Li4V2Mn3Cu3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form LiO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-66°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent Cu(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the second V site, V(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CuO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the second Cu site, Cu(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CuO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 44°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(1), one Mn(2), and one Cu(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one V(1), and two equivalent Cu(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Mn(1), and two equivalent Cu(1) atoms to form distorted OLiMnCu2 tetrahedra that share  a cornercorner with one O(12)LiMn2V tetrahedra, corners with three equivalent O(4)LiMnCu2 tetrahedra, corners with two equivalent O(9)LiMnVCu trigonal pyramids, and edges with two equivalent O(6)LiMnVCu trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(3), one Mn(1), and two equivalent Cu(1) atoms to form OLiMnCu2 tetrahedra that share corners with three equivalent O(3)LiMnCu2 tetrahedra and corners with four equivalent O(6)LiMnVCu trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Mn(2), and one Cu(2) atom to form OLiMn2Cu tetrahedra that share corners with two equivalent O(12)LiMn2V tetrahedra, corners with three equivalent O(10)LiMn2Cu tetrahedra, and corners with four equivalent O(9)LiMnVCu trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Mn(1), and one Cu(1) atom to form distorted OLiMnVCu trigonal pyramids that share  a cornercorner with one O(10)LiMn2Cu tetrahedra, corners with two equivalent O(4)LiMnCu2 tetrahedra,  a cornercorner with one O(6)LiMnVCu trigonal pyramid,  an edgeedge with one O(3)LiMnCu2 tetrahedra, and  an edgeedge with one O(6)LiMnVCu trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent Cu(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), and two equivalent Mn(2) atoms. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one Mn(2), and one Cu(2) atom to form distorted OLiMnVCu trigonal pyramids that share  a cornercorner with one O(12)LiMn2V tetrahedra,  a cornercorner with one O(3)LiMnCu2 tetrahedra, corners with two equivalent O(5)LiMn2Cu tetrahedra,  a cornercorner with one O(9)LiMnVCu trigonal pyramid,  an edgeedge with one O(10)LiMn2Cu tetrahedra,  an edgeedge with one O(12)LiMn2V tetrahedra, and  an edgeedge with one O(9)LiMnVCu trigonal pyramid. In the tenth O site, O(10) is bonded to one Li(4), two equivalent Mn(2), and one Cu(2) atom to form distorted OLiMn2Cu tetrahedra that share corners with three equivalent O(5)LiMn2Cu tetrahedra, corners with two equivalent O(6)LiMnVCu trigonal pyramids,  an edgeedge with one O(12)LiMn2V tetrahedra, and edges with two equivalent O(9)LiMnVCu trigonal pyramids. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Mn(1), and one Cu(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one V(2), and two equivalent Mn(2) atoms to form distorted OLiMn2V tetrahedra that share  a cornercorner with one O(3)LiMnCu2 tetrahedra, corners with two equivalent O(5)LiMn2Cu tetrahedra, corners with two equivalent O(9)LiMnVCu trigonal pyramids,  an edgeedge with one O(10)LiMn2Cu tetrahedra, and edges with two equivalent O(9)LiMnVCu trigonal pyramids.
