Li3V3FeO8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six 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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra, edges with four equivalent O(2)Li2V2Fe square pyramids, edges with four equivalent O(3)Li2V2Fe square pyramids, and edges with four equivalent O(4)Li2V2Fe square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(2), one V(3), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(3)Li2V2Fe square pyramids, corners with two equivalent O(4)Li2V2Fe square pyramids, corners with five equivalent O(2)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li2V2Fe square pyramids, and edges with two equivalent O(4)Li2V2Fe square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(2)Li2V2Fe square pyramids, corners with two equivalent O(4)Li2V2Fe square pyramids, corners with five equivalent O(3)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li2V2Fe square pyramids, and edges with two equivalent O(4)Li2V2Fe square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(2)Li2V2Fe square pyramids, corners with two equivalent O(3)Li2V2Fe square pyramids, corners with five equivalent O(4)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li2V2Fe square pyramids, and edges with two equivalent O(3)Li2V2Fe square pyramids.
Li3V3FeO8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both Li(1)-O(1) bond lengths are 2.21 Å. Both Li(1)-O(3) bond lengths are 2.20 Å. Both Li(1)-O(4) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(2)-O(1) bond lengths are 2.12 Å. Both Li(2)-O(2) bond lengths are 2.20 Å. Both Li(2)-O(4) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(3)-O(1) bond lengths are 2.13 Å. Both Li(3)-O(2) bond lengths are 2.15 Å. Both Li(3)-O(3) bond lengths are 2.19 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both V(1)-O(1) bond lengths are 2.02 Å. Both V(1)-O(3) bond lengths are 2.01 Å. Both V(1)-O(4) bond lengths are 1.94 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both V(2)-O(1) bond lengths are 2.03 Å. Both V(2)-O(2) bond lengths are 2.01 Å. Both V(2)-O(4) bond lengths are 2.09 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six 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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both V(3)-O(1) bond lengths are 2.08 Å. Both V(3)-O(2) bond lengths are 2.01 Å. Both V(3)-O(3) bond lengths are 2.04 Å. Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both Fe(1)-O(2) bond lengths are 1.96 Å. Both Fe(1)-O(3) bond lengths are 1.96 Å. Both Fe(1)-O(4) bond lengths are 1.98 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra, edges with four equivalent O(2)Li2V2Fe square pyramids, edges with four equivalent O(3)Li2V2Fe square pyramids, and edges with four equivalent O(4)Li2V2Fe square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(2), one V(3), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(3)Li2V2Fe square pyramids, corners with two equivalent O(4)Li2V2Fe square pyramids, corners with five equivalent O(2)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li2V2Fe square pyramids, and edges with two equivalent O(4)Li2V2Fe square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(2)Li2V2Fe square pyramids, corners with two equivalent O(4)Li2V2Fe square pyramids, corners with five equivalent O(3)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li2V2Fe square pyramids, and edges with two equivalent O(4)Li2V2Fe square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Fe(1) atom to form OLi2V2Fe square pyramids that share corners with two equivalent O(2)Li2V2Fe square pyramids, corners with two equivalent O(3)Li2V2Fe square pyramids, corners with five equivalent O(4)Li2V2Fe square pyramids, edges with four equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li2V2Fe square pyramids, and edges with two equivalent O(3)Li2V2Fe square pyramids.