V6Mo12Ni2C40PH48(N8O17)2 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(5) and four equivalent O(4) atoms. The V(1)-O(5) bond length is 1.63 Å. All V(1)-O(4) bond lengths are 1.92 Å. In the second V site, V(2) is bonded in a distorted trigonal pyramidal geometry to two equivalent O(2) and two equivalent O(3) atoms. Both V(2)-O(2) bond lengths are 2.04 Å. Both V(2)-O(3) bond lengths are 2.08 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), and two equivalent O(4) atoms. The Mo(1)-O(2) bond length is 1.82 Å. The Mo(1)-O(3) bond length is 1.79 Å. There is one shorter (2.02 Å) and one longer (2.05 Å) Mo(1)-O(4) bond length. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Mo(2)-O(1) bond lengths are 2.55 Å. Both Mo(2)-O(2) bond lengths are 1.92 Å. Both Mo(2)-O(3) bond lengths are 1.92 Å. Ni(1) is bonded in a square pyramidal geometry to four equivalent N(1) and one O(5) atom. All Ni(1)-N(1) bond lengths are 2.09 Å. The Ni(1)-O(5) bond length is 2.06 Å. There are five inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one C(5), and one N(1) atom. The C(1)-C(2) bond length is 1.38 Å. The C(1)-C(5) bond length is 1.50 Å. The C(1)-N(1) bond length is 1.36 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(2), and one C(3) atom. The C(2)-C(2) bond length is 1.47 Å. The C(2)-C(3) bond length is 1.37 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(2), one C(4), and one N(2) atom. The C(3)-C(4) bond length is 1.51 Å. The C(3)-N(2) bond length is 1.36 Å. In the fourth C site, C(4) is bonded in a trigonal non-coplanar geometry to one C(3), one H(1), one H(2), and one H(3) atom. The C(4)-H(1) bond length is 0.96 Å. The C(4)-H(2) bond length is 0.96 Å. The C(4)-H(3) bond length is 0.96 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(1) and three equivalent H(4,5,6) atoms. All C(5)-H(4,5,6) bond lengths are 0.96 Å. P(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. All P(1)-O(1) bond lengths are 1.53 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Ni(1), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.36 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one C(3) and one N(1) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(4,5,6) is bonded in a single-bond geometry to one C(5) atom. There are five inequivalent O sites. In the first O site, O(5) is bonded in a linear geometry to one V(1) and one Ni(1) atom. In the second O site, O(1) is bonded in a single-bond geometry to one Mo(2) and one P(1) atom. In the third O site, O(2) is bonded in a distorted T-shaped geometry to one V(2), one Mo(1), and one Mo(2) atom. In the fourth O site, O(3) is bonded in a distorted T-shaped geometry to one V(2), one Mo(1), and one Mo(2) atom. In the fifth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent Mo(1) atoms. Linkers: 5 CC1=NN=C(C)[C]1C1=C(C)[N]N=C1C ,2 C[C]1N=NC(C)=C1C1=C(C)[N]N=C1C ,1 CC1=N[N]C(C)=C1C1=C(C)[N]N=C1C. Metal clusters: 2 [Ni]O[V]123O[Mo]4O[Mo]56O[Mo](O[Mo]78O[Mo](O[Mo]9%10O[Mo](O[Mo]%11(O4)O[Mo](O5)O[V](O[Ni])(O[Mo](O6)O7)(O[Mo](O%11)O9)O[Mo](O8)O%10)O1)O2)O3.[V].[V].[V].[V]. The MOF has largest included sphere 7.87 A, density 1.74 g/cm3, surface area 2458.09 m2/g, accessible volume 0.32 cm3/g