W18Cu3C12P2N6H12O47 crystallizes in the trigonal R32 space group. There are six inequivalent W sites. In the first W site, W(1) is bonded to one O(12), one O(16), one O(8), and two equivalent O(13) atoms to form distorted WO5 square pyramids that share  a cornercorner with one W(2)O5 square pyramid,  a cornercorner with one W(5)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and edges with two equivalent W(1)O5 square pyramids. The W(1)-O(12) bond length is 1.88 Å. The W(1)-O(16) bond length is 2.38 Å. The W(1)-O(8) bond length is 1.92 Å. There is one shorter (1.93 Å) and one longer (1.95 Å) W(1)-O(13) bond length. In the second W site, W(2) is bonded to one O(1), one O(10), one O(12), one O(2), and one O(7) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one W(5)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(5)O5 square pyramid. The W(2)-O(1) bond length is 1.88 Å. The W(2)-O(10) bond length is 1.91 Å. The W(2)-O(12) bond length is 1.93 Å. The W(2)-O(2) bond length is 1.91 Å. The W(2)-O(7) bond length is 2.35 Å. In the third W site, W(3) is bonded to one O(11), one O(15), one O(17), and two equivalent O(9) atoms to form distorted WO5 square pyramids that share  a cornercorner with one W(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and edges with two equivalent W(3)O5 square pyramids. The W(3)-O(11) bond length is 1.88 Å. The W(3)-O(15) bond length is 1.91 Å. The W(3)-O(17) bond length is 2.38 Å. There is one shorter (1.92 Å) and one longer (1.94 Å) W(3)-O(9) bond length. In the fourth W site, W(4) is bonded to one O(1), one O(15), one O(3), one O(4), and one O(5) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(2)O5 square pyramid,  a cornercorner with one W(3)O5 square pyramid, and  a cornercorner with one P(2)O4 tetrahedra. The W(4)-O(1) bond length is 1.92 Å. The W(4)-O(15) bond length is 1.93 Å. The W(4)-O(3) bond length is 1.91 Å. The W(4)-O(4) bond length is 1.91 Å. The W(4)-O(5) bond length is 2.35 Å. In the fifth W site, W(5) is bonded to one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form distorted WO5 square pyramids that share  a cornercorner with one W(1)O5 square pyramid,  a cornercorner with one W(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one W(2)O5 square pyramid. The W(5)-O(10) bond length is 1.89 Å. The W(5)-O(2) bond length is 1.92 Å. The W(5)-O(6) bond length is 1.92 Å. The W(5)-O(7) bond length is 2.36 Å. The W(5)-O(8) bond length is 1.90 Å. In the sixth W site, W(6) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(3), one O(4), one O(5), and one O(6) atom. The W(6)-O(11) bond length is 1.96 Å. The W(6)-O(14) bond length is 1.74 Å. The W(6)-O(3) bond length is 1.90 Å. The W(6)-O(4) bond length is 1.89 Å. The W(6)-O(5) bond length is 2.34 Å. The W(6)-O(6) bond length is 1.89 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to two equivalent N(1) atoms. Both Cu(1)-N(1) bond lengths are 1.91 Å. In the second Cu site, Cu(2) is bonded in a trigonal pyramidal geometry to two equivalent N(2) and two equivalent O(14) atoms. Both Cu(2)-N(2) bond lengths are 2.00 Å. Both Cu(2)-O(14) bond lengths are 2.18 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(3), one N(1), and one H(1) atom. The C(1)-C(3) bond length is 1.34 Å. The C(1)-N(1) bond length is 1.33 Å. The C(1)-H(1) bond length is 0.93 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(4), one N(1), and one H(2) atom. The C(2)-C(4) bond length is 1.37 Å. The C(2)-N(1) bond length is 1.30 Å. The C(2)-H(2) bond length is 0.93 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(1), one N(2), and one H(3) atom. The C(3)-N(2) bond length is 1.33 Å. The C(3)-H(3) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(2), and one H(4) atom. The C(4)-N(2) bond length is 1.33 Å. The C(4)-H(4) bond length is 0.93 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(16) and three equivalent O(7) atoms to form PO4 tetrahedra that share corners with three equivalent W(1)O5 square pyramids, corners with three equivalent W(2)O5 square pyramids, and corners with three equivalent W(5)O5 square pyramids. The P(1)-O(16) bond length is 1.57 Å. All P(1)-O(7) bond lengths are 1.54 Å. In the second P site, P(2) is bonded to one O(17) and three equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent W(3)O5 square pyramids and corners with three equivalent W(4)O5 square pyramids. The P(2)-O(17) bond length is 1.57 Å. All P(2)-O(5) bond lengths are 1.55 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(3), and one C(4) atom. There are four 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(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. There are seventeen inequivalent O sites. In the first O site, O(16) is bonded in a distorted single-bond geometry to three equivalent W(1) and one P(1) atom. In the second O site, O(17) is bonded in a distorted single-bond geometry to three equivalent W(3) and one P(2) atom. In the third O site, O(1) is bonded in a linear geometry to one W(2) and one W(4) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one W(2) and one W(5) atom. In the fifth O site, O(3) is bonded in a bent 120 degrees geometry to one W(4) and one W(6) atom. In the sixth O site, O(4) is bonded in a bent 150 degrees geometry to one W(4) and one W(6) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one W(4), one W(6), and one P(2) atom. In the eighth O site, O(6) is bonded in a linear geometry to one W(5) and one W(6) atom. In the ninth O site, O(7) is bonded in a distorted single-bond geometry to one W(2), one W(5), and one P(1) atom. In the tenth O site, O(8) is bonded in a bent 150 degrees geometry to one W(1) and one W(5) atom. In the eleventh O site, O(9) is bonded in a bent 120 degrees geometry to two equivalent W(3) atoms. In the twelfth O site, O(10) is bonded in a bent 150 degrees geometry to one W(2) and one W(5) atom. In the thirteenth O site, O(11) is bonded in a bent 150 degrees geometry to one W(3) and one W(6) atom. In the fourteenth O site, O(12) is bonded in a bent 150 degrees geometry to one W(1) and one W(2) atom. In the fifteenth O site, O(13) is bonded in a bent 120 degrees geometry to two equivalent W(1) atoms. In the sixteenth O site, O(14) is bonded in a bent 120 degrees geometry to one W(6) and one Cu(2) atom. In the seventeenth O site, O(15) is bonded in a bent 150 degrees geometry to one W(3) and one W(4) atom. Linkers: 18 c1cnccn1. Metal clusters: 18 [Cu] ,108 [W]. The MOF has largest included sphere 5.68 A, density 3.33 g/cm3, surface area 1182.23 m2/g, accessible volume 0.14 cm3/g