K4Na2Sm4W30P5(CO50)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a single-bond geometry to one O(43) atom. The K(1)-O(43) bond length is 2.56 Å. In the second K site, K(2) is bonded in a 2-coordinate geometry to one O(33) and one O(50) atom. The K(2)-O(33) bond length is 2.53 Å. The K(2)-O(50) bond length is 2.65 Å. Na(1) is bonded in a pentagonal planar geometry to one O(1), one O(36), one O(41), one O(49), and one O(8) atom. The Na(1)-O(1) bond length is 2.64 Å. The Na(1)-O(36) bond length is 2.67 Å. The Na(1)-O(41) bond length is 2.58 Å. The Na(1)-O(49) bond length is 2.59 Å. The Na(1)-O(8) bond length is 2.68 Å. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a distorted T-shaped geometry to one O(16), one O(45), and one O(7) atom. The Sm(1)-O(16) bond length is 2.44 Å. The Sm(1)-O(45) bond length is 2.41 Å. The Sm(1)-O(7) bond length is 2.50 Å. In the second Sm site, Sm(2) is bonded in a distorted pentagonal planar geometry to one O(34), one O(42), one O(44), one O(47), and one O(50) atom. The Sm(2)-O(34) bond length is 2.33 Å. The Sm(2)-O(42) bond length is 2.34 Å. The Sm(2)-O(44) bond length is 2.37 Å. The Sm(2)-O(47) bond length is 2.43 Å. The Sm(2)-O(50) bond length is 2.33 Å. There are fifteen inequivalent W sites. In the first W site, W(1) is bonded to one O(19), one O(23), one O(38), one O(40), and one O(9) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(10)O6 octahedra,  a cornercorner with one W(3)O5 square pyramid,  a cornercorner with one W(6)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one W(13)O6 octahedra. The corner-sharing octahedral tilt angles are 27°. The W(1)-O(19) bond length is 1.81 Å. The W(1)-O(23) bond length is 1.92 Å. The W(1)-O(38) bond length is 2.10 Å. The W(1)-O(40) bond length is 2.29 Å. The W(1)-O(9) bond length is 1.90 Å. In the second W site, W(2) is bonded to one O(18), one O(20), one O(25), one O(3), one O(32), and one O(45) atom to form distorted WO6 octahedra that share  a cornercorner with one W(14)O5 square pyramid,  a cornercorner with one W(6)O5 square pyramid,  a cornercorner with one W(9)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(15)O5 square pyramid. The W(2)-O(18) bond length is 2.22 Å. The W(2)-O(20) bond length is 2.05 Å. The W(2)-O(25) bond length is 1.92 Å. The W(2)-O(3) bond length is 1.84 Å. The W(2)-O(32) bond length is 1.83 Å. The W(2)-O(45) bond length is 1.73 Å. In the third W site, W(3) is bonded to one O(10), one O(14), one O(15), one O(28), and one O(38) atom to form WO5 square pyramids that share  a cornercorner with one W(10)O6 octahedra,  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(7)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one W(7)O5 square pyramid. The corner-sharing octahedral tilt angles are 33°. The W(3)-O(10) bond length is 1.89 Å. The W(3)-O(14) bond length is 2.03 Å. The W(3)-O(15) bond length is 2.28 Å. The W(3)-O(28) bond length is 1.91 Å. The W(3)-O(38) bond length is 1.82 Å. In the fourth W site, W(4) is bonded to one O(12), one O(22), one O(26), one O(41), and one O(6) atom to form WO5 square pyramids that share  a cornercorner with one W(10)O6 octahedra,  a cornercorner with one W(13)O6 octahedra,  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(7)O5 square pyramid, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-32°. The W(4)-O(12) bond length is 1.90 Å. The W(4)-O(22) bond length is 1.97 Å. The W(4)-O(26) bond length is 1.88 Å. The W(4)-O(41) bond length is 2.21 Å. The W(4)-O(6) bond length is 1.90 Å. In the fifth W site, W(5) is bonded to one O(13), one O(26), one O(33), one O(37), one O(39), and one O(49) atom to form distorted WO6 octahedra that share  a cornercorner with one W(11)O6 octahedra,  a cornercorner with one W(8)O6 octahedra,  a cornercorner with one W(15)O5 square pyramid,  a cornercorner with one W(4)O5 square pyramid, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-27°. The W(5)-O(13) bond length is 1.95 Å. The W(5)-O(26) bond length is 1.90 Å. The W(5)-O(33) bond length is 1.72 Å. The W(5)-O(37) bond length is 1.90 Å. The W(5)-O(39) bond length is 1.87 Å. The W(5)-O(49) bond length is 2.21 Å. In the sixth W site, W(6) is bonded to one O(19), one