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 2-coordinate geometry to two equivalent Cr(2), two equivalent O(3), and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded in a 2-coordinate geometry to one Cr(2), one Cr(3), one O(1), one O(2), one O(3), one O(5), and one O(7) atom. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one Cr(1), one Cr(3), one O(1), one O(7), two equivalent O(2), and two equivalent O(8) atoms. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to two equivalent V(1), two equivalent O(4), and two equivalent O(6) atoms. In the fifth Li site, Li(5) is bonded in a 2-coordinate geometry to one V(1), one Cr(1), one O(1), one O(4), one O(7), and one O(8) atom. V(1) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one O(2), one O(3), one O(4), one O(6), and one O(8) atom. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one O(4), one O(7), one O(8), and two equivalent O(1) atoms. In the second Cr site, Cr(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one O(2), one O(3), one O(5), and one O(8) atom. In the third Cr site, Cr(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one O(1), one O(2), one O(4), and two equivalent O(7) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one Li(5), one Cr(3), two equivalent Cr(1), one O(7), and one O(8) atom. In the second O site, O(2) is bonded in a 8-coordinate geometry to one Li(2), two equivalent Li(3), one V(1), one Cr(2), one Cr(3), one O(5), and one O(7) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one V(1), one Cr(2), one O(3), and one O(5) atom. In the fourth O site, O(4) is bonded in a 8-coordinate geometry to one Li(1), one Li(4), one Li(5), one V(1), one Cr(1), one Cr(3), one O(6), and one O(8) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), one O(2), and one O(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), one O(4), and one O(6) atom. In the seventh O site, O(7) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one Li(5), one Cr(1), two equivalent Cr(3), one O(1), and one O(2) atom. In the eighth O site, O(8) is bonded in a 8-coordinate geometry to one Li(5), two equivalent Li(3), one V(1), one Cr(1), one Cr(2), one O(1), and one O(4) 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 2-coordinate geometry to two equivalent Cr(2), two equivalent O(3), and two equivalent O(4) atoms. Both Li(1)-Cr(2) bond lengths are 1.67 Å. Both Li(1)-O(3) bond lengths are 2.36 Å. Both Li(1)-O(4) bond lengths are 2.69 Å. In the second Li site, Li(2) is bonded in a 2-coordinate geometry to one Cr(2), one Cr(3), one O(1), one O(2), one O(3), one O(5), and one O(7) atom. The Li(2)-Cr(2) bond length is 1.66 Å. The Li(2)-Cr(3) bond length is 1.67 Å. The Li(2)-O(1) bond length is 2.67 Å. The Li(2)-O(2) bond length is 2.35 Å. The Li(2)-O(3) bond length is 2.47 Å. The Li(2)-O(5) bond length is 2.37 Å. The Li(2)-O(7) bond length is 2.46 Å. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one Cr(1), one Cr(3), one O(1), one O(7), two equivalent O(2), and two equivalent O(8) atoms. The Li(3)-Cr(1) bond length is 1.66 Å. The Li(3)-Cr(3) bond length is 1.66 Å. The Li(3)-O(1) bond length is 2.36 Å. The Li(3)-O(7) bond length is 2.36 Å. There is one shorter (2.46 Å) and one longer (2.69 Å) Li(3)-O(2) bond length. There is one shorter (2.46 Å) and one longer (2.71 Å) Li(3)-O(8) bond length. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to two equivalent V(1), two equivalent O(4), and two equivalent O(6) atoms. Both Li(4)-V(1) bond lengths are 1.67 Å. Both Li(4)-O(4) bond lengths are 2.49 Å. Both Li(4)-O(6) bond lengths are 2.33 Å. In the fifth Li site, Li(5) is bonded in a 2-coordinate geometry to one V(1), one Cr(1), one O(1), one O(4), one O(7), and one O(8) atom. The Li(5)-V(1) bond length is 1.67 Å. The Li(5)-Cr(1) bond length is 1.66 Å. The Li(5)-O(1) bond length is 2.46 Å. The Li(5)-O(4) bond length is 2.33 Å. The Li(5)-O(7) bond length is 2.69 Å. The Li(5)-O(8) bond length is 2.37 Å. V(1) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one O(2), one O(3), one O(4), one O(6), and one O(8) atom. The V(1)-O(2) bond length is 2.74 Å. The V(1)-O(3) bond length is 2.69 Å. The V(1)-O(4) bond length is 2.21 Å. The V(1)-O(6) bond length is 2.20 Å. The V(1)-O(8) bond length is 2.55 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one O(4), one O(7), one O(8), and two equivalent O(1) atoms. The Cr(1)-O(4) bond length is 2.52 Å. The Cr(1)-O(7) bond length is 2.53 Å. The Cr(1)-O(8) bond length is 2.17 Å. There is one shorter (2.17 Å) and one longer (2.72 Å) Cr(1)-O(1) bond length. In the second Cr site, Cr(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one O(2), one O(3), one O(5), and one O(8) atom. The Cr(2)-O(2) bond length is 2.53 Å. The Cr(2)-O(3) bond length is 2.19 Å. The Cr(2)-O(5) bond length is 2.17 Å. The Cr(2)-O(8) bond length is 2.72 Å. In the third Cr site, Cr(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one O(1), one O(2), one O(4), and two equivalent O(7) atoms. The Cr(3)-O(1) bond length is 2.54 Å. The Cr(3)-O(2) bond length is 2.17 Å. The Cr(3)-O(4) bond length is 2.71 Å. There is one shorter (2.17 Å) and one longer (2.72 Å) Cr(3)-O(7) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one Li(5), one Cr(3), two equivalent Cr(1), one O(7), and one O(8) atom. The O(1)-O(7) bond length is 1.52 Å. The O(1)-O(8) bond length is 1.81 Å. In the second O site, O(2) is bonded in a 8-coordinate geometry to one Li(2), two equivalent Li(3), one V(1), one Cr(2), one Cr(3), one O(5), and one O(7) atom. The O(2)-O(5) bond length is 1.53 Å. The O(2)-O(7) bond length is 1.81 Å. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one V(1), one Cr(2), one O(3), and one O(5) atom. The O(3)-O(3) bond length is 1.56 Å. The O(3)-O(5) bond length is 1.80 Å. In the fourth O site, O(4) is bonded in a 8-coordinate geometry to one Li(1), one Li(4), one Li(5), one V(1), one Cr(1), one Cr(3), one O(6), and one O(8) atom. The O(4)-O(6) bond length is 1.80 Å. The O(4)-O(8) bond length is 1.53 Å. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), one O(2), and one O(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), one O(4), and one O(6) atom. The O(6)-O(6) bond length is 1.54 Å. In the seventh O site, O(7) is bonded in a 8-coordinate geometry to one Li(2), one Li(3), one Li(5), one Cr(1), two equivalent Cr(3), one O(1), and one O(2) atom. In the eighth O site, O(8) is bonded in a 8-coordinate geometry to one Li(5), two equivalent Li(3), one V(1), one Cr(1), one Cr(2), one O(1), and one O(4) atom.