LiV4CuO12 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(5), and one O(6) atom to form distorted LiO6 pentagonal pyramids that share  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  a faceface with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form distorted VO6 octahedra that share corners with four equivalent V(4)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 30-46°. In the second V site, V(2) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 33-44°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom. In the fourth V site, V(4) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O6 pentagonal pyramid, and  a faceface with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 30-57°. Cu(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form CuO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Cu(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Cu(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Cu(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom.
LiV4CuO12 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(5), and one O(6) atom to form distorted LiO6 pentagonal pyramids that share  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  a faceface with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. The Li(1)-O(10) bond length is 2.01 Å. The Li(1)-O(12) bond length is 2.05 Å. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(5) bond length is 2.12 Å. The Li(1)-O(6) bond length is 2.18 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form distorted VO6 octahedra that share corners with four equivalent V(4)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 30-46°. The V(1)-O(10) bond length is 2.23 Å. The V(1)-O(11) bond length is 1.84 Å. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(3) bond length is 1.70 Å. The V(1)-O(5) bond length is 1.71 Å. The V(1)-O(8) bond length is 2.20 Å. In the second V site, V(2) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 33-44°. The V(2)-O(1) bond length is 1.79 Å. The V(2)-O(12) bond length is 2.08 Å. The V(2)-O(4) bond length is 2.10 Å. The V(2)-O(6) bond length is 1.68 Å. The V(2)-O(7) bond length is 2.20 Å. The V(2)-O(9) bond length is 1.79 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom. The V(3)-O(1) bond length is 2.19 Å. The V(3)-O(11) bond length is 2.15 Å. The V(3)-O(12) bond length is 1.72 Å. The V(3)-O(2) bond length is 1.74 Å. The V(3)-O(4) bond length is 1.79 Å. The V(3)-O(9) bond length is 2.16 Å. In the fourth V site, V(4) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O6 pentagonal pyramid, and  a faceface with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 30-57°. The V(4)-O(10) bond length is 1.70 Å. The V(4)-O(3) bond length is 2.14 Å. The V(4)-O(5) bond length is 2.10 Å. The V(4)-O(6) bond length is 2.14 Å. The V(4)-O(7) bond length is 1.77 Å. The V(4)-O(8) bond length is 1.79 Å. Cu(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form CuO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. The Cu(1)-O(1) bond length is 1.99 Å. The Cu(1)-O(11) bond length is 1.96 Å. The Cu(1)-O(4) bond length is 2.04 Å. The Cu(1)-O(7) bond length is 1.99 Å. The Cu(1)-O(8) bond length is 1.99 Å. The Cu(1)-O(9) bond length is 2.00 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Cu(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Cu(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Cu(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom.