Li6V3W3O16 is Hausmannite-derived structured and crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent W(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(14), one O(16), one O(5), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(4), and one O(6) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom. In the sixth Li site, Li(6) is bonded to one O(13), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and corners with two equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-62°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent W(2)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent W(3)O6 octahedra. In the third V site, V(3) is bonded to one O(10), one O(12), one O(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent W(3)O6 octahedra. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent W(2)O6 octahedra. In the second W site, W(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. In the third W site, W(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form WO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one V(2), and one W(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(6), one W(1), and one W(2) atom to form distorted corner-sharing OLi2W2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one W(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one W(1), and one W(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(2), one V(3), and one W(3) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one W(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one V(1), and one W(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one V(1), and one W(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one W(1), and one W(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(4), one V(2), and one V(3) atom to form distorted OLi2V2 trigonal pyramids that share  a cornercorner with one O(11)Li2VW tetrahedra,  a cornercorner with one O(12)Li2VW tetrahedra, and  a cornercorner with one O(2)Li2W2 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(2), one Li(5), one V(2), and one W(3) atom to form distorted OLi2VW tetrahedra that share  a cornercorner with one O(12)Li2VW tetrahedra,  a cornercorner with one O(10)Li2V2 trigonal pyramid, and  an edgeedge with one O(12)Li2VW tetrahedra. In the twelfth O site, O(12) is bonded to one Li(2), one Li(5), one V(3), and one W(3) atom to form distorted OLi2VW tetrahedra that share  a cornercorner with one O(11)Li2VW tetrahedra,  a cornercorner with one O(10)Li2V2 trigonal pyramid, and  an edgeedge with one O(11)Li2VW tetrahedra. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(6), one V(2), one V(3), and one W(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(1), and one W(1) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), one V(2), and one V(3) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(1), and one W(2) atom.
Li6V3W3O16 is Hausmannite-derived structured and crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.14 Å. The Li(1)-O(10) bond length is 2.18 Å. The Li(1)-O(2) bond length is 2.45 Å. The Li(1)-O(6) bond length is 2.13 Å. The Li(1)-O(7) bond length is 2.59 Å. The Li(1)-O(8) bond length is 2.58 Å. In the second Li site, Li(2) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent W(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. The Li(2)-O(11) bond length is 2.04 Å. The Li(2)-O(12) bond length is 2.03 Å. The Li(2)-O(15) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.13 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(14), one O(16), one O(5), and one O(9) atom. The Li(3)-O(14) bond length is 1.96 Å. The Li(3)-O(16) bond length is 1.97 Å. The Li(3)-O(5) bond length is 1.82 Å. The Li(3)-O(9) bond length is 1.96 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(4), and one O(6) atom. The Li(4)-O(1) bond length is 1.96 Å. The Li(4)-O(10) bond length is 1.92 Å. The Li(4)-O(4) bond length is 1.82 Å. The Li(4)-O(6) bond length is 1.97 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom. The Li(5)-O(11) bond length is 2.47 Å. The Li(5)-O(12) bond length is 2.47 Å. The Li(5)-O(14) bond length is 2.17 Å. The Li(5)-O(15) bond length is 2.59 Å. The Li(5)-O(16) bond length is 2.17 Å. The Li(5)-O(9) bond length is 2.10 Å. In the sixth Li site, Li(6) is bonded to one O(13), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one W(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and corners with two equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-62°. The Li(6)-O(13) bond length is 2.10 Å. The Li(6)-O(2) bond length is 2.01 Å. The Li(6)-O(7) bond length is 2.04 Å. The Li(6)-O(8) bond length is 2.03 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent W(2)O6 octahedra. The V(1)-O(14) bond length is 2.04 Å. The V(1)-O(16) bond length is 2.04 Å. The V(1)-O(3) bond length is 2.13 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(7) bond length is 2.04 Å. The V(1)-O(8) bond length is 2.03 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent W(3)O6 octahedra. The V(2)-O(1) bond length is 2.05 Å. The V(2)-O(10) bond length is 1.89 Å. The V(2)-O(11) bond length is 2.07 Å. The V(2)-O(13) bond length is 2.09 Å. The V(2)-O(15) bond length is 1.84 Å. The V(2)-O(5) bond length is 2.06 Å. In the third V site, V(3) is bonded to one O(10), one O(12), one O(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent W(3)O6 octahedra. The V(3)-O(10) bond length is 2.03 Å. The V(3)-O(12) bond length is 2.04 Å. The V(3)-O(13) bond length is 2.15 Å. The V(3)-O(15) bond length is 2.03 Å. The V(3)-O(5) bond length is 2.12 Å. The V(3)-O(6) bond length is 2.04 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent W(2)O6 octahedra. The W(1)-O(14) bond length is 1.97 Å. The W(1)-O(2) bond length is 2.05 Å. The W(1)-O(3) bond length is 2.07 Å. The W(1)-O(4) bond length is 2.07 Å. The W(1)-O(7) bond length is 1.93 Å. The W(1)-O(9) bond length is 2.06 Å. In the second W site, W(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. The W(2)-O(16) bond length is 1.97 Å. The W(2)-O(2) bond length is 2.05 Å. The W(2)-O(3) bond length is 2.08 Å. The W(2)-O(4) bond length is 2.07 Å. The W(2)-O(8) bond length is 1.92 Å. The W(2)-O(9) bond length is 2.06 Å. In the third W site, W(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form WO6 octahedra that share  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The W(3)-O(1) bond length is 1.97 Å. The W(3)-O(11) bond length is 1.92 Å. The W(3)-O(12) bond length is 1.94 Å. The W(3)-O(13) bond length is 1.98 Å. The W(3)-O(5) bond length is 2.00 Å. The W(3)-O(6) bond length is 1.97 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one V(2), and one W(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(6), one W(1), and one W(2) atom to form distorted corner-sharing OLi2W2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one W(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one W(1), and one W(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(2), one V(3), and one W(3) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one W(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one V(1), and one W(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one V(1), and one W(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one W(1), and one W(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(4), one V(2), and one V(3) atom to form distorted OLi2V2 trigonal pyramids that share  a cornercorner with one O(11)Li2VW tetrahedra,  a cornercorner with one O(12)Li2VW tetrahedra, and  a cornercorner with one O(2)Li2W2 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(2), one Li(5), one V(2), and one W(3) atom to form distorted OLi2VW tetrahedra that share  a cornercorner with one O(12)Li2VW tetrahedra,  a cornercorner with one O(10)Li2V2 trigonal pyramid, and  an edgeedge with one O(12)Li2VW tetrahedra. In the twelfth O site, O(12) is bonded to one Li(2), one Li(5), one V(3), and one W(3) atom to form distorted OLi2VW tetrahedra that share  a cornercorner with one O(11)Li2VW tetrahedra,  a cornercorner with one O(10)Li2V2 trigonal pyramid, and  an edgeedge with one O(11)Li2VW tetrahedra. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(6), one V(2), one V(3), and one W(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(1), and one W(1) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), one V(2), and one V(3) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(1), and one W(2) atom.