Li3V2(FeO4)2 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(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(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Li site, Li(2) 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(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Fe(2)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 5-8°. There are two 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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. 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(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 Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) 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 Fe(2)O6 octahedra. In the second Fe site, Fe(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 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 5-8°. There are four inequivalent O sites. In the first O site, O(1) 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)Li2VFe2 square pyramids, corners with two equivalent O(3)Li2VFe2 square pyramids, corners with five equivalent O(1)Li2V2Fe square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(2)Li2VFe2 square pyramids, and edges with two equivalent O(3)Li2VFe2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), one Fe(1), and one Fe(2) atom to form OLi2VFe2 square pyramids that share corners with two equivalent O(1)Li2V2Fe square pyramids, corners with two equivalent O(3)Li2VFe2 square pyramids, corners with five equivalent O(2)Li2VFe2 square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(1)Li2V2Fe square pyramids, and edges with two equivalent O(3)Li2VFe2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), one Fe(1), and one Fe(2) atom to form OLi2VFe2 square pyramids that share corners with two equivalent O(1)Li2V2Fe square pyramids, corners with two equivalent O(2)Li2VFe2 square pyramids, corners with five equivalent O(3)Li2VFe2 square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(1)Li2V2Fe square pyramids, and edges with two equivalent O(2)Li2VFe2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Fe(2) atom to form OLi3V2Fe octahedra that share corners with six equivalent O(4)Li3V2Fe octahedra, edges with four equivalent O(1)Li2V2Fe square pyramids, edges with four equivalent O(2)Li2VFe2 square pyramids, and edges with four equivalent O(3)Li2VFe2 square pyramids. The corner-sharing octahedra are not tilted.
Li3V2(FeO4)2 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(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(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-O(2) bond lengths are 2.21 Å. Both Li(1)-O(4) bond lengths are 2.12 Å. In the second Li site, Li(2) 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(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Li(2)-O(1) bond lengths are 2.28 Å. Both Li(2)-O(3) bond lengths are 2.21 Å. Both Li(2)-O(4) bond lengths are 2.21 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Fe(2)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 5-8°. Both Li(3)-O(2) bond lengths are 2.17 Å. Both Li(3)-O(3) bond lengths are 2.18 Å. Both Li(3)-O(4) bond lengths are 2.17 Å. There are two 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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both V(1)-O(1) bond lengths are 1.94 Å. Both V(1)-O(3) bond lengths are 2.02 Å. Both V(1)-O(4) bond lengths are 2.03 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(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 Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both V(2)-O(1) bond lengths are 2.06 Å. Both V(2)-O(2) bond lengths are 2.02 Å. Both V(2)-O(4) bond lengths are 2.11 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) 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 Fe(2)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.06 Å. Both Fe(1)-O(2) bond lengths are 2.00 Å. Both Fe(1)-O(3) bond lengths are 2.02 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 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 5-8°. Both Fe(2)-O(2) bond lengths are 2.06 Å. Both Fe(2)-O(3) bond lengths are 2.06 Å. Both Fe(2)-O(4) bond lengths are 2.06 Å. There are four inequivalent O sites. In the first O site, O(1) 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)Li2VFe2 square pyramids, corners with two equivalent O(3)Li2VFe2 square pyramids, corners with five equivalent O(1)Li2V2Fe square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(2)Li2VFe2 square pyramids, and edges with two equivalent O(3)Li2VFe2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), one Fe(1), and one Fe(2) atom to form OLi2VFe2 square pyramids that share corners with two equivalent O(1)Li2V2Fe square pyramids, corners with two equivalent O(3)Li2VFe2 square pyramids, corners with five equivalent O(2)Li2VFe2 square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(1)Li2V2Fe square pyramids, and edges with two equivalent O(3)Li2VFe2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), one Fe(1), and one Fe(2) atom to form OLi2VFe2 square pyramids that share corners with two equivalent O(1)Li2V2Fe square pyramids, corners with two equivalent O(2)Li2VFe2 square pyramids, corners with five equivalent O(3)Li2VFe2 square pyramids, edges with four equivalent O(4)Li3V2Fe octahedra, edges with two equivalent O(1)Li2V2Fe square pyramids, and edges with two equivalent O(2)Li2VFe2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Fe(2) atom to form OLi3V2Fe octahedra that share corners with six equivalent O(4)Li3V2Fe octahedra, edges with four equivalent O(1)Li2V2Fe square pyramids, edges with four equivalent O(2)Li2VFe2 square pyramids, and edges with four equivalent O(3)Li2VFe2 square pyramids. The corner-sharing octahedra are not tilted.