Pr3W12C18N3H6O44(CH)3 crystallizes in the orthorhombic Pbca space group. The structure consists of twenty-four 02329_fluka molecules inside a Pr3W12C18N3H6O44 framework. In the Pr3W12C18N3H6O44 framework, there are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one N(2), one N(3), one O(11), one O(27), one O(28), one O(29), one O(31), and one O(42) atom. The Pr(1)-N(2) bond length is 2.57 Å. The Pr(1)-N(3) bond length is 2.64 Å. The Pr(1)-O(11) bond length is 2.44 Å. The Pr(1)-O(27) bond length is 2.54 Å. The Pr(1)-O(28) bond length is 2.56 Å. The Pr(1)-O(29) bond length is 2.51 Å. The Pr(1)-O(31) bond length is 2.55 Å. The Pr(1)-O(42) bond length is 2.42 Å. In the second Pr site, Pr(2) is bonded in a distorted hexagonal planar geometry to one N(1), one O(16), one O(23), one O(32), one O(35), and one O(44) atom. The Pr(2)-N(1) bond length is 2.65 Å. The Pr(2)-O(16) bond length is 2.47 Å. The Pr(2)-O(23) bond length is 2.45 Å. The Pr(2)-O(32) bond length is 2.64 Å. The Pr(2)-O(35) bond length is 2.45 Å. The Pr(2)-O(44) bond length is 2.46 Å. In the third Pr site, Pr(3) is bonded in a trigonal planar geometry to one O(10), one O(12), and one O(34) atom. The Pr(3)-O(10) bond length is 2.52 Å. The Pr(3)-O(12) bond length is 2.51 Å. The Pr(3)-O(34) bond length is 2.43 Å. There are twelve inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(13), one O(22), one O(39), and one O(5) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(3)O6 octahedra,  a cornercorner with one W(8)O5 square pyramid,  an edgeedge with one W(2)O6 octahedra, and  an edgeedge with one W(11)O5 square pyramid. The corner-sharing octahedral tilt angles are 30°. The W(1)-O(1) bond length is 2.23 Å. The W(1)-O(13) bond length is 1.86 Å. The W(1)-O(22) bond length is 1.98 Å. The W(1)-O(39) bond length is 1.89 Å. The W(1)-O(5) bond length is 1.98 Å. In the second W site, W(2) is bonded to one O(1), one O(12), one O(13), one O(15), one O(36), and one O(41) atom to form a mixture of distorted edge and corner-sharing WO6 octahedra. The W(2)-O(1) bond length is 2.11 Å. The W(2)-O(12) bond length is 1.75 Å. The W(2)-O(13) bond length is 2.05 Å. The W(2)-O(15) bond length is 1.90 Å. The W(2)-O(36) bond length is 1.95 Å. The W(2)-O(41) bond length is 1.83 Å. In the third W site, W(3) is bonded to one O(14), one O(16), one O(2), one O(33), one O(37), and one O(5) atom to form a mixture of distorted edge and corner-sharing WO6 octahedra. The W(3)-O(14) bond length is 1.88 Å. The W(3)-O(16) bond length is 1.74 Å. The W(3)-O(2) bond length is 2.20 Å. The W(3)-O(33) bond length is 1.94 Å. The W(3)-O(37) bond length is 1.97 Å. The W(3)-O(5) bond length is 1.84 Å. In the fourth W site, W(4) is bonded to one O(2), one O(20), one O(37), one O(7), and one O(8) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(7)O5 square pyramid,  an edgeedge with one W(3)O6 octahedra, and  an edgeedge with one W(9)O5 square pyramid. The corner-sharing octahedral tilt angles are 29°. The W(4)-O(2) bond length is 2.25 Å. The W(4)-O(20) bond length is 1.96 Å. The W(4)-O(37) bond length is 1.88 Å. The W(4)-O(7) bond length is 1.95 Å. The W(4)-O(8) bond length is 1.88 Å. In the fifth W site, W(5) is bonded to one O(20), one O(21), one O(28), one O(30), one O(43), and one O(9) atom to form distorted WO6 octahedra that share  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one W(7)O5 square pyramid,  an edgeedge with one W(6)O6 octahedra, and  an edgeedge with one W(12)O5 square pyramid. The W(5)-O(20) bond length is 1.86 Å. The W(5)-O(21) bond length is 1.88 Å. The W(5)-O(28) bond length is 1.71 Å. The W(5)-O(30) bond length is 1.92 Å. The W(5)-O(43) bond length is 2.17 Å. The W(5)-O(9) bond length is 1.99 Å. In the sixth W site, W(6) is bonded to one O(17), one O(21), one O(23), one O(25), one O(4), and one O(43) atom to form distorted WO6 octahedra that share  a cornercorner with one W(11)O5 square pyramid,  a cornercorner with one W(9)O5 square pyramid,  an edgeedge with one W(5)O6 octahedra, and  an edgeedge with one W(12)O5 square pyramid. The W(6)-O(17) bond length is 1.92 Å. The W(6)-O(21) bond length is 2.00 Å. The W(6)-O(23) bond length is 1.74 Å. The W(6)-O(25) bond length is 1.96 Å. The W(6)-O(4) bond length is 1.85 Å. The W(6)-O(43) bond length is 2.16 Å. In the seventh W site, W(7) is bonded to one O(19), one O(24), one O(3), one O(30), and one O(8) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(5)O6 octahedra,  a cornercorner with one W(4)O5 square pyramid,  an edgeedge with one W(10)O5 square pyramid, and  an edgeedge with one W(8)O5 square pyramid. The corner-sharing octahedral tilt angles are 29°. The W(7)-O(19) bond length is 1.98 Å. The W(7)-O(24) bond length is 1.91 Å. The W(7)-O(3) bond length is 2.29 Å. The W(7)-O(30) bond length is 1.89 Å. The W(7)-O(8) bond length is 1.95 Å. In the eighth W site, W(8) is bonded to one O(14), one O(19), one O(3), one O(31), and one O(39) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(3)O6 octahedra,  a cornercorner with one W(1)O5 square pyramid,  an edgeedge with one W(10)O5 square pyramid, and  an edgeedge with one W(7)O5 square pyramid. The corner-sharing octahedral tilt angles are 30°. The W(8)-O(14) bond length is 1.95 Å. The W(8)-O(19) bond length is 1.89 Å. The W(8)-O(3) bond length is 2.19 Å. The W(8)-O(31) bond length is 1.94 Å. The W(8)-O(39) bond length is 1.92 Å. In the ninth W site, W(9) is bonded to one O(17), one O(2), one O(26), one O(33), and one O(7) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(6)O6 octahedra,  a cornercorner with one W(11)O5 square pyramid,  an edgeedge with one W(3)O6 octahedra, and  an edgeedge with one W(4)O5 square pyramid. The corner-sharing octahedral tilt angles are 31°. The W(9)-O(17) bond length is 1.91 Å. The W(9)-O(2) bond length is 2.24 Å. The W(9)-O(26) bond length is 1.92 Å. The W(9)-O(33) bond length is 1.93 Å. The W(9)-O(7) bond length is 1.92 Å. In the tenth W site, W(10) is bonded to one O(15), one O(18), one O(24), one O(3), and one O(31) atom to form WO5 square pyramids that share  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(12)O5 square pyramid,  an edgeedge with one W(7)O5 square pyramid, and  an edgeedge with one W(8)O5 square pyramid. The corner-sharing octahedral tilt angles are 32°. The W(10)-O(15) bond length is 1.89 Å. The W(10)-O(18) bond length is 1.86 Å. The W(10)-O(24) bond length is 1.95 Å. The W(10)-O(3) bond length is 2.15 Å. The W(10)-O(31) bond length is 2.02 Å. In the eleventh W site, W(11) is bonded to one O(1), one O(22), one O(26), one O(36), and one O(4) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(6)O6 octahedra,  a cornercorner with one W(9)O5 square pyramid,  an edgeedge with one W(2)O6 octahedra, and  an edgeedge with one W(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 29°. The W(11)-O(1) bond length is 2.24 Å. The W(11)-O(22) bond length is 1.89 Å. The W(11)-O(26) bond length is 1.90 Å. The W(11)-O(36) bond length is 1.96 Å. The W(11)-O(4) bond length is 1.97 Å. In the twelfth W site, W(12) is bonded to one O(18), one O(25), one O(41), one O(43), and one O(9) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one W(10)O5 square pyramid,  an edgeedge with one W(5)O6 octahedra, and  an edgeedge with one W(6)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. The W(12)-O(18) bond length is 1.95 Å. The W(12)-O(25) bond length is 1.90 Å. The W(12)-O(41) bond length is 1.98 Å. The W(12)-O(43) bond length is 2.26 Å. The W(12)-O(9) bond length is 1.87 Å. There are eighteen inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one C(6), and one N(1) atom. The C(1)-C(2) bond length is 1.33 Å. The C(1)-C(6) bond length is 1.42 Å. The C(1)-N(1) bond length is 1.36 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1) and one H(1) atom. The C(2)-H(1) bond length is 0.93 Å. In the third C site, C(5) is bonded in a distorted single-bond geometry to one N(1) atom. The C(5)-N(1) bond length is 1.30 Å. In the fourth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(32), and one O(6) atom. The C(6)-O(32) bond length is 1.22 Å. The C(6)-O(6) bond length is 1.35 Å. In the fifth C site, C(7) is bonded in a 2-coordinate geometry to one O(34) and one O(44) atom. The C(7)-O(34) bond length is 1.32 Å. The C(7)-O(44) bond length is 1.20 Å. In the sixth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(13), one C(9), and one N(2) atom. The C(8)-C(13) bond length is 1.43 Å. The C(8)-C(9) bond length is 1.45 Å. The C(8)-N(2) bond length is 1.34 Å. In the seventh C site, C(9) is bonded in a distorted single-bond geometry to one C(8) and one H(4) atom. The C(9)-H(4) bond length is 0.93 Å. In the eighth C site, C(11) is bonded in a distorted single-bond geometry to one C(12) and one H(6) atom. The C(11)-C(12) bond length is 1.38 Å. The C(11)-H(6) bond length is 0.93 Å. In the ninth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(11), one C(14), and one N(2) atom. The C(12)-C(14) bond length is 1.44 Å. The C(12)-N(2) bond length is 1.30 Å. In the tenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one C(8), one O(35), and one O(42) atom. The C(13)-O(35) bond length is 1.29 Å. The C(13)-O(42) bond length is 1.23 Å. In the eleventh C site, C(14) is bonded in a distorted bent 120 degrees geometry to one C(12), one O(29), and one O(40) atom. The C(14)-O(29) bond length is 1.25 Å. The C(14)-O(40) bond length is 1.30 Å. In the twelfth C site, C(15) is bonded in a distorted trigonal planar geometry to one C(16), one C(20), and one N(3) atom. The C(15)-C(16) bond length is 1.41 Å. The C(15)-C(20) bond length is 1.49 Å. The C(15)-N(3) bond length is 1.32 Å. In the thirteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(15) and one H(7) atom. The C(16)-H(7) bond length is 0.93 Å. In the fourteenth C site, C(17) is bonded in a distorted single-bond geometry to one C(18) and one H(8) atom. The C(17)-C(18) bond length is 1.34 Å. The C(17)-H(8) bond length is 0.93 Å. In the fifteenth C site, C(18) is bonded in a distorted trigonal planar geometry to one C(17), one C(19), and one H(9) atom. The C(18)-C(19) bond length is 1.34 Å. The C(18)-H(9) bond length is 0.93 Å. In the sixteenth C site, C(19) is bonded in a distorted single-bond geometry to one C(18) and one N(3) atom. The C(19)-N(3) bond length is 1.34 Å. In the seventeenth C site, C(20) is bonded in a distorted bent 120 degrees geometry to one C(15), one O(27), and one O(38) atom. The C(20)-O(27) bond length is 1.23 Å. The C(20)-O(38) bond length is 1.29 Å. In the eighteenth C site, C(21) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(11) atom. The C(21)-O(10) bond length is 1.22 Å. The C(21)-O(11) bond length is 1.28 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 120 degrees geometry to one Pr(2), one C(1), and one C(5) atom. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Pr(1), one C(12), and one C(8) atom. In the third N site, N(3) is bonded in a distorted bent 120 degrees geometry to one Pr(1), one C(15), and one C(19) atom. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(4) is bonded in a single-bond geometry to one C(9) atom. In the third H site, H(6) is bonded in a single-bond geometry to one C(11) atom. In the fourth H site, H(7) is bonded in a single-bond geometry to one C(16) atom. In the fifth H site, H(8) is bonded in a single-bond geometry to one C(17) atom. In the sixth H site, H(9) is bonded in a single-bond geometry to one C(18) atom. There are forty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one W(1), one W(11), and one W(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one W(3), one W(4), and one W(9) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one