Li6VFe5O12 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and  a faceface with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and  a faceface with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-54°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra, corners with three equivalent Fe(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-52°. V(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra, edges with three equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and faces with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the second Fe site, Fe(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third Fe site, Fe(3) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(3)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. In the fifth Fe site, Fe(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, corners with six equivalent Li(3)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(4)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li6VFe5O12 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and  a faceface with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. The Li(1)-O(1) bond length is 2.42 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.11 Å. The Li(1)-O(4) bond length is 2.36 Å. The Li(1)-O(5) bond length is 2.20 Å. The Li(1)-O(6) bond length is 2.09 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and  a faceface with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-54°. The Li(2)-O(1) bond length is 2.32 Å. The Li(2)-O(2) bond length is 2.13 Å. The Li(2)-O(3) bond length is 2.28 Å. The Li(2)-O(4) bond length is 2.04 Å. The Li(2)-O(5) bond length is 2.13 Å. The Li(2)-O(6) bond length is 2.22 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with three equivalent Fe(4)O6 octahedra, corners with three equivalent Fe(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-52°. The Li(3)-O(1) bond length is 2.06 Å. The Li(3)-O(2) bond length is 2.18 Å. The Li(3)-O(3) bond length is 2.25 Å. The Li(3)-O(4) bond length is 2.25 Å. The Li(3)-O(5) bond length is 2.15 Å. The Li(3)-O(6) bond length is 2.16 Å. V(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both V(1)-O(2) bond lengths are 2.08 Å. Both V(1)-O(5) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 2.03 Å. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra, edges with three equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and faces with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. Both Fe(1)-O(1) bond lengths are 1.99 Å. Both Fe(1)-O(3) bond lengths are 2.00 Å. Both Fe(1)-O(4) bond lengths are 2.00 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. Both Fe(2)-O(2) bond lengths are 2.03 Å. Both Fe(2)-O(5) bond lengths are 2.06 Å. Both Fe(2)-O(6) bond lengths are 2.04 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both Fe(3)-O(2) bond lengths are 2.03 Å. Both Fe(3)-O(5) bond lengths are 2.05 Å. Both Fe(3)-O(6) bond lengths are 2.06 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(3)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. Both Fe(4)-O(1) bond lengths are 1.98 Å. Both Fe(4)-O(3) bond lengths are 1.99 Å. Both Fe(4)-O(4) bond lengths are 2.04 Å. In the fifth Fe site, Fe(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, corners with six equivalent Li(3)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(4)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. Both Fe(5)-O(1) bond lengths are 2.06 Å. Both Fe(5)-O(3) bond lengths are 2.07 Å. Both Fe(5)-O(4) bond lengths are 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Fe(1), one Fe(4), and one Fe(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi3VFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.