Li4V2Mn3Cu3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. The Li(1)-O(12) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.04 Å. Both Li(1)-O(9) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form LiO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. The Li(2)-O(5) bond length is 1.81 Å. The Li(2)-O(7) bond length is 1.98 Å. Both Li(2)-O(11) bond lengths are 1.96 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. The Li(3)-O(4) bond length is 1.83 Å. The Li(3)-O(8) bond length is 1.96 Å. Both Li(3)-O(1) bond lengths are 2.00 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-66°. The Li(4)-O(10) bond length is 2.03 Å. The Li(4)-O(2) bond length is 1.92 Å. Both Li(4)-O(6) bond lengths are 1.95 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent Cu(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(8) bond length is 2.46 Å. Both V(1)-O(1) bond lengths are 1.83 Å. Both V(1)-O(6) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Cu(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The V(2)-O(12) bond length is 2.15 Å. The V(2)-O(7) bond length is 1.71 Å. Both V(2)-O(11) bond lengths are 1.90 Å. Both V(2)-O(9) bond lengths are 2.03 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The Mn(1)-O(3) bond length is 1.92 Å. The Mn(1)-O(4) bond length is 1.93 Å. Both Mn(1)-O(11) bond lengths are 2.08 Å. Both Mn(1)-O(6) bond lengths are 1.91 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 53°. The Mn(2)-O(1) bond length is 2.06 Å. The Mn(2)-O(10) bond length is 1.93 Å. The Mn(2)-O(12) bond length is 1.97 Å. The Mn(2)-O(5) bond length is 1.92 Å. The Mn(2)-O(8) bond length is 1.96 Å. The Mn(2)-O(9) bond length is 1.88 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CuO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Cu(1)-O(11) bond length is 2.10 Å. The Cu(1)-O(2) bond length is 2.23 Å. The Cu(1)-O(3) bond length is 1.90 Å. The Cu(1)-O(4) bond length is 1.90 Å. The Cu(1)-O(6) bond length is 2.17 Å. The Cu(1)-O(7) bond length is 2.23 Å. In the second Cu site, Cu(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CuO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 44°. The Cu(2)-O(10) bond length is 1.92 Å. The Cu(2)-O(5) bond length is 1.92 Å. Both Cu(2)-O(1) bond lengths are 2.14 Å. Both Cu(2)-O(9) bond lengths are 2.18 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(1), one Mn(2), and one Cu(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one V(1), and two equivalent Cu(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Mn(1), and two equivalent Cu(1) atoms to form distorted OLiMnCu2 tetrahedra that share  a cornercorner with one O(12)LiMn2V tetrahedra, corners with three equivalent O(4)LiMnCu2 tetrahedra, corners with two equivalent O(9)LiMnVCu trigonal pyramids, and edges with two equivalent O(6)LiMnVCu trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(3), one Mn(1), and two equivalent Cu(1) atoms to form OLiMnCu2 tetrahedra that share corners with three equivalent O(3)LiMnCu2 tetrahedra and corners with four equivalent O(6)LiMnVCu trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Mn(2), and one Cu(2) atom to form OLiMn2Cu tetrahedra that share corners with two equivalent O(12)LiMn2V tetrahedra, corners with three equivalent O(10)LiMn2Cu tetrahedra, and corners with four equivalent O(9)LiMnVCu trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Mn(1), and one Cu(1) atom to form distorted OLiMnVCu trigonal pyramids that share  a cornercorner with one O(10)LiMn2Cu tetrahedra, corners with two equivalent O(4)LiMnCu2 tetrahedra,  a cornercorner with one O(6)LiMnVCu trigonal pyramid,  an edgeedge with one O(3)LiMnCu2 tetrahedra, and  an edgeedge with one O(6)LiMnVCu trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent Cu(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), and two equivalent Mn(2) atoms. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one Mn(2), and one Cu(2) atom to form distorted OLiMnVCu trigonal pyramids that share  a cornercorner with one O(12)LiMn2V tetrahedra,  a cornercorner with one O(3)LiMnCu2 tetrahedra, corners with two equivalent O(5)LiMn2Cu tetrahedra,  a cornercorner with one O(9)LiMnVCu trigonal pyramid,  an edgeedge with one O(10)LiMn2Cu tetrahedra,  an edgeedge with one O(12)LiMn2V tetrahedra, and  an edgeedge with one O(9)LiMnVCu trigonal pyramid. In the tenth O site, O(10) is bonded to one Li(4), two equivalent Mn(2), and one Cu(2) atom to form distorted OLiMn2Cu tetrahedra that share corners with three equivalent O(5)LiMn2Cu tetrahedra, corners with two equivalent O(6)LiMnVCu trigonal pyramids,  an edgeedge with one O(12)LiMn2V tetrahedra, and edges with two equivalent O(9)LiMnVCu trigonal pyramids. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Mn(1), and one Cu(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one V(2), and two equivalent Mn(2) atoms to form distorted OLiMn2V tetrahedra that share  a cornercorner with one O(3)LiMnCu2 tetrahedra, corners with two equivalent O(5)LiMn2Cu tetrahedra, corners with two equivalent O(9)LiMnVCu trigonal pyramids,  an edgeedge with one O(10)LiMn2Cu tetrahedra, and edges with two equivalent O(9)LiMnVCu trigonal pyramids.