Li4V3MnO8 is Stannite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. Mn(1) is bonded to one O(1), one O(2), one O(6), and one O(8) atom to form MnO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one V(1), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(4), one V(2), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(2), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(5)Li2V2 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one V(1), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(5)Li2V2 tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra.
Li4V3MnO8 is Stannite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.10 Å. The Li(1)-O(7) bond length is 2.03 Å. The Li(1)-O(8) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.11 Å. The Li(2)-O(6) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The Li(3)-O(3) bond length is 2.03 Å. The Li(3)-O(4) bond length is 2.07 Å. The Li(3)-O(6) bond length is 2.06 Å. The Li(3)-O(8) bond length is 2.00 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The Li(4)-O(1) bond length is 1.94 Å. The Li(4)-O(2) bond length is 2.00 Å. The Li(4)-O(5) bond length is 2.10 Å. The Li(4)-O(7) bond length is 2.01 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The V(1)-O(1) bond length is 1.91 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(7) bond length is 1.97 Å. The V(1)-O(8) bond length is 1.91 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent Mn(1)O4 tetrahedra. The V(2)-O(2) bond length is 1.79 Å. The V(2)-O(4) bond length is 1.88 Å. The V(2)-O(5) bond length is 1.88 Å. The V(2)-O(6) bond length is 1.80 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. The V(3)-O(3) bond length is 1.91 Å. The V(3)-O(4) bond length is 1.96 Å. The V(3)-O(5) bond length is 1.97 Å. The V(3)-O(7) bond length is 1.91 Å. Mn(1) is bonded to one O(1), one O(2), one O(6), and one O(8) atom to form MnO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. The Mn(1)-O(1) bond length is 2.03 Å. The Mn(1)-O(2) bond length is 2.10 Å. The Mn(1)-O(6) bond length is 2.07 Å. The Mn(1)-O(8) bond length is 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one V(1), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(4), one V(2), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(5)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(2), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(5)Li2V2 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one V(1), and one V(3) atom to form OLi2V2 tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(8)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(5)Li2V2 tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), and one Mn(1) atom to form OLi2MnV tetrahedra that share corners with two equivalent O(1)Li2MnV tetrahedra, corners with two equivalent O(2)Li2MnV tetrahedra, corners with two equivalent O(6)Li2MnV tetrahedra, corners with two equivalent O(3)Li2V2 tetrahedra, corners with two equivalent O(4)Li2V2 tetrahedra, and corners with two equivalent O(7)Li2V2 tetrahedra.