Li4VCr3O8 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to two equivalent Cr(2), two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Cr(2), one Cr(3), one O(1), one O(2), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded in a 8-coordinate geometry to one Cr(1), one Cr(3), one O(2), one O(8), two equivalent O(1), and two equivalent O(7) atoms. In the fourth Li site, Li(4) is bonded in a 8-coordinate geometry to two equivalent V(1), two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms. In the fifth Li site, Li(5) is bonded in a 8-coordinate geometry to one V(1), one Cr(1), one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. V(1) is bonded in a 8-coordinate geometry to one Li(4), one Li(5), one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 8-coordinate geometry to one Li(3), one Li(5), one O(2), one O(5), one O(7), one O(8), and two equivalent O(1) atoms. In the second Cr site, Cr(2) is bonded in a 8-coordinate geometry to one Li(1), one Li(2), one O(3), one O(4), one O(5), one O(8), and two equivalent O(6) atoms. In the third Cr site, Cr(3) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one O(1), one O(2), one O(4), one O(8), and two equivalent O(7) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), one Cr(3), and two equivalent Cr(1) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(5), one V(1), one Cr(1), and one Cr(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one Li(5), two equivalent V(1), and one Cr(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one V(1), one Cr(2), and one Cr(3) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Li(5), one V(1), one Cr(1), and one Cr(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), one V(1), and two equivalent Cr(2) atoms. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent Li(3), one Cr(1), and two equivalent Cr(3) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Cr(1), one Cr(2), and one Cr(3) atom.
Li4VCr3O8 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to two equivalent Cr(2), two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. Both Li(1)-Cr(2) bond lengths are 2.27 Å. Both Li(1)-O(3) bond lengths are 2.24 Å. Both Li(1)-O(4) bond lengths are 2.10 Å. Both Li(1)-O(6) bond lengths are 2.54 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Cr(2), one Cr(3), one O(1), one O(2), one O(5), and one O(6) atom. The Li(2)-Cr(2) bond length is 2.25 Å. The Li(2)-Cr(3) bond length is 2.26 Å. The Li(2)-O(1) bond length is 2.09 Å. The Li(2)-O(2) bond length is 2.24 Å. The Li(2)-O(5) bond length is 2.24 Å. The Li(2)-O(6) bond length is 2.13 Å. In the third Li site, Li(3) is bonded in a 8-coordinate geometry to one Cr(1), one Cr(3), one O(2), one O(8), two equivalent O(1), and two equivalent O(7) atoms. The Li(3)-Cr(1) bond length is 2.26 Å. The Li(3)-Cr(3) bond length is 2.26 Å. The Li(3)-O(2) bond length is 2.10 Å. The Li(3)-O(8) bond length is 2.11 Å. There is one shorter (2.24 Å) and one longer (2.57 Å) Li(3)-O(1) bond length. There is one shorter (2.24 Å) and one longer (2.56 Å) Li(3)-O(7) bond length. In the fourth Li site, Li(4) is bonded in a 8-coordinate geometry to two equivalent V(1), two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms. Both Li(4)-V(1) bond lengths are 2.27 Å. Both Li(4)-O(3) bond lengths are 2.54 Å. Both Li(4)-O(5) bond lengths are 2.10 Å. Both Li(4)-O(6) bond lengths are 2.22 Å. In the fifth Li site, Li(5) is bonded in a 8-coordinate geometry to one V(1), one Cr(1), one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. The Li(5)-V(1) bond length is 2.27 Å. The Li(5)-Cr(1) bond length is 2.25 Å. The Li(5)-O(2) bond length is 2.56 Å. The Li(5)-O(3) bond length is 2.10 Å. The Li(5)-O(4) bond length is 2.21 Å. The Li(5)-O(5) bond length is 2.56 Å. The Li(5)-O(7) bond length is 2.10 Å. The Li(5)-O(8) bond length is 2.25 Å. V(1) is bonded in a 8-coordinate geometry to one Li(4), one Li(5), one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.09 Å. The V(1)-O(5) bond length is 2.46 Å. The V(1)-O(6) bond length is 2.09 Å. There is one shorter (2.05 Å) and one longer (2.44 Å) V(1)-O(3) bond length. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 8-coordinate geometry to one Li(3), one Li(5), one O(2), one O(5), one O(7), one O(8), and two equivalent O(1) atoms. The Cr(1)-O(2) bond length is 2.44 Å. The Cr(1)-O(5) bond length is 2.06 Å. The Cr(1)-O(7) bond length is 2.44 Å. The Cr(1)-O(8) bond length is 2.06 Å. Both Cr(1)-O(1) bond lengths are 2.06 Å. In the second Cr site, Cr(2) is bonded in a 8-coordinate geometry to one Li(1), one Li(2), one O(3), one O(4), one O(5), one O(8), and two equivalent O(6) atoms. The Cr(2)-O(3) bond length is 2.07 Å. The Cr(2)-O(4) bond length is 2.44 Å. The Cr(2)-O(5) bond length is 2.06 Å. The Cr(2)-O(8) bond length is 2.06 Å. There is one shorter (2.04 Å) and one longer (2.45 Å) Cr(2)-O(6) bond length. In the third Cr site, Cr(3) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one O(1), one O(2), one O(4), one O(8), and two equivalent O(7) atoms. The Cr(3)-O(1) bond length is 2.44 Å. The Cr(3)-O(2) bond length is 2.06 Å. The Cr(3)-O(4) bond length is 2.06 Å. The Cr(3)-O(8) bond length is 2.44 Å. Both Cr(3)-O(7) bond lengths are 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), one Cr(3), and two equivalent Cr(1) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(5), one V(1), one Cr(1), and one Cr(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one Li(5), two equivalent V(1), and one Cr(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one V(1), one Cr(2), and one Cr(3) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Li(5), one V(1), one Cr(1), and one Cr(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), one V(1), and two equivalent Cr(2) atoms. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent Li(3), one Cr(1), and two equivalent Cr(3) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Cr(1), one Cr(2), and one Cr(3) atom.