Li3Co2(CO3)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(13), one O(3), one O(5), and one O(7) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the second Li site, Li(2) is bonded to one O(14), one O(4), one O(6), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra and  an edgeedge with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 44°. In the third Li site, Li(3) is bonded to one O(15), one O(17), one O(22), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra and  a cornercorner with one Li(5)O5 square pyramid. The corner-sharing octahedral tilt angles are 37°. In the fourth Li site, Li(4) is bonded to one O(10), one O(16), one O(18), and one O(21) atom to form LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 61°. In the fifth Li site, Li(5) is bonded to one O(15), one O(19), one O(2), one O(21), and one O(24) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Co(2)O5 trigonal bipyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(16), one O(20), one O(22), and one O(23) atom. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(17), one O(2), one O(21), one O(24), one O(5), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(5)O5 square pyramid. In the second Co site, Co(2) is bonded to one O(10), one O(11), one O(14), one O(19), and one O(4) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the third Co site, Co(3) is bonded in a 6-coordinate geometry to one O(1), one O(18), one O(22), one O(23), one O(6), and one O(7) atom. In the fourth Co site, Co(4) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(15), one O(20), one O(3), and one O(9) atom. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(11), and one O(4) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(3) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(5), one O(8), and one O(9) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(6), and one O(7) atom. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(13), one O(17), and one O(21) atom. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(14), one O(18), and one O(22) atom. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(15), one O(20), and one O(23) atom. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one O(16), one O(19), and one O(24) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(6), one Co(3), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(5), one Co(1), and one C(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Co(4), and one C(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Co(2), and one C(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Co(3), and one C(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(3), and one C(4) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Co(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one Co(4), and one C(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(4), one Co(2), and one C(4) atom. In the eleventh O site, O(11) is bonded in an L-shaped geometry to one Co(2) and one C(1) atom. In the twelfth O site, O(12) is bonded in an L-shaped geometry to one Co(4) and one C(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(4), and one C(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(2), and one C(6) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Co(4), and one C(7) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Li(6), and one C(8) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(3), one Co(1), and one C(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(4), one Co(3), and one C(6) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(5), one Co(2), and one C(8) atom. In the twentieth O site, O(20) is bonded in a T-shaped geometry to one Li(6), one Co(4), and one C(7) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Co(1), and one C(5) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Co(3), and one C(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(6), one Co(3), and one C(7) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one Li(5), one Co(1), and one C(8) atom.
Li3Co2(CO3)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(13), one O(3), one O(5), and one O(7) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Li(1)-O(13) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(5) bond length is 1.92 Å. The Li(1)-O(7) bond length is 1.92 Å. In the second Li site, Li(2) is bonded to one O(14), one O(4), one O(6), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra and  an edgeedge with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 44°. The Li(2)-O(14) bond length is 2.00 Å. The Li(2)-O(4) bond length is 2.15 Å. The Li(2)-O(6) bond length is 1.91 Å. The Li(2)-O(8) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one O(15), one O(17), one O(22), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra and  a cornercorner with one Li(5)O5 square pyramid. The corner-sharing octahedral tilt angles are 37°. The Li(3)-O(15) bond length is 2.08 Å. The Li(3)-O(17) bond length is 1.98 Å. The Li(3)-O(22) bond length is 1.98 Å. The Li(3)-O(9) bond length is 2.04 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(16), one O(18), and one O(21) atom to form LiO4 trigonal pyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 61°. The Li(4)-O(10) bond length is 2.03 Å. The Li(4)-O(16) bond length is 2.04 Å. The Li(4)-O(18) bond length is 1.99 Å. The Li(4)-O(21) bond length is 2.01 Å. In the fifth Li site, Li(5) is bonded to one O(15), one