V4Cu3C4H4(NO2)6 crystallizes in the triclinic P1 space group. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(13), one O(5), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one V(5)O4 tetrahedra, and  a cornercorner with one V(8)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The V(1)-O(1) bond length is 1.78 Å. The V(1)-O(13) bond length is 1.62 Å. The V(1)-O(5) bond length is 1.78 Å. The V(1)-O(9) bond length is 1.76 Å. In the second V site, V(2) is bonded to one O(10), one O(14), one O(2), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one V(6)O4 tetrahedra, and  a cornercorner with one V(7)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The V(2)-O(10) bond length is 1.76 Å. The V(2)-O(14) bond length is 1.62 Å. The V(2)-O(2) bond length is 1.78 Å. The V(2)-O(6) bond length is 1.78 Å. In the third V site, V(3) is bonded to one O(11), one O(15), one O(3), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one V(6)O4 tetrahedra, and  a cornercorner with one V(7)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. The V(3)-O(11) bond length is 1.76 Å. The V(3)-O(15) bond length is 1.62 Å. The V(3)-O(3) bond length is 1.78 Å. The V(3)-O(7) bond length is 1.77 Å. In the fourth V site, V(4) is bonded to one O(12), one O(16), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one V(5)O4 tetrahedra, and  a cornercorner with one V(8)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. The V(4)-O(12) bond length is 1.76 Å. The V(4)-O(16) bond length is 1.62 Å. The V(4)-O(4) bond length is 1.78 Å. The V(4)-O(8) bond length is 1.77 Å. In the fifth V site, V(5) is bonded to one O(1), one O(17), one O(23), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The V(5)-O(1) bond length is 1.79 Å. The V(5)-O(17) bond length is 1.68 Å. The V(5)-O(23) bond length is 1.64 Å. The V(5)-O(8) bond length is 1.82 Å. In the sixth V site, V(6) is bonded to one O(18), one O(2), one O(24), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one V(2)O4 tetrahedra, and  a cornercorner with one V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The V(6)-O(18) bond length is 1.68 Å. The V(6)-O(2) bond length is 1.79 Å. The V(6)-O(24) bond length is 1.64 Å. The V(6)-O(7) bond length is 1.82 Å. In the seventh V site, V(7) is bonded to one O(19), one O(21), one O(3), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one V(2)O4 tetrahedra, and  a cornercorner with one V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The V(7)-O(19) bond length is 1.68 Å. The V(7)-O(21) bond length is 1.64 Å. The V(7)-O(3) bond length is 1.80 Å. The V(7)-O(6) bond length is 1.82 Å. In the eighth V site, V(8) is bonded to one O(20), one O(22), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The V(8)-O(20) bond length is 1.68 Å. The V(8)-O(22) bond length is 1.64 Å. The V(8)-O(4) bond length is 1.79 Å. The V(8)-O(5) bond length is 1.81 Å. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(5), one N(7), one O(11), one O(21), one O(23), and one O(9) atom to form distorted CuN2O4 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra,  a cornercorner with one V(5)O4 tetrahedra, and  a cornercorner with one V(7)O4 tetrahedra. The Cu(1)-N(5) bond length is 1.93 Å. The Cu(1)-N(7) bond length is 1.93 Å. The Cu(1)-O(11) bond length is 2.01 Å. The Cu(1)-O(21) bond length is 2.54 Å. The Cu(1)-O(23) bond length is 2.55 Å. The Cu(1)-O(9) bond length is 2.01 Å. In the second Cu site, Cu(2) is bonded to one N(6), one N(8), one O(10), one O(12), one O(22), and one O(24) atom to form distorted CuN2O4 octahedra that share  a cornercorner with one V(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra,  a cornercorner with one V(6)O4 tetrahedra, and  a cornercorner with one V(8)O4 tetrahedra. The Cu(2)-N(6) bond length is 1.93 Å. The Cu(2)-N(8) bond length is 1.93 Å. The Cu(2)-O(10) bond length is 2.01 Å. The Cu(2)-O(12) bond length is 2.01 Å. The Cu(2)-O(22) bond length is 2.54 Å. The Cu(2)-O(24) bond length is 2.55 Å. In the third Cu site, Cu(3) is bonded in a 5-coordinate geometry to one N(1), one N(12), one O(15), one O(20), and one O(9) atom. The Cu(3)-N(1) bond length is 1.97 Å. The Cu(3)-N(12) bond length is 1.96 Å. The Cu(3)-O(15) bond length is 2.44 Å. The Cu(3)-O(20) bond length is 1.94 Å. The Cu(3)-O(9) bond length is 2.01 Å. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one N(11), one N(2), one O(10), one O(16), and one O(19) atom. The Cu(4)-N(11) bond length is 1.96 Å. The Cu(4)-N(2) bond length is 1.96 Å. The Cu(4)-O(10) bond length is 2.01 Å. The Cu(4)-O(16) bond length is 2.44 Å. The Cu(4)-O(19) bond length is 1.94 Å. In the fifth Cu site, Cu(5) is bonded in a 5-coordinate geometry to one N(10), one N(3), one O(11), one O(13), and one O(18) atom. The Cu(5)-N(10) bond length is 1.96 Å. The Cu(5)-N(3) bond length is 1.96 Å. The Cu(5)-O(11) bond length is 2.01 Å. The Cu(5)-O(13) bond length is 2.44 Å. The Cu(5)-O(18) bond length is 1.93 Å. In the sixth Cu site, Cu(6) is bonded in a 5-coordinate geometry to one N(4), one N(9), one O(12), one O(14), and one O(17) atom. The Cu(6)-N(4) bond length is 1.97 Å. The Cu(6)-N(9) bond length is 1.96 Å. The Cu(6)-O(12) bond length is 2.01 Å. The Cu(6)-O(14) bond length is 2.44 Å. The