Li3V2(CO3)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(18), one O(19), one O(21), and one O(23) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(17), one O(20), one O(22), and one O(24) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(17), and one O(5) atom. In the fourth Li site, Li(4) is bonded to one O(11), one O(18), one O(2), one O(6), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. In the fifth Li site, Li(5) is bonded to one O(11), one O(19), one O(3), one O(7), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the sixth Li site, Li(6) is bonded to one O(10), one O(12), one O(20), one O(4), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-65°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(14), one O(16), one O(2), one O(3), and one O(9) atom to form distorted VO6 octahedra that share  a faceface with one Li(4)O5 square pyramid and  a faceface with one Li(5)O5 square pyramid. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(13), one O(15), and one O(4) atom to form VO6 octahedra that share  a faceface with one Li(6)O5 square pyramid. In the third V site, V(3) is bonded to one O(18), one O(20), one O(22), one O(23), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Li(6)O5 square pyramid. In the fourth V site, V(4) is bonded to one O(17), one O(19), one O(21), one O(24), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Li(6)O5 square pyramid. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(13), one O(24), and one O(9) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(14), and one O(23) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(15), and one O(22) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(12), one O(16), and one O(21) atom. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(17), one O(4), and one O(5) atom. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(18), one O(3), and one O(6) atom. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(19), one O(2), and one O(7) atom. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one O(1), one O(20), and one O(8) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(8) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(7) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one C(6) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(6), one V(2), and one C(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one C(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(4), and one C(6) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(5), one V(3), and one C(7) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(6), one V(4), and one C(8) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(1), and one C(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one V(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(1), and one C(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one V(2), and one C(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one C(1) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one C(2) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(2) and one C(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one V(1) and one C(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(4), and one C(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one C(6) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(5), one V(4), and one C(7) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(6), one V(3), and one C(8) atom. In the twenty-first O site, O(21) is bonded in a trigonal planar geometry to one Li(1), one V(4), and one C(4) atom. In the twenty-second O site, O(22) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one C(3) atom. In the twenty-third O site, O(23) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one C(2) atom. In the twenty-fourth O site, O(24) is bonded in a trigonal planar geometry to one Li(2), one V(4), and one C(1) atom.
Li3V2(CO3)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(18), one O(19), one O(21), and one O(23) atom. The Li(1)-O(18) bond length is 2.33 Å. The Li(1)-O(19) bond length is 2.34 Å. The Li(1)-O(21) bond length is 1.90 Å. The Li(1)-O(23) bond length is 1.97 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(17), one O(20), one O(22), and one O(24) atom. The Li(2)-O(17) bond length is 2.49 Å. The Li(2)-O(20) bond length is 2.33 Å. The Li(2)-O(22) bond length is 1.95 Å. The Li(2)-O(24) bond length is 1.88 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(17), and one O(5) atom. The Li(3)-O(1) bond length is 1.99 Å. The Li(3)-O(10) bond length is 2.51 Å. The Li(3)-O(12) bond length is 2.01 Å. The Li(3)-O(17) bond length is 2.10 Å. The Li(3)-O(5) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded to one O(11), one O(18), one O(2), one O(6), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. The Li(4)-O(11) bond length is 2.06 Å. The Li(4)-O(18) bond length is 2.25 Å. The Li(4)-O(2) bond length is 1.98 Å. The Li(4)-O(6) bond length is 1.98 Å. The Li(4)-O(9) bond length is 2.26 Å. In the fifth Li site, Li(5) is bonded to one O(11), one O(19), one O(3), one O(7), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Li(5)-O(11) bond length is 2.33 Å. The Li(5)-O(19) bond length is 2.11 Å. The Li(5)-O(3) bond length is 1.96 Å. The Li(5)-O(7) bond length is 2.03 Å. The Li(5)-O(9) bond length is 2.04 Å. In