Li4V3Fe5O16 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(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. 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 Fe(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. There are two inequivalent V sites. In the first V site, V(1) 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 Fe(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the second V site, V(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 VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are four inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent Fe(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. In the second Fe site, Fe(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Fe(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the third Fe site, Fe(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(4)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the fourth Fe site, Fe(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. 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(2), one Fe(2), and one Fe(3) atom. In the second O site, O(2) is bonded to one Li(4), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Fe(1) atoms to form distorted OLiVFe2 tetrahedra that share corners with two equivalent O(2)LiFe3 tetrahedra and corners with four equivalent O(6)LiVFe2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Fe(3) atom to form distorted OLiV2Fe tetrahedra that share corners with two equivalent O(12)LiV2Fe tetrahedra and corners with four equivalent O(9)LiVFe2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Fe(1), and one Fe(2) atom to form distorted OLiVFe2 trigonal pyramids that share  a cornercorner with one O(2)LiFe3 tetrahedra, corners with two equivalent O(4)LiVFe2 tetrahedra,  a cornercorner with one O(6)LiVFe2 trigonal pyramid,  an edgeedge with one O(2)LiFe3 tetrahedra, and  an edgeedge with one O(6)LiVFe2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(4), and two equivalent Fe(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one Fe(2) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one Fe(3), and one Fe(4) atom to form distorted OLiVFe2 tetrahedra that share  a cornercorner with one O(12)LiV2Fe tetrahedra,  a cornercorner with one O(9)LiVFe2 tetrahedra, corners with two equivalent O(5)LiV2Fe tetrahedra,  an edgeedge with one O(12)LiV2Fe tetrahedra, and  an edgeedge with one O(9)LiVFe2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Fe(3) 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 Fe(1), and one Fe(4) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Fe(4) atom to form distorted OLiV2Fe tetrahedra that share corners with two equivalent O(5)LiV2Fe tetrahedra, corners with two equivalent O(9)LiVFe2 tetrahedra, and edges with two equivalent O(9)LiVFe2 tetrahedra.
Li4V3Fe5O16 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(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(3) bond length is 2.03 Å. Both Li(1)-O(9) bond lengths are 1.98 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 1.78 Å. The Li(2)-O(7) bond length is 1.94 Å. Both Li(2)-O(11) bond lengths are 1.96 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 1.78 Å. The Li(3)-O(8) bond length is 1.95 Å. Both Li(3)-O(1) bond lengths are 1.96 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 Fe(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. The Li(4)-O(10) bond length is 2.00 Å. The Li(4)-O(2) bond length is 1.95 Å. Both Li(4)-O(6) bond lengths are 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) 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 Fe(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(1)-O(3) bond length is 1.89 Å. The V(1)-O(4) bond length is 1.91 Å. Both V(1)-O(11) bond lengths are 1.95 Å. Both V(1)-O(6) bond lengths are 1.91 Å. In the second V site, V(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 VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(2)-O(1) bond length is 1.96 Å. The V(2)-O(10) bond length is 1.99 Å. The V(2)-O(12) bond length is 2.02 Å. The V(2)-O(5) bond length is 1.96 Å. The V(2)-O(8) bond length is 2.02 Å. The V(2)-O(9) bond length is 1.90 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent Fe(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. The Fe(1)-O(11) bond length is 2.11 Å. The Fe(1)-O(2) bond length is 1.99 Å. The Fe(1)-O(3) bond length is 2.05 Å. The Fe(1)-O(4) bond length is 2.00 Å. The Fe(1)-O(6) bond length is 2.07 Å. The Fe(1)-O(7) bond length is 2.02 Å. In the second Fe site, Fe(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Fe(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Fe(2)-O(2) bond length is 2.08 Å. The Fe(2)-O(8) bond length is 2.07 Å. Both Fe(2)-O(1) bond lengths are 2.05 Å. Both Fe(2)-O(6) bond lengths are 2.13 Å. In the third Fe site, Fe(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(4)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Fe(3)-O(10) bond length is 2.01 Å. The Fe(3)-O(5) bond length is 1.99 Å. Both Fe(3)-O(1) bond lengths are 2.06 Å. Both Fe(3)-O(9) bond lengths are 2.06 Å. In the fourth Fe site, Fe(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Fe(4)-O(12) bond length is 2.09 Å. The Fe(4)-O(7) bond length is 2.00 Å. Both Fe(4)-O(11) bond lengths are 2.07 Å. Both Fe(4)-O(9) bond lengths are 2.13 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(2), one Fe(2), and one Fe(3) atom. In the second O site, O(2) is bonded to one Li(4), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Fe(1) atoms to form distorted OLiVFe2 tetrahedra that share corners with two equivalent O(2)LiFe3 tetrahedra and corners with four equivalent O(6)LiVFe2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Fe(3) atom to form distorted OLiV2Fe tetrahedra that share corners with two equivalent O(12)LiV2Fe tetrahedra and corners with four equivalent O(9)LiVFe2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Fe(1), and one Fe(2) atom to form distorted OLiVFe2 trigonal pyramids that share  a cornercorner with one O(2)LiFe3 tetrahedra, corners with two equivalent O(4)LiVFe2 tetrahedra,  a cornercorner with one O(6)LiVFe2 trigonal pyramid,  an edgeedge with one O(2)LiFe3 tetrahedra, and  an edgeedge with one O(6)LiVFe2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(4), and two equivalent Fe(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one Fe(2) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one Fe(3), and one Fe(4) atom to form distorted OLiVFe2 tetrahedra that share  a cornercorner with one O(12)LiV2Fe tetrahedra,  a cornercorner with one O(9)LiVFe2 tetrahedra, corners with two equivalent O(5)LiV2Fe tetrahedra,  an edgeedge with one O(12)LiV2Fe tetrahedra, and  an edgeedge with one O(9)LiVFe2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Fe(3) 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 Fe(1), and one Fe(4) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Fe(4) atom to form distorted OLiV2Fe tetrahedra that share corners with two equivalent O(5)LiV2Fe tetrahedra, corners with two equivalent O(9)LiVFe2 tetrahedra, and edges with two equivalent O(9)LiVFe2 tetrahedra.