VCuC4AsH3(NO3)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(5), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. The V(1)-O(10) bond length is 1.64 Å. The V(1)-O(11) bond length is 1.64 Å. The V(1)-O(5) bond length is 1.85 Å. The V(1)-O(8) bond length is 1.85 Å. In the second V site, V(2) is bonded to one O(12), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)N2O4 octahedra,  a cornercorner with one Cu(2)N2O4 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. The V(2)-O(12) bond length is 1.64 Å. The V(2)-O(6) bond length is 1.85 Å. The V(2)-O(7) bond length is 1.85 Å. The V(2)-O(9) bond length is 1.64 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(1), one N(3), one O(1), one O(11), one O(3), and one O(9) atom to form CuN2O4 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, and corners with two equivalent As(1)O4 tetrahedra. The Cu(1)-N(1) bond length is 2.07 Å. The Cu(1)-N(3) bond length is 2.03 Å. The Cu(1)-O(1) bond length is 1.95 Å. The Cu(1)-O(11) bond length is 2.41 Å. The Cu(1)-O(3) bond length is 1.96 Å. The Cu(1)-O(9) bond length is 2.34 Å. In the second Cu site, Cu(2) is bonded to one N(2), one N(4), one O(10), one O(12), one O(2), and one O(4) atom to form CuN2O4 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, and corners with two equivalent As(2)O4 tetrahedra. The Cu(2)-N(2) bond length is 2.07 Å. The Cu(2)-N(4) bond length is 2.03 Å. The Cu(2)-O(10) bond length is 2.34 Å. The Cu(2)-O(12) bond length is 2.42 Å. The Cu(2)-O(2) bond length is 1.95 Å. The Cu(2)-O(4) bond length is 1.95 Å. There are seven inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(1), one N(1), and one N(3) atom. The C(1)-C(1) bond length is 1.45 Å. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(3) bond length is 1.33 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(2), one N(2), and one N(4) atom. The C(2)-C(2) bond length is 1.45 Å. The C(2)-N(2) bond length is 1.34 Å. The C(2)-N(4) bond length is 1.33 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(5,6); one N(3); and one H(1,2) atom. The C(3)-C(5,6) bond length is 1.39 Å. The C(3)-N(3) bond length is 1.34 Å. The C(3)-H(1,2) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(5,6); one N(4); and one H(1,2) atom. The C(4)-C(5,6) bond length is 1.39 Å. The C(4)-N(4) bond length is 1.34 Å. The C(4)-H(1,2) bond length is 1.09 Å. In the fifth C site, C(5,6) is bonded in a distorted single-bond geometry to one C(3) and one H(3) atom. The C(5,6)-H(3) bond length is 1.09 Å. In the sixth C site, C(7) is bonded in a distorted bent 120 degrees geometry to one N(1) and one H(5,6) atom. The C(7)-N(1) bond length is 1.34 Å. The C(7)-H(5,6) bond length is 1.09 Å. In the seventh C site, C(8) is bonded in a distorted bent 120 degrees geometry to one N(2) and one H(5,6) atom. The C(8)-N(2) bond length is 1.34 Å. The C(8)-H(5,6) bond length is 1.09 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(1)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-54°. The As(1)-O(1) bond length is 1.70 Å. The As(1)-O(3) bond length is 1.70 Å. The As(1)-O(5) bond length is 1.75 Å. The As(1)-O(7) bond length is 1.76 Å. In the second As site, As(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form AsO4 tetrahedra that share corners with two equivalent Cu(2)N2O4 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-54°. The As(2)-O(2) bond length is 1.70 Å. The As(2)-O(4) bond length is 1.70 Å. The As(2)-O(6) bond length is 1.75 Å. The As(2)-O(8) bond length is 1.76 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(7) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(2), and one C(8) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(3) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Cu(2), one C(2), and one C(4) atom. There are four inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(5,6) atom. In the third H site, H(4) is bonded in a single-bond geometry to one C(5,6) atom. The H(4)-C(5,6) bond length is 1.09 Å. In the fourth H site, H(5,6) is bonded in a single-bond geometry to one C(7) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(1) and one As(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(2) and one As(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Cu(1) and one As(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(2) and one As(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one As(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(2) and one As(1) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one V(1) and one As(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one V(2) and one Cu(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Cu(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Cu(1) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one V(2) and one Cu(2) atom. Linkers: 2 c1cnc(-c2ncccn2)nc1. Metal clusters: 4 [V] ,4 [Cu]. The MOF has largest included sphere 2.70 A, density 2.78 g/cm3, surface area 2255.76 m2/g, accessible volume 0.08 cm3/g