the sixth Li site, Li(6) is bonded to one O(10), one O(12), one O(20), one O(4), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-65°. The Li(6)-O(10) bond length is 2.02 Å. The Li(6)-O(12) bond length is 2.33 Å. The Li(6)-O(20) bond length is 2.23 Å. The Li(6)-O(4) bond length is 2.00 Å. The Li(6)-O(8) bond length is 2.00 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(14), one O(16), one O(2), one O(3), and one O(9) atom to form distorted VO6 octahedra that share  a faceface with one Li(4)O5 square pyramid and  a faceface with one Li(5)O5 square pyramid. The V(1)-O(11) bond length is 2.26 Å. The V(1)-O(14) bond length is 2.11 Å. The V(1)-O(16) bond length is 2.11 Å. The V(1)-O(2) bond length is 2.14 Å. The V(1)-O(3) bond length is 2.15 Å. The V(1)-O(9) bond length is 2.22 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(13), one O(15), and one O(4) atom to form VO6 octahedra that share  a faceface with one Li(6)O5 square pyramid. The V(2)-O(1) bond length is 2.03 Å. The V(2)-O(10) bond length is 2.14 Å. The V(2)-O(12) bond length is 2.10 Å. The V(2)-O(13) bond length is 1.99 Å. The V(2)-O(15) bond length is 2.01 Å. The V(2)-O(4) bond length is 2.03 Å. In the third V site, V(3) is bonded to one O(18), one O(20), one O(22), one O(23), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Li(6)O5 square pyramid. The V(3)-O(18) bond length is 2.11 Å. The V(3)-O(20) bond length is 2.15 Å. The V(3)-O(22) bond length is 2.04 Å. The V(3)-O(23) bond length is 2.00 Å. The V(3)-O(5) bond length is 2.08 Å. The V(3)-O(7) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one O(17), one O(19), one O(21), one O(24), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Li(6)O5 square pyramid. The V(4)-O(17) bond length is 2.26 Å. The V(4)-O(19) bond length is 2.24 Å. The V(4)-O(21) bond length is 2.15 Å. The V(4)-O(24) bond length is 2.16 Å. The V(4)-O(6) bond length is 2.17 Å. The V(4)-O(8) bond length is 2.18 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(13), one O(24), and one O(9) atom. The C(1)-O(13) bond length is 1.29 Å. The C(1)-O(24) bond length is 1.29 Å. The C(1)-O(9) bond length is 1.30 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(14), and one O(23) atom. The C(2)-O(10) bond length is 1.31 Å. The C(2)-O(14) bond length is 1.25 Å. The C(2)-O(23) bond length is 1.32 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(15), and one O(22) atom. The C(3)-O(11) bond length is 1.29 Å. The C(3)-O(15) bond length is 1.28 Å. The C(3)-O(22) bond length is 1.32 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(12), one O(16), and one O(21) atom. The C(4)-O(12) bond length is 1.33 Å. The C(4)-O(16) bond length is 1.27 Å. The C(4)-O(21) bond length is 1.29 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(17), one O(4), and one O(5) atom. The C(5)-O(17) bond length is 1.29 Å. The C(5)-O(4) bond length is 1.30 Å. The C(5)-O(5) bond length is 1.29 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(18), one O(3), and one O(6) atom. The C(6)-O(18) bond length is 1.33 Å. The C(6)-O(3) bond length is 1.28 Å. The C(6)-O(6) bond length is 1.28 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(19), one O(2), and one O(7) atom. The C(7)-O(19) bond length is 1.31 Å. The C(7)-O(2) bond length is 1.28 Å. The C(7)-O(7) bond length is 1.31 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one O(1), one O(20), and one O(8) atom. The C(8)-O(1) bond length is 1.30 Å. The C(8)-O(20) bond length is 1.32 Å. The C(8)-O(8) bond length is 1.27 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(8) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(7) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one C(6) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(6), one V(2), and one C(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one C(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(4), and one C(6) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(5), one V(3), and one C(7) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(6), one V(4), and one C(8) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(1), and one C(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one V(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(1), and one C(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one V(2), and one C(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one C(1) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one C(2) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(2) and one C(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one V(1) and one C(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(4), and one C(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one C(6) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(5), one V(4), and one C(7) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(6), one V(3), and one C(8) atom. In the twenty-first O site, O(21) is bonded in a trigonal planar geometry to one Li(1), one V(4), and one C(4) atom. In the twenty-second O site, O(22) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one C(3) atom. In the twenty-third O site, O(23) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one C(2) atom. In the twenty-fourth O site, O(24) is bonded in a trigonal planar geometry to one Li(2), one V(4), and one C(1) atom.