Li2V(CO3)2 crystallizes in the monoclinic C2 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form distorted LiO4 trigonal pyramids that share edges with two equivalent V(1)O6 octahedra. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(6) atoms. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(10), one O(2), and one O(3) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(4), one O(7), one O(8), and one O(9) atom. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(11) atoms. In the sixth Li site, Li(6) is bonded to two equivalent O(12) and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share edges with two equivalent V(1)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(3), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  an edgeedge with one Li(1)O4 trigonal pyramid and  an edgeedge with one Li(6)O4 trigonal pyramid. In the second V site, V(2) is bonded in an octahedral geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(9) atoms. In the third V site, V(3) is bonded in an octahedral geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(8) atoms. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(5), 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(10), one O(3), and one O(7) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(9) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(5), one V(1), and one C(1) atom to form distorted edge-sharing OLi3VC trigonal bipyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one C(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(6), one V(1), and one C(3) atom to form distorted edge-sharing OLi3VC trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(4), one V(3), and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one C(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one C(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(5), one V(3), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(6), one V(1), and one C(4) atom.
Li2V(CO3)2 crystallizes in the monoclinic C2 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form distorted LiO4 trigonal pyramids that share edges with two equivalent V(1)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-O(5) bond lengths are 1.88 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Li(2)-O(3) bond lengths are 2.09 Å. Both Li(2)-O(6) bond lengths are 1.96 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(10), one O(2), and one O(3) atom. The Li(3)-O(1) bond length is 2.27 Å. The Li(3)-O(10) bond length is 1.92 Å. The Li(3)-O(2) bond length is 1.93 Å. The Li(3)-O(3) bond length is 2.20 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(4), one O(7), one O(8), and one O(9) atom. The Li(4)-O(4) bond length is 1.98 Å. The Li(4)-O(7) bond length is 1.99 Å. The Li(4)-O(8) bond length is 1.95 Å. The Li(4)-O(9) bond length is 1.96 Å. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(11) atoms. Both Li(5)-O(1) bond lengths are 2.12 Å. Both Li(5)-O(11) bond lengths are 1.97 Å. In the sixth Li site, Li(6) is bonded to two equivalent O(12) and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share edges with two equivalent V(1)O6 octahedra. Both Li(6)-O(12) bond lengths are 1.87 Å. Both Li(6)-O(3) bond lengths are 2.29 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(3), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  an edgeedge with one Li(1)O4 trigonal pyramid and  an edgeedge with one Li(6)O4 trigonal pyramid. The V(1)-O(1) bond length is 2.19 Å. The V(1)-O(12) bond length is 2.11 Å. The V(1)-O(3) bond length is 2.20 Å. The V(1)-O(4) bond length is 2.19 Å. The V(1)-O(5) bond length is 2.12 Å. The V(1)-O(7) bond length is 2.17 Å. In the second V site, V(2) is bonded in an octahedral geometry to two equivalent O(2), two equivalent O(6), and two equivalent O(9) atoms. Both V(2)-O(2) bond lengths are 2.16 Å. Both V(2)-O(6) bond lengths are 2.22 Å. Both V(2)-O(9) bond lengths are 2.16 Å. In the third V site, V(3) is bonded in an octahedral geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(8) atoms. Both V(3)-O(10) bond lengths are 2.16 Å. Both V(3)-O(11) bond lengths are 2.21 Å. Both V(3)-O(8) bond lengths are 2.17 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. The C(1)-O(1) bond length is 1.32 Å. The C(1)-O(2) bond length is 1.29 Å. The C(1)-O(4) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(5), one O(6), and one O(8) atom. The C(2)-O(5) bond length is 1.30 Å. The C(2)-O(6) bond length is 1.30 Å. The C(2)-O(8) bond length is 1.29 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(10), one O(3), and one O(7) atom. The C(3)-O(10) bond length is 1.29 Å. The C(3)-O(3) bond length is 1.32 Å. The C(3)-O(7) bond length is 1.28 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(9) atom. The C(4)-O(11) bond length is 1.30 Å. The C(4)-O(12) bond length is 1.30 Å. The C(4)-O(9) bond length is 1.29 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(5), one V(1), and one C(1) atom to form distorted edge-sharing OLi3VC trigonal bipyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one C(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(6), one V(1), and one C(3) atom to form distorted edge-sharing OLi3VC trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(4), one V(3), and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one C(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one C(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(5), one V(3), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(6), one V(1), and one C(4) atom.