O(19), one O(2), one O(21), and one O(24) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Co(2)O5 trigonal bipyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The Li(5)-O(15) bond length is 2.10 Å. The Li(5)-O(19) bond length is 2.36 Å. The Li(5)-O(2) bond length is 2.02 Å. The Li(5)-O(21) bond length is 2.21 Å. The Li(5)-O(24) bond length is 2.14 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(16), one O(20), one O(22), and one O(23) atom. The Li(6)-O(1) bond length is 2.02 Å. The Li(6)-O(16) bond length is 2.01 Å. The Li(6)-O(20) bond length is 2.15 Å. The Li(6)-O(22) bond length is 2.18 Å. The Li(6)-O(23) bond length is 2.29 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(17), one O(2), one O(21), one O(24), one O(5), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(5)O5 square pyramid. The Co(1)-O(17) bond length is 2.14 Å. The Co(1)-O(2) bond length is 2.07 Å. The Co(1)-O(21) bond length is 2.27 Å. The Co(1)-O(24) bond length is 2.07 Å. The Co(1)-O(5) bond length is 2.19 Å. The Co(1)-O(8) bond length is 2.11 Å. In the second Co site, Co(2) is bonded to one O(10), one O(11), one O(14), one O(19), and one O(4) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Co(2)-O(10) bond length is 2.01 Å. The Co(2)-O(11) bond length is 1.95 Å. The Co(2)-O(14) bond length is 2.01 Å. The Co(2)-O(19) bond length is 1.88 Å. The Co(2)-O(4) bond length is 1.96 Å. In the third Co site, Co(3) is bonded in a 6-coordinate geometry to one O(1), one O(18), one O(22), one O(23), one O(6), and one O(7) atom. The Co(3)-O(1) bond length is 2.08 Å. The Co(3)-O(18) bond length is 2.11 Å. The Co(3)-O(22) bond length is 2.33 Å. The Co(3)-O(23) bond length is 2.04 Å. The Co(3)-O(6) bond length is 2.26 Å. The Co(3)-O(7) bond length is 2.07 Å. In the fourth Co site, Co(4) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(15), one O(20), one O(3), and one O(9) atom. The Co(4)-O(12) bond length is 2.05 Å. The Co(4)-O(13) bond length is 1.98 Å. The Co(4)-O(15) bond length is 2.28 Å. The Co(4)-O(20) bond length is 2.02 Å. The Co(4)-O(3) bond length is 2.10 Å. The Co(4)-O(9) bond length is 1.96 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(11), and one O(4) atom. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(11) bond length is 1.30 Å. The C(1)-O(4) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(3) atom. The C(2)-O(12) bond length is 1.30 Å. The C(2)-O(2) bond length is 1.28 Å. The C(2)-O(3) bond length is 1.30 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(5), one O(8), and one O(9) atom. The C(3)-O(5) bond length is 1.28 Å. The C(3)-O(8) bond length is 1.30 Å. The C(3)-O(9) bond length is 1.32 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(6), and one O(7) atom. The C(4)-O(10) bond length is 1.32 Å. The C(4)-O(6) bond length is 1.28 Å. The C(4)-O(7) bond length is 1.30 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(13), one O(17), and one O(21) atom. The C(5)-O(13) bond length is 1.31 Å. The C(5)-O(17) bond length is 1.29 Å. The C(5)-O(21) bond length is 1.30 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(14), one O(18), and one O(22) atom. The C(6)-O(14) bond length is 1.31 Å. The C(6)-O(18) bond length is 1.29 Å. The C(6)-O(22) bond length is 1.29 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(15), one O(20), and one O(23) atom. The C(7)-O(15) bond length is 1.31 Å. The C(7)-O(20) bond length is 1.31 Å. The C(7)-O(23) bond length is 1.27 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one O(16), one O(19), and one O(24) atom. The C(8)-O(16) bond length is 1.28 Å. The C(8)-O(19) bond length is 1.32 Å. The C(8)-O(24) bond length is 1.28 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(6), one Co(3), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(5), one Co(1), and one C(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Co(4), and one C(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Co(2), and one C(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Co(3), and one C(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(3), and one C(4) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Co(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one Co(4), and one C(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(4), one Co(2), and one C(4) atom. In the eleventh O site, O(11) is bonded in an L-shaped geometry to one Co(2) and one C(1) atom. In the twelfth O site, O(12) is bonded in an L-shaped geometry to one Co(4) and one C(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(4), and one C(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(2), and one C(6) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Co(4), and one C(7) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Li(6), and one C(8) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(3), one Co(1), and one C(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(4), one Co(3), and one C(6) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(5), one Co(2), and one C(8) atom. In the twentieth O site, O(20) is bonded in a T-shaped geometry to one Li(6), one Co(4), and one C(7) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Co(1), and one C(5) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Co(3), and one C(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(6), one Co(3), and one C(7) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one Li(5), one Co(1), and one C(8) atom.