonded in a 7-coordinate geometry to one O(14), one O(15), one O(2), one O(25), one O(29), one O(31), and one O(9) atom. The K(2)-O(14) bond length is 3.26 Å. The K(2)-O(15) bond length is 2.84 Å. The K(2)-O(2) bond length is 2.75 Å. The K(2)-O(25) bond length is 2.85 Å. The K(2)-O(29) bond length is 2.95 Å. The K(2)-O(31) bond length is 3.02 Å. The K(2)-O(9) bond length is 2.70 Å. In the third K site, K(3) is bonded in a 7-coordinate geometry to one O(21), one O(23), one O(27), one O(39), one O(4), one O(40), and one O(7) atom. The K(3)-O(21) bond length is 2.83 Å. The K(3)-O(23) bond length is 2.76 Å. The K(3)-O(27) bond length is 2.90 Å. The K(3)-O(39) bond length is 2.77 Å. The K(3)-O(4) bond length is 2.74 Å. The K(3)-O(40) bond length is 3.22 Å. The K(3)-O(7) bond length is 2.89 Å. In the fourth K site, K(4) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(17), one O(29), one O(32), one O(38), and one O(40) atom. The K(4)-O(1) bond length is 2.77 Å. The K(4)-O(10) bond length is 2.62 Å. The K(4)-O(17) bond length is 2.93 Å. The K(4)-O(29) bond length is 3.19 Å. The K(4)-O(32) bond length is 2.86 Å. The K(4)-O(38) bond length is 3.11 Å. The K(4)-O(40) bond length is 2.93 Å. There are ten inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(13), one O(17), one O(2), one O(21), and one O(25) atom. The V(1)-O(1) bond length is 1.62 Å. The V(1)-O(13) bond length is 2.00 Å. The V(1)-O(17) bond length is 1.98 Å. The V(1)-O(2) bond length is 2.35 Å. The V(1)-O(21) bond length is 1.97 Å. The V(1)-O(25) bond length is 2.01 Å. In the second V site, V(2) is bonded to one O(14), one O(18), one O(2), one O(22), and one O(5) atom to form distorted VO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one V(4)O5 trigonal bipyramid. The V(2)-O(14) bond length is 1.94 Å. The V(2)-O(18) bond length is 2.07 Å. The V(2)-O(2) bond length is 1.64 Å. The V(2)-O(22) bond length is 1.97 Å. The V(2)-O(5) bond length is 1.96 Å. In the third V site, V(3) is bonded to one O(1), one O(15), one O(26), one O(29), and one O(6) atom to form distorted VO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The V(3)-O(1) bond length is 2.49 Å. The V(3)-O(15) bond length is 1.96 Å. The V(3)-O(26) bond length is 2.04 Å. The V(3)-O(29) bond length is 2.00 Å. The V(3)-O(6) bond length is 1.94 Å. In the fourth V site, V(4) is bonded to one O(18), one O(3), one O(30), one O(33), and one O(5) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one V(2)O5 square pyramid. The V(4)-O(18) bond length is 2.08 Å. The V(4)-O(3) bond length is 1.61 Å. The V(4)-O(30) bond length is 1.92 Å. The V(4)-O(33) bond length is 1.95 Å. The V(4)-O(5) bond length is 1.95 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(26), one O(34), one O(37), one O(4), and one O(6) atom. The V(5)-O(26) bond length is 2.06 Å. The V(5)-O(34) bond length is 2.01 Å. The V(5)-O(37) bond length is 1.95 Å. The V(5)-O(4) bond length is 1.58 Å. The V(5)-O(6) bond length is 1.96 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(19), one O(27), one O(31), one O(38), one O(7), and one O(8) atom. The V(6)-O(19) bond length is 1.98 Å. The V(6)-O(27) bond length is 2.00 Å. The V(6)-O(31) bond length is 1.96 Å. The V(6)-O(38) bond length is 1.98 Å. The V(6)-O(7) bond length is 1.59 Å. The V(6)-O(8) bond length is 2.41 Å. In the seventh V site, V(7) is bonded to one O(11), one O(23), one O(28), one O(39), and one O(8) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. The V(7)-O(11) bond length is 1.95 Å. The V(7)-O(23) bond length is 1.95 Å. The V(7)-O(28) bond length is 2.06 Å. The V(7)-O(39) bond length is 2.00 Å. The V(7)-O(8) bond length is 1.61 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(12), one O(20), one O(32), one O(40), and one O(7) atom. The V(8)-O(12) bond length is 2.02 Å. The V(8)-O(20) bond length is 2.06 Å. The V(8)-O(32) bond length is 1.97 Å. The V(8)-O(40) bond length is 1.93 Å. The V(8)-O(7) bond length is 2.45 Å. In the ninth V site, V(9) is bonded to one O(10), one O(12), one O(20), one O(24), and one O(36) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The V(9)-O(10) bond length is 1.62 Å. The V(9)-O(12) bond length is 1.92 Å. The V(9)-O(20) bond length is 2.10 Å. The V(9)-O(24) bond length is 1.93 Å. The V(9)-O(36) bond length is 1.94 Å. In the tenth V site, V(10) is bonded in a 5-coordinate geometry to one O(11), one O(16), one O(28), one O(35), and one O(9) atom. The V(10)-O(11) bond length is 1.92 Å. The V(10)-O(16) bond length is 1.94 Å. The V(10)-O(28) bond length is 2.08 Å. The V(10)-O(35) bond length is 2.00 Å. The V(10)-O(9) bond length is 1.55 Å. There are seven inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O5 square pyramid and  a cornercorner with one V(3)O5 square pyramid. The P(1)-O(13) bond length is 1.54 Å. The P(1)-O(14) bond length is 1.54 Å. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(16) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(17), one O(18), one O(19), and one O(20) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O5 square pyramid,  a cornercorner with one V(4)O5 trigonal bipyramid, and  a cornercorner with one V(9)O5 trigonal bipyramid. The P(2)-O(17) bond length is 1.50 Å. The P(2)-O(18) bond length is 1.57 Å. The P(2)-O(19) bond length is 1.50 Å. The P(2)-O(20) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(21), one O(22), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O5 square pyramid,  a cornercorner with one V(7)O5 trigonal bipyramid, and  a cornercorner with one V(9)O5 trigonal bipyramid. The P(3)-O(21) bond length is 1.53 Å. The P(3)-O(22) bond length is 1.52 Å. The P(3)-O(23) bond length is 1.54 Å. The P(3)-O(24) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(25), one O(26), one O(27), and one O(28) atom to form PO4 tetrahedra that share  a cornercorner with one V(3)O5 square pyramid and  a cornercorner with one V(7)O5 trigonal bipyramid. The P(4)-O(25) bond length is 1.52 Å. The P(4)-O(26) bond length is 1.56 Å. The P(4)-O(27) bond length is 1.51 Å. The P(4)-O(28) bond length is 1.55 Å. In the fifth P site, P(5) is bonded to one O(29), one O(30), one O(31), and one O(32) atom to form PO4 tetrahedra that share  a cornercorner with one V(3)O5 square pyramid and  a cornercorner with one V(4)O5 trigonal bipyramid. The P(5)-O(29) bond length is 1.53 Å. The P(5)-O(30) bond length is 1.55 Å. The P(5)-O(31) bond length is 1.53 Å. The P(5)-O(32) bond length is 1.51 Å. In the sixth P site, P(6) is bonded to one O(33), one O(34), one O(35), and one O(36) atom to form PO4 tetrahedra that share  a cornercorner with one V(4)O5 trigonal bipyramid and  a cornercorner with one V(9)O5 trigonal bipyramid. The P(6)-O(33) bond length is 1.56 Å. The P(6)-O(34) bond length is 1.50 Å. The P(6)-O(35) bond length is 1.53 Å. The P(6)-O(36) bond length is 1.56 Å. In the seventh P site, P(7) is bonded to one O(37), one O(38), one O(39), and one O(40) atom to form PO4 tetrahedra that share  a cornercorner with one V(7)O5 trigonal bipyramid. The P(7)-O(37) bond length is 1.52 Å. The P(7)-O(38) bond length is 1.53 Å. The P(7)-O(39) bond length is 1.54 Å. The P(7)-O(40) bond length is 1.54 Å. There are forty inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(4), one V(1), and one V(3) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(2), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(3) and one V(5) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one V(2) and one V(4) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one V(3) and one V(5) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one K(3), one V(6), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(1), one V(6), and one V(7) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one K(2) and one V(10) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one K(4) and one V(9) atom. In the eleventh O site, O(11) is bonded in a water-like geometry to one V(10) and one V(7) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one V(8) and one V(9) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one K(1), one V(1), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one K(1), one K(2), one V(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one K(2), one V(3), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(10) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one K(4), one V(1), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one P(2) atom. In the nineteenth O site, O(19) is bonded in a 2-coordinate geometry to one K(1), one V(6), and one P(2) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one V(8), one V(9), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one K(3), one V(1), and one P(3) atom. In the twenty-second O site, O(22) is bonded in a 2-coordinate geometry to one K(1), one V(2), and one P(3) atom. In the twenty-third O site, O(23) is bonded in a 2-coordinate geometry to one K(1), one K(3), one V(7), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(9) and one P(3) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to one K(2), one V(1), and one P(4) atom. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one P(4) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 150 degrees geometry to one K(3), one V(6), and one P(4) atom. In the twenty-eighth O site, O(28) is bonded in a distorted trigonal planar geometry to one V(10), one V(7), and one P(4) atom. In the twenty-ninth O site, O(29) is bonded in a 2-coordinate geometry to one K(2), one K(4), one V(3), and one P(5) atom. In the thirtieth O site, O(30) is bonded in a bent 150 degrees geometry to one V(4) and one P(5) atom. In the thirty-first O site, O(31) is bonded in a distorted bent 120 degrees geometry to one K(2), one V(6), and one P(5) atom. In the thirty-second O site, O(32) is bonded in a 2-coordinate geometry to one K(4), one V(8), and one P(5) atom. In the thirty-third O site, O(33) is bonded in a bent 150 degrees geometry to one V(4) and one P(6) atom. In the thirty-fourth O site, O(34) is bonded in a bent 150 degrees geometry to one V(5) and one P(6) atom. In the thirty-fifth O site, O(35) is bonded in a bent 150 degrees geometry to one V(10) and one P(6) atom. In the thirty-sixth O site, O(36) is bonded in a bent 150 degrees geometry to one V(9) and one P(6) atom. In the thirty-seventh O site, O(37) is bonded in a bent 150 degrees geometry to one V(5) and one P(7) atom. In the thirty-eighth O site, O(38) is bonded in a 2-coordinate geometry to one K(4), one V(6), and one P(7) atom. In the thirty-ninth O site, O(39) is bonded in a 3-coordinate geometry to one K(3), one V(7), and one P(7) atom. In the fortieth O site, O(40) is bonded in a 2-coordinate geometry to one K(3), one K(4), one V(8), and one P(7) atom. Linkers: 28 [O]P([O])([O])=O. Metal clusters: 16 [K] ,40 [V]. The MOF has largest included sphere 4.67 A, density 2.25 g/cm3, surface area 1471.34 m2/g, accessible volume 0.12 cm3/g