O(2), one O(20), one O(30), and one O(48) atom to form WO5 square pyramids that share  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(9)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(11)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. The W(6)-O(19) bond length is 2.05 Å. The W(6)-O(2) bond length is 1.91 Å. The W(6)-O(20) bond length is 1.83 Å. The W(6)-O(30) bond length is 1.92 Å. The W(6)-O(48) bond length is 2.29 Å. In the seventh W site, W(7) is bonded to one O(14), one O(15), one O(22), one O(28), and one O(35) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(13)O6 octahedra,  a cornercorner with one W(3)O5 square pyramid,  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one W(3)O5 square pyramid. The corner-sharing octahedral tilt angles are 29°. The W(7)-O(14) bond length is 1.84 Å. The W(7)-O(15) bond length is 2.23 Å. The W(7)-O(22) bond length is 1.86 Å. The W(7)-O(28) bond length is 1.92 Å. The W(7)-O(35) bond length is 2.06 Å. In the eighth W site, W(8) is bonded to one O(17), one O(27), one O(34), one O(36), one O(39), and one O(4) atom to form distorted WO6 octahedra that share  a cornercorner with one W(12)O6 octahedra,  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(14)O5 square pyramid,  a cornercorner with one W(9)O5 square pyramid, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-26°. The W(8)-O(17) bond length is 1.97 Å. The W(8)-O(27) bond length is 1.90 Å. The W(8)-O(34) bond length is 1.74 Å. The W(8)-O(36) bond length is 2.18 Å. The W(8)-O(39) bond length is 1.91 Å. The W(8)-O(4) bond length is 1.85 Å. In the ninth W site, W(9) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form WO5 square pyramids that share  a cornercorner with one W(10)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(8)O6 octahedra,  a cornercorner with one W(6)O5 square pyramid, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 18-25°. The W(9)-O(1) bond length is 2.23 Å. The W(9)-O(2) bond length is 1.90 Å. The W(9)-O(3) bond length is 1.96 Å. The W(9)-O(4) bond length is 1.93 Å. The W(9)-O(5) bond length is 1.88 Å. In the tenth W site, W(10) is bonded to one O(10), one O(5), one O(6), one O(7), one O(8), and one O(9) atom to form distorted WO6 octahedra that share  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(3)O5 square pyramid,  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one W(9)O5 square pyramid, and  a cornercorner with one P(2)O4 tetrahedra. The W(10)-O(10) bond length is 1.91 Å. The W(10)-O(5) bond length is 1.90 Å. The W(10)-O(6) bond length is 1.90 Å. The W(10)-O(7) bond length is 1.74 Å. The W(10)-O(8) bond length is 2.19 Å. The W(10)-O(9) bond length is 1.92 Å. In the eleventh W site, W(11) is bonded to one O(13), one O(30), one O(31), one O(43), one O(46), and one O(48) atom to form distorted WO6 octahedra that share  a cornercorner with one W(13)O6 octahedra,  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(15)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(6)O5 square pyramid. The corner-sharing octahedral tilt angles range from 21-27°. The W(11)-O(13) bond length is 1.87 Å. The W(11)-O(30) bond length is 1.95 Å. The W(11)-O(31) bond length is 2.07 Å. The W(11)-O(43) bond length is 1.73 Å. The W(11)-O(46) bond length is 1.81 Å. The W(11)-O(48) bond length is 2.25 Å. In the twelfth W site, W(12) is bonded to one O(11), one O(17), one O(21), one O(24), one O(29), and one O(42) atom to form distorted WO6 octahedra that share  a cornercorner with one W(8)O6 octahedra,  a cornercorner with one W(14)O5 square pyramid,  a cornercorner with one W(15)O5 square pyramid,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one W(14)O5 square pyramid. The corner-sharing octahedral tilt angles are 26°. The W(12)-O(11) bond length is 2.25 Å. The W(12)-O(17) bond length is 1.85 Å. The W(12)-O(21) bond length is 2.05 Å. The W(12)-O(24) bond length is 1.80 Å. The W(12)-O(29) bond length is 1.95 Å. The W(12)-O(42) bond length is 1.75 Å. In the thirteenth W site, W(13) is bonded to one O(12), one O(16), one O(23), one O(35), one O(40), and one O(46) atom to form distorted WO6 octahedra that share  a cornercorner with one W(11)O6 octahedra,  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one W(7)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one W(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 21°. The W(13)-O(12) bond length is 1.90 Å. The W(13)-O(16) bond length is 1.73 Å. The W(13)-O(23) bond length is 1.92 Å. The W(13)-O(35) bond length is 1.82 Å. The W(13)-O(40) bond length is 2.23 Å. The W(13)-O(46) bond length is 2.06 Å. In the fourteenth W site, W(14) is bonded to one O(11), one O(21), one O(27), one O(29), and one O(32) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(12)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(8)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one W(12)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-33°. The W(14)-O(11) bond length is 2.28 Å. The W(14)-O(21) bond length is 1.85 Å. The W(14)-O(27) bond length is 1.91 Å. The W(14)-O(29) bond length is 1.90 Å. The W(14)-O(32) bond length is 2.04 Å. In the fifteenth W site, W(15) is bonded to one O(18), one O(24), one O(25), one O(31), and one O(37) atom to form WO5 square pyramids that share  a cornercorner with one W(11)O6 octahedra,  a cornercorner with one W(12)O6 octahedra,  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-33°. The W(15)-O(18) bond length is 2.31 Å. The W(15)-O(24) bond length is 2.06 Å. The W(15)-O(25) bond length is 1.92 Å. The W(15)-O(31) bond length is 1.82 Å. The W(15)-O(37) bond length is 1.91 Å. C(1) is bonded in a 2-coordinate geometry to one O(44) and one O(47) atom. The C(1)-O(44) bond length is 1.26 Å. The C(1)-O(47) bond length is 1.21 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(18), one O(48), and one O(49) atom to form PO4 tetrahedra that share  a cornercorner with one W(11)O6 octahedra,  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(15)O5 square pyramid,  a cornercorner with one W(6)O5 square pyramid, and  a cornercorner with one W(9)O5 square pyramid. The corner-sharing octahedral tilt angles are 50°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(18) bond length is 1.57 Å. The P(1)-O(48) bond length is 1.54 Å. The P(1)-O(49) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(15), one O(40), one O(41), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one W(10)O6 octahedra,  a cornercorner with one W(13)O6 octahedra,  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(3)O5 square pyramid,  a cornercorner with one W(4)O5 square pyramid, and  a cornercorner with one W(7)O5 square pyramid. The corner-sharing octahedral tilt angles range from 47-55°. The P(2)-O(15) bond length is 1.58 Å. The P(2)-O(40) bond length is 1.58 Å. The P(2)-O(41) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.50 Å. In the third P site, P(3) is bonded to two equivalent O(11) and two equivalent O(36) atoms to form PO4 tetrahedra that share corners with two equivalent W(12)O6 octahedra, corners with two equivalent W(8)O6 octahedra, and corners with two equivalent W(14)O5 square pyramids. The corner-sharing octahedral tilt angles range from 48-51°. Both P(3)-O(11) bond lengths are 1.54 Å. Both P(3)-O(36) bond lengths are 1.51 Å. There are fifty inequivalent O sites. In the first O site, O(43) is bonded in a distorted single-bond geometry to one K(1) and one W(11) atom. In the second O site, O(18) is bonded in a distorted single-bond geometry to one W(15), one W(2), and one P(1) atom. In the third O site, O(23) is bonded in a bent 120 degrees geometry to one W(1) and one W(13) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one W(2) and one W(9) atom. In the fifth O site, O(1) is bonded in a distorted single-bond geometry to one Na(1), one W(9), and one P(1) atom. In the sixth O site, O(2) is bonded in a bent 150 degrees geometry to one W(6) and one W(9) atom. In the seventh O site, O(4) is bonded in a distorted bent 150 degrees geometry to one W(8) and one W(9) atom. In the eighth O site, O(5) is bonded in a distorted linear geometry to one W(10) and one W(9) atom. In the ninth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(10) and one W(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one W(10) and one W(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one W(12), one W(14), and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one W(13) and one W(4) atom. In the thirteenth O site, O(7) is bonded in a distorted linear geometry to one Sm(1) and one W(10) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one W(3) and one W(7) atom. