Li4V3Cr5O16 is Spinel-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 V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, corners with three equivalent Cr(4)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. 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 Cr(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. There are two inequivalent V sites. In the first V site, V(1) 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 VO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Cr(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are four inequivalent Cr sites. In the first Cr site, Cr(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 CrO6 octahedra that share corners with two equivalent Cr(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. In the second Cr site, Cr(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the third Cr site, Cr(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(4)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the fourth Cr site, Cr(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form CrO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. 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 Cr(2), and one Cr(3) atom. In the second O site, O(2) is bonded to one Li(4), one Cr(2), and two equivalent Cr(1) atoms to form a mixture of distorted edge and corner-sharing OLiCr3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent Cr(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(2), and two equivalent Cr(1) atoms to form distorted OLiVCr2 tetrahedra that share corners with two equivalent O(2)LiCr3 tetrahedra and corners with four equivalent O(6)LiVCr2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(1), and one Cr(3) atom to form distorted OLiV2Cr tetrahedra that share corners with two equivalent O(12)LiV2Cr tetrahedra and corners with four equivalent O(9)LiVCr2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(2), one Cr(1), and one Cr(2) atom to form distorted OLiVCr2 trigonal pyramids that share  a cornercorner with one O(2)LiCr3 tetrahedra, corners with two equivalent O(4)LiVCr2 tetrahedra,  a cornercorner with one O(6)LiVCr2 trigonal pyramid,  an edgeedge with one O(2)LiCr3 tetrahedra, and  an edgeedge with one O(6)LiVCr2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Cr(4), and two equivalent Cr(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(1), and one Cr(2) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(1), one Cr(3), and one Cr(4) atom to form distorted OLiVCr2 tetrahedra that share  a cornercorner with one O(12)LiV2Cr tetrahedra,  a cornercorner with one O(9)LiVCr2 tetrahedra, corners with two equivalent O(5)LiV2Cr tetrahedra,  an edgeedge with one O(12)LiV2Cr tetrahedra, and  an edgeedge with one O(9)LiVCr2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one Cr(3) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Cr(1), and one Cr(4) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(1), and one Cr(4) atom to form distorted OLiV2Cr tetrahedra that share corners with two equivalent O(5)LiV2Cr tetrahedra, corners with two equivalent O(9)LiVCr2 tetrahedra, and edges with two equivalent O(9)LiVCr2 tetrahedra.
Li4V3Cr5O16 is Spinel-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 V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, corners with three equivalent Cr(4)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. The Li(1)-O(12) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.02 Å. Both Li(1)-O(9) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(2)-O(5) bond length is 1.76 Å. The Li(2)-O(7) bond length is 1.89 Å. Both Li(2)-O(11) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.77 Å. The Li(3)-O(8) bond length is 1.97 Å. Both Li(3)-O(1) bond lengths are 1.97 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 Cr(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and corners with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. The Li(4)-O(10) bond length is 2.01 Å. The Li(4)-O(2) bond length is 1.92 Å. Both Li(4)-O(6) bond lengths are 1.99 Å. There are two inequivalent V sites. In the first V site, V(1) 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 VO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The V(1)-O(1) bond length is 1.91 Å. The V(1)-O(10) bond length is 1.98 Å. The V(1)-O(12) bond length is 2.01 Å. The V(1)-O(5) bond length is 1.96 Å. The V(1)-O(8) bond length is 1.99 Å. The V(1)-O(9) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Cr(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(2)-O(3) bond length is 1.87 Å. The V(2)-O(4) bond length is 1.91 Å. Both V(2)-O(11) bond lengths are 1.91 Å. Both V(2)-O(6) bond lengths are 1.94 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(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 CrO6 octahedra that share corners with two equivalent Cr(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Cr(1)-O(11) bond length is 2.06 Å. The Cr(1)-O(2) bond length is 2.00 Å. The Cr(1)-O(3) bond length is 2.02 Å. The Cr(1)-O(4) bond length is 1.98 Å. The Cr(1)-O(6) bond length is 2.04 Å. The Cr(1)-O(7) bond length is 2.01 Å. In the second Cr site, Cr(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. The Cr(2)-O(2) bond length is 2.01 Å. The Cr(2)-O(8) bond length is 2.09 Å. Both Cr(2)-O(1) bond lengths are 2.08 Å. Both Cr(2)-O(6) bond lengths are 2.04 Å. In the third Cr site, Cr(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CrO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(4)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Cr(3)-O(10) bond length is 1.99 Å. The Cr(3)-O(5) bond length is 1.98 Å. Both Cr(3)-O(1) bond lengths are 2.06 Å. Both Cr(3)-O(9) bond lengths are 2.03 Å. In the fourth Cr site, Cr(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form CrO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Cr(4)-O(12) bond length is 2.05 Å. The Cr(4)-O(7) bond length is 2.01 Å. Both Cr(4)-O(11) bond lengths are 2.10 Å. Both Cr(4)-O(9) bond lengths are 2.05 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 Cr(2), and one Cr(3) atom. In the second O site, O(2) is bonded to one Li(4), one Cr(2), and two equivalent Cr(1) atoms to form a mixture of distorted edge and corner-sharing OLiCr3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent Cr(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(2), and two equivalent Cr(1) atoms to form distorted OLiVCr2 tetrahedra that share corners with two equivalent O(2)LiCr3 tetrahedra and corners with four equivalent O(6)LiVCr2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(1), and one Cr(3) atom to form distorted OLiV2Cr tetrahedra that share corners with two equivalent O(12)LiV2Cr tetrahedra and corners with four equivalent O(9)LiVCr2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(2), one Cr(1), and one Cr(2) atom to form distorted OLiVCr2 trigonal pyramids that share  a cornercorner with one O(2)LiCr3 tetrahedra, corners with two equivalent O(4)LiVCr2 tetrahedra,  a cornercorner with one O(6)LiVCr2 trigonal pyramid,  an edgeedge with one O(2)LiCr3 tetrahedra, and  an edgeedge with one O(6)LiVCr2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Cr(4), and two equivalent Cr(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(1), and one Cr(2) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(1), one Cr(3), and one Cr(4) atom to form distorted OLiVCr2 tetrahedra that share  a cornercorner with one O(12)LiV2Cr tetrahedra,  a cornercorner with one O(9)LiVCr2 tetrahedra, corners with two equivalent O(5)LiV2Cr tetrahedra,  an edgeedge with one O(12)LiV2Cr tetrahedra, and  an edgeedge with one O(9)LiVCr2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one Cr(3) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Cr(1), and one Cr(4) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(1), and one Cr(4) atom to form distorted OLiV2Cr tetrahedra that share corners with two equivalent O(5)LiV2Cr tetrahedra, corners with two equivalent O(9)LiVCr2 tetrahedra, and edges with two equivalent O(9)LiVCr2 tetrahedra.