MgV2(CuO3)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MgO6 octahedra that share corners with three equivalent Cu(1)O6 octahedra, corners with three equivalent Cu(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra,  a faceface with one Cu(1)O6 octahedra, and  a faceface with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Cu(1)O6 octahedra, corners with six equivalent Cu(2)O6 octahedra, edges with three equivalent Mg(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and  a faceface with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Cu(2)O6 octahedra, corners with six equivalent Cu(1)O6 octahedra, edges with three equivalent Mg(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and  a faceface with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with six equivalent V(2)O6 octahedra, edges with three equivalent Cu(2)O6 octahedra,  a faceface with one Mg(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with six equivalent V(1)O6 octahedra, edges with three equivalent Cu(1)O6 octahedra,  a faceface with one Mg(1)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing OMgV2Cu2 trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the sixth O site, O(6) is bonded to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing OMgV2Cu2 trigonal bipyramids.
MgV2(CuO3)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MgO6 octahedra that share corners with three equivalent Cu(1)O6 octahedra, corners with three equivalent Cu(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra,  a faceface with one Cu(1)O6 octahedra, and  a faceface with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Mg(1)-O(1) bond length is 2.07 Å. The Mg(1)-O(2) bond length is 2.09 Å. The Mg(1)-O(3) bond length is 2.06 Å. The Mg(1)-O(4) bond length is 2.07 Å. The Mg(1)-O(5) bond length is 2.05 Å. The Mg(1)-O(6) bond length is 2.09 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Cu(1)O6 octahedra, corners with six equivalent Cu(2)O6 octahedra, edges with three equivalent Mg(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and  a faceface with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(1)-O(1) bond length is 1.86 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(4) bond length is 2.16 Å. The V(1)-O(5) bond length is 2.09 Å. The V(1)-O(6) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Cu(2)O6 octahedra, corners with six equivalent Cu(1)O6 octahedra, edges with three equivalent Mg(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and  a faceface with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(2)-O(1) bond length is 2.15 Å. The V(2)-O(2) bond length is 2.04 Å. The V(2)-O(3) bond length is 2.08 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(5) bond length is 1.94 Å. The V(2)-O(6) bond length is 1.98 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with six equivalent V(2)O6 octahedra, edges with three equivalent Cu(2)O6 octahedra,  a faceface with one Mg(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The Cu(1)-O(1) bond length is 2.37 Å. The Cu(1)-O(2) bond length is 2.33 Å. The Cu(1)-O(3) bond length is 2.41 Å. The Cu(1)-O(4) bond length is 2.22 Å. The Cu(1)-O(5) bond length is 2.14 Å. The Cu(1)-O(6) bond length is 2.18 Å. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with six equivalent V(1)O6 octahedra, edges with three equivalent Cu(1)O6 octahedra,  a faceface with one Mg(1)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The Cu(2)-O(1) bond length is 2.21 Å. The Cu(2)-O(2) bond length is 2.15 Å. The Cu(2)-O(3) bond length is 2.18 Å. The Cu(2)-O(4) bond length is 2.32 Å. The Cu(2)-O(5) bond length is 2.43 Å. The Cu(2)-O(6) bond length is 2.35 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing OMgV2Cu2 trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom. In the sixth O site, O(6) is bonded to one Mg(1), one V(1), one V(2), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing OMgV2Cu2 trigonal bipyramids.