Li4V3Cu(PO4)4 is Spinel-derived structured and crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), one O(6), one O(7), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-68°. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(3) atom to form LiO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-72°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-68°. In the second V site, V(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-65°. In the third V site, V(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-66°. Cu(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-72°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cu(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Cu(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(3), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one Cu(1), and one P(4) atom.
Li4V3Cu(PO4)4 is Spinel-derived structured and crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), one O(6), one O(7), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-68°. The Li(1)-O(4) bond length is 2.13 Å. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.13 Å. The Li(1)-O(7) bond length is 2.09 Å. The Li(1)-O(8) bond length is 2.18 Å. The Li(1)-O(9) bond length is 2.27 Å. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(3) atom to form LiO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-72°. The Li(2)-O(1) bond length is 2.14 Å. The Li(2)-O(10) bond length is 2.24 Å. The Li(2)-O(11) bond length is 2.19 Å. The Li(2)-O(12) bond length is 2.11 Å. The Li(2)-O(2) bond length is 2.18 Å. The Li(2)-O(3) bond length is 2.20 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-68°. The V(1)-O(3) bond length is 2.22 Å. The V(1)-O(7) bond length is 2.17 Å. Both V(1)-O(11) bond lengths are 2.21 Å. Both V(1)-O(5) bond lengths are 2.16 Å. In the second V site, V(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-65°. The V(2)-O(10) bond length is 2.19 Å. The V(2)-O(6) bond length is 2.11 Å. Both V(2)-O(2) bond lengths are 2.14 Å. Both V(2)-O(8) bond lengths are 2.08 Å. In the third V site, V(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-66°. The V(3)-O(1) bond length is 2.17 Å. The V(3)-O(9) bond length is 2.20 Å. Both V(3)-O(11) bond lengths are 2.16 Å. Both V(3)-O(5) bond lengths are 2.22 Å. Cu(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-72°. The Cu(1)-O(12) bond length is 2.09 Å. The Cu(1)-O(4) bond length is 2.23 Å. Both Cu(1)-O(2) bond lengths are 2.10 Å. Both Cu(1)-O(8) bond lengths are 2.42 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(10) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.53 Å. Both P(2)-O(5) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. The P(3)-O(4) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.56 Å. Both P(3)-O(8) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(3) bond length is 1.53 Å. Both P(4)-O(11) bond lengths are 1.58 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Cu(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Cu(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(3), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one Cu(1), and one P(4) atom.