LiV2(CO3)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(10), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra and  an edgeedge with one V(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 44-49°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(8) atom to form distorted VO6 pentagonal pyramids that share  an edgeedge with one Li(1)O4 trigonal pyramid. In the second V site, V(2) is bonded to one O(10), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids. 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(3), and one O(4) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(6) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(7), and one O(8) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(12), and one O(9) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one V(1) and one C(2) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one V(2) and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted L-shaped geometry to one V(2) and one C(1) atom. In the fifth O site, O(5) is bonded in an L-shaped geometry to one V(1) and one C(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(2) and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(4) atom. In the eleventh O site, O(11) is bonded in an L-shaped geometry to one V(1) and one C(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one V(1) and one C(4) atom.
LiV2(CO3)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(10), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra and  an edgeedge with one V(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 44-49°. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-O(10) bond length is 1.97 Å. The Li(1)-O(8) bond length is 2.10 Å. The Li(1)-O(9) bond length is 1.99 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(8) atom to form distorted VO6 pentagonal pyramids that share  an edgeedge with one Li(1)O4 trigonal pyramid. The V(1)-O(1) bond length is 1.94 Å. The V(1)-O(11) bond length is 2.01 Å. The V(1)-O(12) bond length is 1.91 Å. The V(1)-O(2) bond length is 1.94 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(8) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(10), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids. The V(2)-O(10) bond length is 2.18 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(4) bond length is 2.12 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(7) bond length is 2.00 Å. The V(2)-O(9) bond length is 2.11 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(3), and one O(4) atom. The C(1)-O(1) bond length is 1.34 Å. The C(1)-O(3) bond length is 1.29 Å. The C(1)-O(4) bond length is 1.27 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(6) atom. The C(2)-O(2) bond length is 1.33 Å. The C(2)-O(5) bond length is 1.29 Å. The C(2)-O(6) bond length is 1.27 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(7), and one O(8) atom. The C(3)-O(11) bond length is 1.31 Å. The C(3)-O(7) bond length is 1.27 Å. The C(3)-O(8) bond length is 1.31 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(12), and one O(9) atom. The C(4)-O(10) bond length is 1.28 Å. The C(4)-O(12) bond length is 1.30 Å. The C(4)-O(9) bond length is 1.30 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one V(1) and one C(2) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one V(2) and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted L-shaped geometry to one V(2) and one C(1) atom. In the fifth O site, O(5) is bonded in an L-shaped geometry to one V(1) and one C(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(2) and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(4) atom. In the eleventh O site, O(11) is bonded in an L-shaped geometry to one V(1) and one C(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one V(1) and one C(4) atom.