W21Ni12C6P2H33(N3O17)4(CH3)6(CH)3(CH2)3 crystallizes in the cubic P2_13 space group. The structure consists of twelve 02329_fluka molecules, twelve 02329_fluka molecules, and twenty-four 02329_fluka molecules inside a W21Ni12C6P2H33(N3O17)4 framework. In the W21Ni12C6P2H33(N3O17)4 framework, there are seven inequivalent W sites. In the first W site, W(1) is bonded in a 5-coordinate geometry to one O(1), one O(14), one O(18), one O(6), and one O(7) atom. The W(1)-O(1) bond length is 1.81 Å. The W(1)-O(14) bond length is 1.91 Å. The W(1)-O(18) bond length is 2.01 Å. The W(1)-O(6) bond length is 2.40 Å. The W(1)-O(7) bond length is 1.93 Å. In the second W site, W(2) is bonded in a 3-coordinate geometry to one O(18), one O(20), one O(6), and two equivalent O(12) atoms. The W(2)-O(18) bond length is 1.89 Å. The W(2)-O(20) bond length is 1.89 Å. The W(2)-O(6) bond length is 2.47 Å. There is one shorter (1.91 Å) and one longer (1.92 Å) W(2)-O(12) bond length. In the third W site, W(3) is bonded in a 5-coordinate geometry to one O(14), one O(20), one O(5), one O(6), and one O(7) atom. The W(3)-O(14) bond length is 1.93 Å. The W(3)-O(20) bond length is 2.01 Å. The W(3)-O(5) bond length is 1.80 Å. The W(3)-O(6) bond length is 2.41 Å. The W(3)-O(7) bond length is 1.91 Å. In the fourth W site, W(4) is bonded to one O(16), one O(17), one O(22), and two equivalent O(11) atoms to form distorted WO5 square pyramids that share corners with two equivalent W(4)O5 square pyramids and  a cornercorner with one P(2)O4 tetrahedra. The W(4)-O(16) bond length is 1.85 Å. The W(4)-O(17) bond length is 1.90 Å. The W(4)-O(22) bond length is 2.47 Å. There is one shorter (1.89 Å) and one longer (1.95 Å) W(4)-O(11) bond length. In the fifth W site, W(5) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(16), one O(22), and one O(9) atom. The W(5)-O(10) bond length is 1.88 Å. The W(5)-O(13) bond length is 1.96 Å. The W(5)-O(16) bond length is 2.01 Å. The W(5)-O(22) bond length is 2.45 Å. The W(5)-O(9) bond length is 1.81 Å. In the sixth W site, W(6) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(17), one O(22), and one O(8) atom. The W(6)-O(10) bond length is 1.96 Å. The W(6)-O(13) bond length is 1.89 Å. The W(6)-O(17) bond length is 1.99 Å. The W(6)-O(22) bond length is 2.41 Å. The W(6)-O(8) bond length is 1.81 Å. In the seventh W site, W(7) is bonded to one O(15), one O(19), one O(21), and one O(3) atom to form WO4 tetrahedra that share  a cornercorner with one Ni(2)N2O4 octahedra,  a cornercorner with one Ni(3)N2O4 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. The W(7)-O(15) bond length is 1.78 Å. The W(7)-O(19) bond length is 1.75 Å. The W(7)-O(21) bond length is 1.78 Å. The W(7)-O(3) bond length is 1.77 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(23), one O(3), one O(5), and two equivalent O(4) atoms to form NiO6 octahedra that share  a cornercorner with one W(7)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, edges with two equivalent Ni(2)N2O4 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The Ni(1)-O(1) bond length is 2.07 Å. The Ni(1)-O(23) bond length is 2.16 Å. The Ni(1)-O(3) bond length is 2.02 Å. The Ni(1)-O(5) bond length is 2.09 Å. There is one shorter (2.01 Å) and one longer (2.02 Å) Ni(1)-O(4) bond length. In the second Ni site, Ni(2) is bonded to one N(1), one N(2), one O(1), one O(21), one O(4), and one O(5) atom to form NiN2O4 octahedra that share  a cornercorner with one W(7)O4 tetrahedra and edges with two equivalent Ni(1)O6 octahedra. The Ni(2)-N(1) bond length is 2.09 Å. The Ni(2)-N(2) bond length is 2.06 Å. The Ni(2)-O(1) bond length is 2.15 Å. The Ni(2)-O(21) bond length is 2.10 Å. The Ni(2)-O(4) bond length is 2.03 Å. The Ni(2)-O(5) bond length is 2.13 Å. In the third Ni site, Ni(3) is bonded to one N(3), one N(4), one O(15), one O(2), one O(8), and one O(9) atom to form NiN2O4 octahedra that share  a cornercorner with one W(7)O4 tetrahedra and edges with two equivalent Ni(4)O6 octahedra. The Ni(3)-N(3) bond length is 2.05 Å. The Ni(3)-N(4) bond length is 2.09 Å. The Ni(3)-O(15) bond length is 2.09 Å. The Ni(3)-O(2) bond length is 2.06 Å. The Ni(3)-O(8) bond length is 2.12 Å. The Ni(3)-O(9) bond length is 2.13 Å. In the fourth Ni site, Ni(4) is bonded to one O(19), one O(24), one O(8), one O(9), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one W(7)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, edges with two equivalent Ni(3)N2O4 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The Ni(4)-O(19) bond length is 2.06 Å. The Ni(4)-O(24) bond length is 2.19 Å. The Ni(4)-O(8) bond length is 2.06 Å. The Ni(4)-O(9) bond length is 2.07 Å. There is one shorter (2.01 Å) and one longer (2.03 Å) Ni(4)-O(2) bond length. