Li4VCo3O8 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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. V(1) is bonded to one O(1), one O(2), one O(6), 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 Co(1)O4 tetrahedra, and corners with two equivalent Co(2)O4 tetrahedra. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(3), one O(7), and one O(8) atom to form CoO4 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 Co(3)O4 tetrahedra. In the second Co site, Co(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form CoO4 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 Co(3)O4 tetrahedra. In the third Co site, Co(3) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form CoO4 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 Co(1)O4 tetrahedra, and corners with two equivalent Co(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 Co(1) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(4), one V(1), and one Co(2) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Co(1), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Co(2), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Co(2), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(6)Li2VCo tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(1), and one Co(2) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one Co(1), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), and one Co(1) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(6)Li2VCo tetrahedra.
Li4VCo3O8 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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(4) bond length is 1.94 Å. The Li(1)-O(7) bond length is 1.93 Å. The Li(1)-O(8) bond length is 2.07 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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The Li(2)-O(1) bond length is 2.11 Å. The Li(2)-O(3) bond length is 1.97 Å. The Li(2)-O(5) bond length is 1.92 Å. The Li(2)-O(6) bond length is 2.09 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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The Li(3)-O(3) bond length is 1.96 Å. The Li(3)-O(4) bond length is 1.95 Å. The Li(3)-O(6) bond length is 2.08 Å. The Li(3)-O(8) bond length is 2.09 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 Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The Li(4)-O(1) bond length is 2.11 Å. The Li(4)-O(2) bond length is 2.13 Å. The Li(4)-O(5) bond length is 1.95 Å. The Li(4)-O(7) bond length is 1.99 Å. V(1) is bonded to one O(1), one O(2), one O(6), 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 Co(1)O4 tetrahedra, and corners with two equivalent Co(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.76 Å. The V(1)-O(2) bond length is 1.76 Å. The V(1)-O(6) bond length is 1.76 Å. The V(1)-O(8) bond length is 1.75 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(3), one O(7), and one O(8) atom to form CoO4 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 Co(3)O4 tetrahedra. The Co(1)-O(1) bond length is 2.03 Å. The Co(1)-O(3) bond length is 1.91 Å. The Co(1)-O(7) bond length is 1.92 Å. The Co(1)-O(8) bond length is 2.05 Å. In the second Co site, Co(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form CoO4 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 Co(3)O4 tetrahedra. The Co(2)-O(2) bond length is 2.04 Å. The Co(2)-O(4) bond length is 1.94 Å. The Co(2)-O(5) bond length is 1.91 Å. The Co(2)-O(6) bond length is 2.05 Å. In the third Co site, Co(3) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form CoO4 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 Co(1)O4 tetrahedra, and corners with two equivalent Co(2)O4 tetrahedra. The Co(3)-O(3) bond length is 1.89 Å. The Co(3)-O(4) bond length is 1.89 Å. The Co(3)-O(5) bond length is 1.89 Å. The Co(3)-O(7) bond length is 1.87 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 Co(1) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(4), one V(1), and one Co(2) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Co(1), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Co(2), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, corners with two equivalent O(6)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Co(2), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(6)Li2VCo tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(1), and one Co(2) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one Co(1), and one Co(3) atom to form OLi2Co2 tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(5)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(8)Li2VCo tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), and one Co(1) atom to form OLi2VCo tetrahedra that share corners with two equivalent O(3)Li2Co2 tetrahedra, corners with two equivalent O(4)Li2Co2 tetrahedra, corners with two equivalent O(7)Li2Co2 tetrahedra, corners with two equivalent O(1)Li2VCo tetrahedra, corners with two equivalent O(2)Li2VCo tetrahedra, and corners with two equivalent O(6)Li2VCo tetrahedra.