W(10), one W(7), and one W(8) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(11) and one W(6) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one W(1) and one W(3) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one C(6) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one W(4) and one W(9) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one W(4) and one W(7) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one W(12) and one W(5) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Pr(3) and one C(21) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Pr(1) and one C(21) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Pr(3) and one W(2) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one W(1) and one W(2) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one W(3) and one W(8) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one W(10) and one W(2) atom. In the sixteenth O site, O(16) is bonded in a distorted single-bond geometry to one Pr(2) and one W(3) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one W(6) and one W(9) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one W(10) and one W(12) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one W(7) and one W(8) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one W(4) and one W(5) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one W(5) and one W(6) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one W(1) and one W(11) atom. In the twenty-third O site, O(23) is bonded in a distorted linear geometry to one Pr(2) and one W(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one W(10) and one W(7) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one W(12) and one W(6) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one W(11) and one W(9) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one Pr(1) and one C(20) atom. In the twenty-eighth O site, O(28) is bonded in a distorted single-bond geometry to one Pr(1) and one W(5) atom. In the twenty-ninth O site, O(29) is bonded in a distorted single-bond geometry to one Pr(1) and one C(14) atom. In the thirtieth O site, O(30) is bonded in a bent 150 degrees geometry to one W(5) and one W(7) atom. In the thirty-first O site, O(31) is bonded in a trigonal planar geometry to one Pr(1), one W(10), and one W(8) atom. In the thirty-second O site, O(32) is bonded in a single-bond geometry to one Pr(2) and one C(6) atom. In the thirty-third O site, O(33) is bonded in a bent 120 degrees geometry to one W(3) and one W(9) atom. In the thirty-fourth O site, O(34) is bonded in a bent 150 degrees geometry to one Pr(3) and one C(7) atom. In the thirty-fifth O site, O(35) is bonded in a distorted bent 150 degrees geometry to one Pr(2) and one C(13) atom. In the thirty-sixth O site, O(36) is bonded in a bent 120 degrees geometry to one W(11) and one W(2) atom. In the thirty-seventh O site, O(37) is bonded in a bent 120 degrees geometry to one W(3) and one W(4) atom. In the thirty-eighth O site, O(38) is bonded in a single-bond geometry to one C(20) atom. In the thirty-ninth O site, O(39) is bonded in a bent 150 degrees geometry to one W(1) and one W(8) atom. In the fortieth O site, O(40) is bonded in a single-bond geometry to one C(14) atom. In the forty-first O site, O(41) is bonded in a bent 150 degrees geometry to one W(12) and one W(2) atom. In the forty-second O site, O(42) is bonded in a bent 120 degrees geometry to one Pr(1) and one C(13) atom. In the forty-third O site, O(43) is bonded in a distorted T-shaped geometry to one W(12), one W(5), and one W(6) atom. In the forty-fourth O site, O(44) is bonded in a distorted single-bond geometry to one Pr(2) and one C(7) atom. Linkers: 24 [O]C(=O)c1cccc(C([O])=O)n1. Metal clusters: 24 [Pr] ,96 [W]. The MOF has largest included sphere 5.42 A, density 3.41 g/cm3, surface area 1420.94 m2/g, accessible volume 0.12 cm3/g