V6Co4C20N8H12O23 crystallizes in the tetragonal I4 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Co(1)N2O4 octahedra,  a cornercorner with one Co(2)N2O4 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-35°. The V(1)-O(5) bond length is 1.65 Å. The V(1)-O(6) bond length is 1.64 Å. The V(1)-O(7) bond length is 1.79 Å. The V(1)-O(8) bond length is 1.78 Å. In the second V site, V(2) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Co(1)N2O4 octahedra,  a cornercorner with one Co(2)N2O4 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-20°. The V(2)-O(10) bond length is 1.64 Å. The V(2)-O(11) bond length is 1.82 Å. The V(2)-O(8) bond length is 1.79 Å. The V(2)-O(9) bond length is 1.63 Å. In the third V site, V(3) is bonded in a trigonal non-coplanar geometry to one O(11), one O(12), and one O(7) atom. The V(3)-O(11) bond length is 1.75 Å. The V(3)-O(12) bond length is 1.76 Å. The V(3)-O(7) bond length is 1.75 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one N(1), one N(4), one O(1), one O(10), one O(2), and one O(5) atom to form CoN2O4 octahedra that share  a cornercorner with one V(1)O4 tetrahedra and  a cornercorner with one V(2)O4 tetrahedra. The Co(1)-N(1) bond length is 2.14 Å. The Co(1)-N(4) bond length is 2.12 Å. The Co(1)-O(1) bond length is 2.09 Å. The Co(1)-O(10) bond length is 2.07 Å. The Co(1)-O(2) bond length is 2.04 Å. The Co(1)-O(5) bond length is 2.11 Å. In the second Co site, Co(2) is bonded to one N(2), one N(3), one O(3), one O(4), one O(6), and one O(9) atom to form CoN2O4 octahedra that share  a cornercorner with one V(1)O4 tetrahedra and  a cornercorner with one V(2)O4 tetrahedra. The Co(2)-N(2) bond length is 2.12 Å. The Co(2)-N(3) bond length is 2.11 Å. The Co(2)-O(3) bond length is 2.10 Å. The Co(2)-O(4) bond length is 2.05 Å. The Co(2)-O(6) bond length is 2.10 Å. The Co(2)-O(9) bond length is 2.04 Å. There are ten inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(1) atom. The C(1)-N(1) bond length is 1.33 Å. The C(1)-H(1) bond length is 0.94 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one N(2) and one H(2) atom. The C(2)-N(2) bond length is 1.35 Å. The C(2)-H(2) bond length is 0.97 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4), one N(2), and one H(3) atom. The C(3)-C(4) bond length is 1.38 Å. The C(3)-N(2) bond length is 1.35 Å. The C(3)-H(3) bond length is 1.08 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one N(1) atom. The C(4)-N(1) bond length is 1.36 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(5)-O(1) bond length is 1.26 Å. The C(5)-O(2) bond length is 1.25 Å. In the sixth C site, C(6) is bonded in a distorted water-like geometry to one N(3) and one H(4) atom. The C(6)-N(3) bond length is 1.33 Å. The C(6)-H(4) bond length is 1.11 Å. In the seventh C site, C(7) is bonded in a 2-coordinate geometry to one N(4) and one H(5) atom. The C(7)-N(4) bond length is 1.35 Å. The C(7)-H(5) bond length is 0.90 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one N(4) and one H(6) atom. The C(8)-N(4) bond length is 1.34 Å. The C(8)-H(6) bond length is 0.84 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one N(3) atom. The C(9)-N(3) bond length is 1.34 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(10)-O(3) bond length is 1.24 Å. The C(10)-O(4) bond length is 1.25 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Co(1), one C(1), and one C(4) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Co(2), one C(2), and one C(3) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Co(2), one C(6), and one C(9) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Co(1), one C(7), and one C(8) 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(6) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(1) and one C(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Co(1) and one C(5) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Co(2) and one C(10) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Co(2) and one C(10) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one Co(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one Co(2) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one V(2) and one Co(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the twelfth O site, O(12) is bonded in a linear geometry to two equivalent V(3) atoms. Linkers: 7 [O]C(=O)c1cnccn1. Metal clusters: 12 [V] ,8 [Co]. The MOF has largest included sphere 4.11 A, density 2.17 g/cm3, surface area 2751.85 m2/g, accessible volume 0.12 cm3/g