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one W(3), one W(7), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one W(13) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one W(12) and one W(8) atom. In the eighteenth O site, O(8) is bonded in a distorted single-bond geometry to one Na(1), one W(10), and one P(2) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one W(1) and one W(6) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one W(2) and one W(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one W(12) and one W(14) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one W(4) and one W(7) atom. In the twenty-third O site, O(9) is bonded in a bent 150 degrees geometry to one W(1) and one W(10) atom. In the twenty-fourth O site, O(24) is bonded in a distorted bent 150 degrees geometry to one W(12) and one W(15) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one W(15) and one W(2) atom. In the twenty-sixth O site, O(26) is bonded in a distorted bent 150 degrees geometry to one W(4) and one W(5) atom. In the twenty-seventh O site, O(27) is bonded in a bent 150 degrees geometry to one W(14) and one W(8) atom. In the twenty-eighth O site, O(28) is bonded in a bent 120 degrees geometry to one W(3) and one W(7) atom. In the twenty-ninth O site, O(29) is bonded in a bent 120 degrees geometry to one W(12) and one W(14) atom. In the thirtieth O site, O(30) is bonded in a bent 120 degrees geometry to one W(11) and one W(6) atom. In the thirty-first O site, O(31) is bonded in a bent 150 degrees geometry to one W(11) and one W(15) atom. In the thirty-second O site, O(32) is bonded in a distorted single-bond geometry to one W(14) and one W(2) atom. In the thirty-third O site, O(33) is bonded in a distorted linear geometry to one K(2) and one W(5) atom. In the thirty-fourth O site, O(34) is bonded in a distorted single-bond geometry to one Sm(2) and one W(8) atom. In the thirty-fifth O site, O(35) is bonded in a distorted bent 150 degrees geometry to one W(13) and one W(7) atom. In the thirty-sixth O site, O(36) is bonded in a distorted single-bond geometry to one Na(1), one W(8), and one P(3) atom. In the thirty-seventh O site, O(37) is bonded in a bent 150 degrees geometry to one W(15) and one W(5) atom. In the thirty-eighth O site, O(38) is bonded in a bent 150 degrees geometry to one W(1) and one W(3) atom. In the thirty-ninth O site, O(39) is bonded in a bent 150 degrees geometry to one W(5) and one W(8) atom. In the fortieth O site, O(40) is bonded in a distorted single-bond geometry to one W(1), one W(13), and one P(2) atom. In the forty-first O site, O(41) is bonded in a distorted single-bond geometry to one Na(1), one W(4), and one P(2) atom. In the forty-second O site, O(42) is bonded in a distorted bent 150 degrees geometry to one Sm(2) and one W(12) atom. In the forty-third O site, O(13) is bonded in a bent 150 degrees geometry to one W(11) and one W(5) atom. In the forty-fourth O site, O(44) is bonded in a distorted single-bond geometry to one Sm(2) and one C(1) atom. In the forty-fifth O site, O(45) is bonded in a distorted single-bond geometry to one Sm(1) and one W(2) atom. In the forty-sixth O site, O(46) is bonded in a bent 150 degrees geometry to one W(11) and one W(13) atom. In the forty-seventh O site, O(47) is bonded in a distorted bent 120 degrees geometry to one Sm(2) and one C(1) atom. In the forty-eighth O site, O(48) is bonded in a distorted single-bond geometry to one W(11), one W(6), and one P(1) atom. In the forty-ninth O site, O(49) is bonded in a distorted single-bond geometry to one Na(1), one W(5), and one P(1) atom. In the fiftieth O site, O(50) is bonded in a bent 120 degrees geometry to one K(2) and one Sm(2) atom. Linkers: 3 [O]C(=O)C([O])=O. Metal clusters: 16 [K] ,8 [Na] ,16 [Sm] ,120 [W]. The MOF has largest included sphere 5.25 A, density 3.60 g/cm3, surface area 1092.46 m2/g, accessible volume 0.12 cm3/g