Li4V3(CO3)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one O(7), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(9), two equivalent O(4), and two equivalent O(8) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(9) atom. In the second V site, V(2) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(7) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(6), and one O(8) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one C(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one C(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(2), and one C(3) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(2), and one C(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one C(3) atom.
Li4V3(CO3)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one O(7), and two equivalent O(2) atoms. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(5) bond length is 2.07 Å. The Li(1)-O(6) bond length is 2.51 Å. The Li(1)-O(7) bond length is 2.55 Å. There is one shorter (2.09 Å) and one longer (2.52 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(9), two equivalent O(4), and two equivalent O(8) atoms. The Li(2)-O(1) bond length is 2.43 Å. The Li(2)-O(9) bond length is 1.99 Å. There is one shorter (2.02 Å) and one longer (2.57 Å) Li(2)-O(4) bond length. There is one shorter (2.08 Å) and one longer (2.42 Å) Li(2)-O(8) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(9) atom. The V(1)-O(2) bond length is 2.14 Å. The V(1)-O(3) bond length is 2.08 Å. The V(1)-O(5) bond length is 2.07 Å. The V(1)-O(6) bond length is 2.04 Å. The V(1)-O(7) bond length is 2.07 Å. The V(1)-O(9) bond length is 2.09 Å. In the second V site, V(2) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms. Both V(2)-O(1) bond lengths are 2.07 Å. Both V(2)-O(4) bond lengths are 2.11 Å. Both V(2)-O(8) bond lengths are 2.11 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(7) atom. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(5) bond length is 1.30 Å. The C(1)-O(7) bond length is 1.28 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(6), and one O(8) atom. The C(2)-O(1) bond length is 1.29 Å. The C(2)-O(6) bond length is 1.29 Å. The C(2)-O(8) bond length is 1.32 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(9) atom. The C(3)-O(3) bond length is 1.29 Å. The C(3)-O(4) bond length is 1.30 Å. The C(3)-O(9) bond length is 1.29 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one C(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one C(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(2), and one C(3) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(2), and one C(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one C(3) atom.