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 2-coordinate geometry to one N(1) and one H(9) atom. The C(1)-N(1) bond length is 1.48 Å. The C(1)-H(9) bond length is 0.98 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one N(2) and two equivalent H(10,11) atoms. The C(2)-N(2) bond length is 1.47 Å. Both C(2)-H(10,11) bond lengths are 0.97 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(23) and three equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. The P(1)-O(23) bond length is 1.57 Å. All P(1)-O(6) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(24) and three equivalent O(22) atoms to form PO4 tetrahedra that share corners with three equivalent Ni(4)O6 octahedra and corners with three equivalent W(4)O5 square pyramids. The corner-sharing octahedral tilt angles are 56°. The P(2)-O(24) bond length is 1.54 Å. All P(2)-O(22) bond lengths are 1.56 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 2-coordinate geometry to one Ni(2); one C(1); and two equivalent H(1,2) atoms. Both N(1)-H(1,2) bond lengths are 0.90 Å. In the second N site, N(2) is bonded in a 2-coordinate geometry to one Ni(2), one C(2), one H(3), and one H(4) atom. The N(2)-H(3) bond length is 0.90 Å. The N(2)-H(4) bond length is 0.90 Å. In the third N site, N(3) is bonded in a distorted water-like geometry to one Ni(3) and two equivalent H(5,6) atoms. Both N(3)-H(5,6) bond lengths are 0.90 Å. In the fourth N site, N(4) is bonded in a distorted water-like geometry to one Ni(3), one H(7), and one H(8) atom. The N(4)-H(7) bond length is 0.90 Å. The N(4)-H(8) bond length is 0.90 Å. There are eight inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one N(1) atom. In the second H site, H(3) is bonded in a single-bond geometry to one N(2) atom. In the third H site, H(4) is bonded in a single-bond geometry to one N(2) atom. In the fourth H site, H(5,6) is bonded in a single-bond geometry to one N(3) atom. In the fifth H site, H(7) is bonded in a single-bond geometry to one N(4) atom. In the sixth H site, H(8) is bonded in a single-bond geometry to one N(4) atom. In the seventh H site, H(9) is bonded in a single-bond geometry to one C(1) atom. In the eighth H site, H(10,11) is bonded in a single-bond geometry to one C(2) atom. There are twenty-four inequivalent O sites. In the first O site, O(10) is bonded in a bent 120 degrees geometry to one W(5) and one W(6) atom. In the second O site, O(13) is bonded in a bent 150 degrees geometry to one W(5) and one W(6) atom. In the third O site, O(14) is bonded in a bent 120 degrees geometry to one W(1) and one W(3) atom. In the fourth O site, O(15) is bonded in a bent 120 degrees geometry to one W(7) and one Ni(3) atom. In the fifth O site, O(16) is bonded in a bent 120 degrees geometry to one W(4) and one W(5) atom. In the sixth O site, O(17) is bonded in a bent 120 degrees geometry to one W(4) and one W(6) atom. In the seventh O site, O(18) is bonded in a bent 120 degrees geometry to one W(1) and one W(2) atom. In the eighth O site, O(19) is bonded in a bent 120 degrees geometry to one W(7) and one Ni(4) atom. In the ninth O site, O(20) is bonded in a bent 120 degrees geometry to one W(2) and one W(3) atom. In the tenth O site, O(21) is bonded in a bent 120 degrees geometry to one W(7) and one Ni(2) atom. In the eleventh O site, O(22) is bonded in a single-bond geometry to one W(4), one W(5), one W(6), and one P(2) atom. In the twelfth O site, O(23) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ni(1) and one P(1) atom. In the thirteenth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ni(4) and one P(2) atom. In the fourteenth O site, O(9) is bonded in a distorted trigonal planar geometry to one W(5), one Ni(3), and one Ni(4) atom. In the fifteenth O site, O(1) is bonded in a distorted trigonal planar geometry to one W(1), one Ni(1), and one Ni(2) atom. In the sixteenth O site, O(2) is bonded in a trigonal non-coplanar geometry to one Ni(3) and two equivalent Ni(4) atoms. In the seventeenth O site, O(3) is bonded in a bent 120 degrees geometry to one W(7) and one Ni(1) atom. In the eighteenth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Ni(2) and two equivalent Ni(1) atoms. In the nineteenth O site, O(5) is bonded in a distorted trigonal planar geometry to one W(3), one Ni(1), and one Ni(2) atom. In the twentieth O site, O(6) is bonded in a distorted single-bond geometry to one W(1), one W(2), one W(3), and one P(1) atom. In the twenty-first O site, O(7) is bonded in a bent 150 degrees geometry to one W(1) and one W(3) atom. In the twenty-second O site, O(8) is bonded in a distorted trigonal planar geometry to one W(6), one Ni(3), and one Ni(4) atom. In the twenty-third O site, O(11) is bonded in a bent 150 degrees geometry to two equivalent W(4) atoms. In the twenty-fourth O site, O(12) is bonded in a bent 150 degrees geometry to two equivalent W(2) atoms. Linkers: 8 [O]P([O])([O])=O. Metal clusters: 48 [Ni] ,84 [W]. The MOF has largest included sphere 8.12 A, density 2.64 g/cm3, surface area 1365.30 m2/g, accessible volume 0.23 cm3/g