V5Zn3C6N9H6O10 crystallizes in the orthorhombic Pbcn space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(2), one O(5), one O(7), and one O(9) atom to form distorted VO5 square pyramids that share  a cornercorner with one V(2)O5 square pyramid,  a cornercorner with one Zn(2)N3O trigonal pyramid,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(2)O5 square pyramid, and  an edgeedge with one V(4)O5 square pyramid. The V(1)-O(10) bond length is 1.86 Å. The V(1)-O(2) bond length is 2.04 Å. The V(1)-O(5) bond length is 1.98 Å. The V(1)-O(7) bond length is 2.25 Å. The V(1)-O(9) bond length is 1.79 Å. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO5 square pyramids that share  a cornercorner with one V(1)O5 square pyramid,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(1)O5 square pyramid, and  an edgeedge with one V(4)O5 square pyramid. The V(2)-O(2) bond length is 1.99 Å. The V(2)-O(5) bond length is 2.01 Å. The V(2)-O(6) bond length is 1.83 Å. The V(2)-O(7) bond length is 2.27 Å. The V(2)-O(8) bond length is 1.83 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(6), one O(7), and one O(9) atom. The V(3)-O(3) bond length is 2.06 Å. The V(3)-O(4) bond length is 1.82 Å. The V(3)-O(6) bond length is 1.87 Å. The V(3)-O(7) bond length is 2.30 Å. The V(3)-O(9) bond length is 1.91 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(7), and one O(8) atom to form distorted VO5 square pyramids that share  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Zn(2)N3O trigonal pyramid,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(1)O5 square pyramid, and  an edgeedge with one V(2)O5 square pyramid. The corner-sharing octahedral tilt angles are 9°. The V(4)-O(1) bond length is 2.04 Å. The V(4)-O(10) bond length is 1.92 Å. The V(4)-O(4) bond length is 1.83 Å. The V(4)-O(7) bond length is 2.31 Å. The V(4)-O(8) bond length is 1.86 Å. In the fifth V site, V(5) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form distorted VO6 octahedra that share corners with two equivalent V(4)O5 square pyramids,  an edgeedge with one V(6)O6 octahedra, edges with two equivalent V(1)O5 square pyramids, and edges with two equivalent V(2)O5 square pyramids. Both V(5)-O(3) bond lengths are 1.69 Å. Both V(5)-O(5) bond lengths are 1.94 Å. Both V(5)-O(7) bond lengths are 2.12 Å. In the sixth V site, V(6) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(7) atoms to form distorted VO6 octahedra that share  an edgeedge with one V(5)O6 octahedra, edges with two equivalent V(1)O5 square pyramids, edges with two equivalent V(2)O5 square pyramids, and edges with two equivalent V(4)O5 square pyramids. Both V(6)-O(1) bond lengths are 1.69 Å. Both V(6)-O(2) bond lengths are 1.93 Å. Both V(6)-O(7) bond lengths are 2.11 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a trigonal non-coplanar geometry to one N(1), one N(2), and one N(9) atom. The Zn(1)-N(1) bond length is 1.98 Å. The Zn(1)-N(2) bond length is 1.99 Å. The Zn(1)-N(9) bond length is 1.99 Å. In the second Zn site, Zn(2) is bonded to one N(3), one N(4), one N(7), and one O(10) atom to form ZnN3O trigonal pyramids that share  a cornercorner with one V(1)O5 square pyramid and  a cornercorner with one V(4)O5 square pyramid. The Zn(2)-N(3) bond length is 2.03 Å. The Zn(2)-N(4) bond length is 2.02 Å. The Zn(2)-N(7) bond length is 2.10 Å. The Zn(2)-O(10) bond length is 1.98 Å. In the third Zn site, Zn(3) is bonded in a distorted T-shaped geometry to one N(5), one N(6), and one N(8) atom. The Zn(3)-N(5) bond length is 2.16 Å. The Zn(3)-N(6) bond length is 2.12 Å. The Zn(3)-N(8) bond length is 2.14 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(2), one N(3), and one H(1) atom. The C(1)-N(2) bond length is 1.34 Å. The C(1)-N(3) bond length is 1.30 Å. The C(1)-H(1) bond length is 0.95 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(7), and one H(2) atom. The C(2)-N(1) bond length is 1.34 Å. The C(2)-N(7) bond length is 1.31 Å. The C(2)-H(2) bond length is 0.95 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(2), one N(5), and one H(3) atom. The C(3)-N(2) bond length is 1.35 Å. The C(3)-N(5) bond length is 1.31 Å. The C(3)-H(3) bond length is 0.95 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(8), one N(9), and one H(4) atom. The C(4)-N(8) bond length is 1.31 Å. The C(4)-N(9) bond length is 1.35 Å. The C(4)-H(4) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one N(1), one N(6), and one H(5) atom. The C(5)-N(1) bond length is 1.35 Å. The C(5)-N(6) bond length is 1.32 Å. The C(5)-H(5) bond length is 0.95 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one N(4), one N(9), and one H(6) atom. The C(6)-N(4) bond length is 1.31 Å. The C(6)-N(9) bond length is 1.34 Å. The C(6)-H(6) bond length is 0.95 Å. There are nine inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(2), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Zn(1), one C(1), and one C(3) atom. In the third N site, N(3) is bonded in a 3-coordinate geometry to one Zn(2), one C(1), and one N(5) atom. The N(3)-N(5) bond length is 1.38 Å. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one Zn(2), one C(6), and one N(8) atom. The N(4)-N(8) bond length is 1.37 Å. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Zn(3), one C(3), and one N(3) atom. In the sixth N site, N(6) is bonded in a distorted trigonal planar geometry to one Zn(3), one C(5), and one N(7) atom. The N(6)-N(7) bond length is 1.38 Å. In the seventh N site, N(7) is bonded in a distorted trigonal planar geometry to one Zn(2), one C(2), and one N(6) atom. In the eighth N site, N(8) is bonded in a distorted trigonal planar geometry to one Zn(3), one C(4), and one N(4) atom. In the ninth N site, N(9) is bonded in a trigonal planar geometry to one Zn(1), one C(4), and one C(6) atom. There are six 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. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(6) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one V(4) and one V(6) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one V(3) and one V(5) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(3) and one V(4) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(5) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the seventh O site, O(7) is bonded to one V(1), one V(2), one V(3), one V(4), one V(5), and one V(6) atom to form edge-sharing OV6 octahedra. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(2) and one V(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one V(1), one V(4), and one Zn(2) atom. Linkers: 8 c1nncn1[Zn](n1cnnc1)n1cnnc1. Metal clusters: 2 N1=N[Zn]2N=N[Zn]1N=N2.N1=N[Zn]2N=N[Zn]1N=N2.O1[V]2O[V@]34O[V]5O[V]678(O[V]9O[V@@]%10%11O[V](O[V]1(O6)(O7)(O3)O%10)O[V@@](O9)(O8)O%11)O[V@](O5)(O2)O4 ,2 N1=N[Zn]2N=N[Zn]1N=N2.N1=N[Zn]2N=N[Zn]1N=N2.O1[V]2O[V@]34O[V]5O[V]678(O[V]9O[V@@]%10%11O[V](O[V]1(O6)(O7)(O3)O%10)O[V@@](O9)(O8)O%11)O[V@@](O2)(O5)O4. The MOF has largest included sphere 6.53 A, density 1.41 g/cm3, surface area 2626.29 m2/g, accessible volume 0.37 cm3/g