LiCu3(CO3)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), two equivalent O(7), and two equivalent O(9) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Cu(6)O4 tetrahedra and edges with two equivalent Li(1)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(27), two equivalent O(10), and two equivalent O(8) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cu(9)O4 tetrahedra and edges with two equivalent Li(2)O5 square pyramids. In the third Li site, Li(3) is bonded to one O(18), two equivalent O(22), and two equivalent O(24) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(8)O4 tetrahedra, and edges with two equivalent Li(3)O5 square pyramids. There are nine inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one O(2), one O(6), one O(7), and two equivalent O(4) atoms. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one O(10), one O(6), and two equivalent O(5) atoms. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one O(14), one O(8), and two equivalent O(15) atoms. In the fourth Cu site, Cu(4) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(13), and two equivalent O(16) atoms. In the fifth Cu site, Cu(5) is bonded to one O(12), one O(21), and two equivalent O(18) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(3)O5 square pyramids and corners with two equivalent Cu(5)O4 tetrahedra. In the sixth Cu site, Cu(6) is bonded to one O(23), one O(9), and two equivalent O(17) atoms to form distorted CuO4 tetrahedra that share corners with two equivalent Cu(6)O4 tetrahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. In the seventh Cu site, Cu(7) is bonded in a 4-coordinate geometry to one O(1), one O(24), and two equivalent O(19) atoms. In the eighth Cu site, Cu(8) is bonded to one O(22), one O(3), and two equivalent O(26) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(3)O5 square pyramids and corners with two equivalent Cu(8)O4 tetrahedra. In the ninth Cu site, Cu(9) is bonded to one O(20), one O(25), and two equivalent O(27) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(2)O5 square pyramids and corners with two equivalent Cu(9)O4 tetrahedra. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(24), and one O(3) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(11), one O(6), and one O(7) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(13), one O(25), 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(12), and one O(14) atom. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(15), one O(17), and one O(4) atom. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(16), one O(18), and one O(19) atom. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(21), one O(22), and one O(23) 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. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one O(26), one O(27), and one O(5) atom. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Cu(7) and one C(8) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Cu(8) and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Cu(1), and one C(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one C(9) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one C(2) atom. In the seventh O site, O(7) is bonded to two equivalent Li(1), one Cu(1), and one C(2) atom to form a mixture of distorted edge and corner-sharing OLi2CuC tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Li(2), one Cu(3), and one C(8) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, corners with two equivalent O(27)LiCu2C tetrahedra, and  an edgeedge with one O(10)Li2CuC tetrahedra. In the ninth O site, O(9) is bonded to two equivalent Li(1), one Cu(6), and one C(3) atom to form a mixture of distorted edge and corner-sharing OLi2CuC tetrahedra. In the tenth O site, O(10) is bonded to two equivalent Li(2), one Cu(2), and one C(4) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, corners with two equivalent O(27)LiCu2C tetrahedra, and  an edgeedge with one O(8)Li2CuC tetrahedra. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(2) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Cu(5) and one C(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Cu(3) and one C(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one C(5) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Cu(4) and one C(6) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Cu(6) and one C(5) atom. In the eighteenth O site, O(18) is bonded to one Li(3), two equivalent Cu(5), and one C(6) atom to form distorted OLiCu2C tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, and corners with two equivalent O(18)LiCu2C tetrahedra. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to two equivalent Cu(7) and one C(6) atom. In the twentieth O site, O(20) is bonded in a distorted bent 120 degrees geometry to one Cu(9) and one C(8) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Cu(5) and one C(7) atom. In the twenty-second O site, O(22) is bonded to two equivalent Li(3), one Cu(8), and one C(7) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, corners with two equivalent O(18)LiCu2C tetrahedra, and  an edgeedge with one O(24)Li2CuC tetrahedra. In the twenty-third O site, O(23) is bonded in a distorted water-like geometry to one Cu(6) and one C(7) atom. In the twenty-fourth O site, O(24) is bonded to two equivalent Li(3), one Cu(7), and one C(1) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, corners with two equivalent O(18)LiCu2C tetrahedra, and  an edgeedge with one O(22)Li2CuC tetrahedra. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one Cu(9) and one C(3) atom. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to two equivalent Cu(8) and one C(9) atom. In the twenty-seventh O site, O(27) is bonded to one Li(2), two equivalent Cu(9), and one C(9) atom to form distorted OLiCu2C tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, and corners with two equivalent O(27)LiCu2C tetrahedra.
LiCu3(CO3)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), two equivalent O(7), and two equivalent O(9) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Cu(6)O4 tetrahedra and edges with two equivalent Li(1)O5 trigonal bipyramids. The Li(1)-O(4) bond length is 1.99 Å. There is one shorter (2.16 Å) and one longer (2.18 Å) Li(1)-O(7) bond length. There is one shorter (2.14 Å) and one longer (2.23 Å) Li(1)-O(9) bond length. In the second Li site, Li(2) is bonded to one O(27), two equivalent O(10), and two equivalent O(8) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cu(9)O4 tetrahedra and edges with two equivalent Li(2)O5 square pyramids. The Li(2)-O(27) bond length is 2.00 Å. There is one shorter (2.17 Å) and one longer (2.25 Å) Li(2)-O(10) bond length. There is one shorter (2.13 Å) and one longer (2.14 Å) Li(2)-O(8) bond length. In the third Li site, Li(3) is bonded to one O(18), two equivalent O(22), and two equivalent O(24) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(8)O4 tetrahedra, and edges with two equivalent Li(3)O5 square pyramids. The Li(3)-O(18) bond length is 2.00 Å. Both Li(3)-O(22) bond lengths are 2.14 Å. There is one shorter (2.20 Å) and one longer (2.28 Å) Li(3)-O(24) bond length. There are nine inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one O(2), one O(6), one O(7), and two equivalent O(4) atoms. The Cu(1)-O(2) bond length is 1.88 Å. The Cu(1)-O(6) bond length is 2.40 Å. The Cu(1)-O(7) bond length is 1.98 Å. There is one shorter (2.27 Å) and one longer (2.40 Å) Cu(1)-O(4) bond length. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one O(10), one O(6), and two equivalent O(5) atoms. The Cu(2)-O(10) bond length is 1.94 Å. The Cu(2)-O(6) bond length is 1.94 Å. There is one shorter (2.18 Å) and one longer (2.20 Å) Cu(2)-O(5) bond length. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one O(14), one O(8), and two equivalent O(15) atoms. The Cu(3)-O(14) bond length is 1.93 Å. The Cu(3)-O(8) bond length is 1.99 Å. There is one shorter (2.04 Å) and one longer (2.08 Å) Cu(3)-O(15) bond length. In the fourth Cu site, Cu(4) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(13), and two equivalent O(16) atoms. The Cu(4)-O(11) bond length is 1.95 Å. The Cu(4)-O(13) bond length is 1.90 Å. There is one shorter (2.14 Å) and one longer (2.17 Å) Cu(4)-O(16) bond length. In the fifth Cu site, Cu(5) is bonded to one O(12), one O(21), and two equivalent O(18) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(3)O5 square pyramids and corners with two equivalent Cu(5)O4 tetrahedra. The Cu(5)-O(12) bond length is 1.92 Å. The Cu(5)-O(21) bond length is 1.96 Å. There is one shorter (2.18 Å) and one longer (2.21 Å) Cu(5)-O(18) bond length. In the sixth Cu site, Cu(6) is bonded to one O(23), one O(9), and two equivalent O(17) atoms to form distorted CuO4 tetrahedra that share corners with two equivalent Cu(6)O4 tetrahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. The Cu(6)-O(23) bond length is 1.94 Å. The Cu(6)-O(9) bond length is 2.03 Å. There is one shorter (1.98 Å) and one longer (2.23 Å) Cu(6)-O(17) bond length. In the seventh Cu site, Cu(7) is bonded in a 4-coordinate geometry to one O(1), one O(24), and two equivalent O(19) atoms. The Cu(7)-O(1) bond length is 1.96 Å. The Cu(7)-O(24) bond length is 2.00 Å. There is one shorter (2.00 Å) and one longer (2.19 Å) Cu(7)-O(19) bond length. In the eighth Cu site, Cu(8) is bonded to one O(22), one O(3), and two equivalent O(26) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(3)O5 square pyramids and corners with two equivalent Cu(8)O4 tetrahedra. The Cu(8)-O(22) bond length is 1.98 Å. The Cu(8)-O(3) bond length is 1.94 Å. There is one shorter (2.06 Å) and one longer (2.13 Å) Cu(8)-O(26) bond length. In the ninth Cu site, Cu(9) is bonded to one O(20), one O(25), and two equivalent O(27) atoms to form CuO4 tetrahedra that share corners with two equivalent Li(2)O5 square pyramids and corners with two equivalent Cu(9)O4 tetrahedra. The Cu(9)-O(20) bond length is 1.97 Å. The Cu(9)-O(25) bond length is 1.89 Å. There is one shorter (2.08 Å) and one longer (2.26 Å) Cu(9)-O(27) bond length. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(24), and one O(3) atom. The C(1)-O(2) bond length is 1.28 Å. The C(1)-O(24) bond length is 1.32 Å. The C(1)-O(3) bond length is 1.28 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(11), one O(6), and one O(7) atom. The C(2)-O(11) bond length is 1.27 Å. The C(2)-O(6) bond length is 1.29 Å. The C(2)-O(7) bond length is 1.31 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(13), one O(25), and one O(9) atom. The C(3)-O(13) bond length is 1.28 Å. The C(3)-O(25) bond length is 1.27 Å. The C(3)-O(9) bond length is 1.33 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(14) atom. The C(4)-O(10) bond length is 1.33 Å. The C(4)-O(12) bond length is 1.27 Å. The C(4)-O(14) bond length is 1.28 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one O(15), one O(17), and one O(4) atom. The C(5)-O(15) bond length is 1.30 Å. The C(5)-O(17) bond length is 1.31 Å. The C(5)-O(4) bond length is 1.29 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one O(16), one O(18), and one O(19) atom. The C(6)-O(16) bond length is 1.28 Å. The C(6)-O(18) bond length is 1.33 Å. The C(6)-O(19) bond length is 1.30 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one O(21), one O(22), and one O(23) atom. The C(7)-O(21) bond length is 1.28 Å. The C(7)-O(22) bond length is 1.32 Å. The C(7)-O(23) bond length is 1.28 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 1.28 Å. The C(8)-O(20) bond length is 1.28 Å. The C(8)-O(8) bond length is 1.32 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one O(26), one O(27), and one O(5) atom. The C(9)-O(26) bond length is 1.30 Å. The C(9)-O(27) bond length is 1.32 Å. The C(9)-O(5) bond length is 1.28 Å. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Cu(7) and one C(8) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Cu(8) and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Cu(1), and one C(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one C(9) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one C(2) atom. In the seventh O site, O(7) is bonded to two equivalent Li(1), one Cu(1), and one C(2) atom to form a mixture of distorted edge and corner-sharing OLi2CuC tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Li(2), one Cu(3), and one C(8) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, corners with two equivalent O(27)LiCu2C tetrahedra, and  an edgeedge with one O(10)Li2CuC tetrahedra. In the ninth O site, O(9) is bonded to two equivalent Li(1), one Cu(6), and one C(3) atom to form a mixture of distorted edge and corner-sharing OLi2CuC tetrahedra. In the tenth O site, O(10) is bonded to two equivalent Li(2), one Cu(2), and one C(4) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, corners with two equivalent O(27)LiCu2C tetrahedra, and  an edgeedge with one O(8)Li2CuC tetrahedra. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(2) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Cu(5) and one C(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Cu(3) and one C(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one C(5) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Cu(4) and one C(6) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Cu(6) and one C(5) atom. In the eighteenth O site, O(18) is bonded to one Li(3), two equivalent Cu(5), and one C(6) atom to form distorted OLiCu2C tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, and corners with two equivalent O(18)LiCu2C tetrahedra. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to two equivalent Cu(7) and one C(6) atom. In the twentieth O site, O(20) is bonded in a distorted bent 120 degrees geometry to one Cu(9) and one C(8) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Cu(5) and one C(7) atom. In the twenty-second O site, O(22) is bonded to two equivalent Li(3), one Cu(8), and one C(7) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, corners with two equivalent O(18)LiCu2C tetrahedra, and  an edgeedge with one O(24)Li2CuC tetrahedra. In the twenty-third O site, O(23) is bonded in a distorted water-like geometry to one Cu(6) and one C(7) atom. In the twenty-fourth O site, O(24) is bonded to two equivalent Li(3), one Cu(7), and one C(1) atom to form distorted OLi2CuC tetrahedra that share corners with two equivalent O(22)Li2CuC tetrahedra, corners with two equivalent O(24)Li2CuC tetrahedra, corners with two equivalent O(18)LiCu2C tetrahedra, and  an edgeedge with one O(22)Li2CuC tetrahedra. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one Cu(9) and one C(3) atom. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to two equivalent Cu(8) and one C(9) atom. In the twenty-seventh O site, O(27) is bonded to one Li(2), two equivalent Cu(9), and one C(9) atom to form distorted OLiCu2C tetrahedra that share corners with two equivalent O(10)Li2CuC tetrahedra, corners with two equivalent O(8)Li2CuC tetrahedra, and corners with two equivalent O(27)LiCu2C tetrahedra.