Cu(6)-O(17) bond length is 1.93 Å. There are seven inequivalent C sites. In the first C site, C(1,4) is bonded in a trigonal planar geometry to one N(1), one N(9), and one H(1) atom. The C(1,4)-N(1) bond length is 1.33 Å. The C(1,4)-N(9) bond length is 1.36 Å. The C(1,4)-H(1) bond length is 1.08 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(10), one N(2), and one H(2) atom. The C(2)-N(10) bond length is 1.36 Å. The C(2)-N(2) bond length is 1.33 Å. The C(2)-H(2) bond length is 1.08 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(11), one N(3), and one H(3) atom. The C(3)-N(11) bond length is 1.36 Å. The C(3)-N(3) bond length is 1.33 Å. The C(3)-H(3) bond length is 1.08 Å. In the fourth C site, C(5) is bonded in a trigonal planar geometry to one N(5), one N(9), and one H(5) atom. The C(5)-N(5) bond length is 1.33 Å. The C(5)-N(9) bond length is 1.35 Å. The C(5)-H(5) bond length is 1.08 Å. In the fifth C site, C(6) is bonded in a trigonal planar geometry to one N(10), one N(6), and one H(6) atom. The C(6)-N(10) bond length is 1.35 Å. The C(6)-N(6) bond length is 1.33 Å. The C(6)-H(6) bond length is 1.08 Å. In the sixth C site, C(7) is bonded in a trigonal planar geometry to one N(11), one N(7), and one H(7) atom. The C(7)-N(11) bond length is 1.35 Å. The C(7)-N(7) bond length is 1.33 Å. The C(7)-H(7) bond length is 1.08 Å. In the seventh C site, C(8) is bonded in a trigonal planar geometry to one N(12), one N(8), and one H(8) atom. The C(8)-N(12) bond length is 1.35 Å. The C(8)-N(8) bond length is 1.33 Å. The C(8)-H(8) bond length is 1.08 Å. There are twelve inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(3); one C(1,4); and one N(5) atom. The N(1)-N(5) bond length is 1.36 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Cu(4), one C(2), and one N(6) atom. The N(2)-N(6) bond length is 1.36 Å. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Cu(5), one C(3), and one N(7) atom. The N(3)-N(7) bond length is 1.36 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(6); one C(1,4); and one N(8) atom. The N(4)-C(1,4) bond length is 1.33 Å. The N(4)-N(8) bond length is 1.36 Å. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Cu(1), one C(5), and one N(1) atom. In the sixth N site, N(6) is bonded in a 3-coordinate geometry to one Cu(2), one C(6), and one N(2) atom. In the seventh N site, N(7) is bonded in a 3-coordinate geometry to one Cu(1), one C(7), and one N(3) atom. In the eighth N site, N(8) is bonded in a 3-coordinate geometry to one Cu(2), one C(8), and one N(4) atom. In the ninth N site, N(9) is bonded in a trigonal planar geometry to one Cu(6); one C(1,4); and one C(5) atom. In the tenth N site, N(10) is bonded in a trigonal planar geometry to one Cu(5), one C(2), and one C(6) atom. In the eleventh N site, N(11) is bonded in a trigonal planar geometry to one Cu(4), one C(3), and one C(7) atom. In the twelfth N site, N(12) is bonded in a trigonal planar geometry to one Cu(3); one C(1,4); and one C(8) atom. The N(12)-C(1,4) bond length is 1.36 Å. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1,4) 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(1,4) atom. The H(4)-C(1,4) bond length is 1.08 Å. 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. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(7) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(8) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(3) and one V(7) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(4) and one V(8) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(8) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(4) and one V(5) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one V(1), one Cu(1), and one Cu(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one V(2), one Cu(2), and one Cu(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one V(3), one Cu(1), and one Cu(5) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one V(4), one Cu(2), and one Cu(6) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one V(1) and one Cu(5) atom. In the fourteenth O site, O(14) is bonded in a distorted single-bond geometry to one V(2) and one Cu(6) atom. In the fifteenth O site, O(15) is bonded in a distorted single-bond geometry to one V(3) and one Cu(3) atom. In the sixteenth O site, O(16) is bonded in a distorted single-bond geometry to one V(4) and one Cu(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(5) and one Cu(6) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(6) and one Cu(5) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(7) and one Cu(4) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one V(8) and one Cu(3) atom. In the twenty-first O site, O(21) is bonded in a distorted single-bond geometry to one V(7) and one Cu(1) atom. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to one V(8) and one Cu(2) atom. In the twenty-third O site, O(23) is bonded in a distorted single-bond geometry to one V(5) and one Cu(1) atom. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one V(6) and one Cu(2) atom. Linkers: 4 C1=NN=C[N]1. Metal clusters: 8 [V] ,6 [Cu]. The MOF has largest included sphere 2.27 A, density 2.88 g/cm3, surface area 2098.70 m2/g, accessible volume 0.06 cm3/g