Li3MgV8O16 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(7) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. In the second Li site, Li(2) is bonded to one O(6) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. Mg(1) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form MgO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. In the third V site, V(3) is bonded to one O(8) and three equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. In the fourth V site, V(4) is bonded to one O(6), one O(8), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(3) and three equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form corner-sharing OLiV3 tetrahedra. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(3), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mg(1), and two equivalent V(4) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2) and three equivalent V(4) atoms. In the seventh O site, O(7) is bonded to one Li(1), one V(2), and two equivalent V(4) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one V(3) and three equivalent V(4) atoms.
Li3MgV8O16 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(7) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. The Li(1)-O(3) bond length is 2.05 Å. All Li(1)-O(7) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to one O(6) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. The Li(2)-O(6) bond length is 1.89 Å. All Li(2)-O(1) bond lengths are 1.92 Å. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(3)-O(2) bond length is 2.05 Å. All Li(3)-O(5) bond lengths are 1.93 Å. Mg(1) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form MgO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. All Mg(1)-O(4) bond lengths are 2.09 Å. All Mg(1)-O(5) bond lengths are 2.07 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.00 Å. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(4) bond lengths are 2.09 Å. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. All V(2)-O(1) bond lengths are 2.01 Å. All V(2)-O(7) bond lengths are 1.98 Å. In the third V site, V(3) is bonded to one O(8) and three equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. The V(3)-O(8) bond length is 1.91 Å. All V(3)-O(4) bond lengths are 1.89 Å. In the fourth V site, V(4) is bonded to one O(6), one O(8), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The V(4)-O(6) bond length is 1.96 Å. The V(4)-O(8) bond length is 2.14 Å. Both V(4)-O(5) bond lengths are 1.95 Å. Both V(4)-O(7) bond lengths are 1.99 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(3) and three equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form corner-sharing OLiV3 tetrahedra. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(3), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mg(1), and two equivalent V(4) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2) and three equivalent V(4) atoms. In the seventh O site, O(7) is bonded to one Li(1), one V(2), and two equivalent V(4) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one V(3) and three equivalent V(4) atoms.