Li2TiCo2O5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Ti(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(1) atoms to form TiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and three equivalent O(4) atoms to form distorted CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second Co site, Co(2) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), two equivalent Ti(1), and one Co(1) atom to form OLi3Ti2Co octahedra that share corners with two equivalent O(4)LiTiCo4 octahedra, corners with four equivalent O(1)Li3Ti2Co octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, and edges with three equivalent O(2)Li3TiCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to three equivalent Li(1), one Ti(1), one Co(1), and one Co(2) atom to form OLi3TiCo2 octahedra that share corners with two equivalent O(5)Li2Ti2Co2 octahedra, corners with two equivalent O(3)Li3Co3 octahedra, corners with two equivalent O(2)Li3TiCo2 octahedra,  an edgeedge with one O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with three equivalent O(1)Li3Ti2Co octahedra, and edges with four equivalent O(4)LiTiCo4 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(2)Li3TiCo2 octahedra, corners with four equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with three equivalent O(1)Li3Ti2Co octahedra, and edges with three equivalent O(4)LiTiCo4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), one Co(2), and three equivalent Co(1) atoms to form distorted OLiTiCo4 octahedra that share corners with two equivalent O(6)Li2Ti2Co2 octahedra, corners with two equivalent O(1)Li3Ti2Co octahedra, corners with two equivalent O(4)LiTiCo4 octahedra,  an edgeedge with one O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(1)Li3Ti2Co octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(2)Li3TiCo2 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the fifth O site, O(5) is bonded to two equivalent Li(2), two equivalent Ti(1), and two equivalent Co(2) atoms to form OLi2Ti2Co2 octahedra that share corners with two equivalent O(5)Li2Ti2Co2 octahedra, corners with four equivalent O(2)Li3TiCo2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(1)Li3Ti2Co octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the sixth O site, O(6) is bonded to two equivalent Li(3), two equivalent Ti(1), and two equivalent Co(2) atoms to form OLi2Ti2Co2 octahedra that share corners with two equivalent O(6)Li2Ti2Co2 octahedra, corners with four equivalent O(4)LiTiCo4 octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(1)Li3Ti2Co octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Li2TiCo2O5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(4) bond length is 2.03 Å. There are a spread of Li(1)-O(2) bond distances ranging from 2.05-2.36 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Li(2)-O(1) bond lengths are 2.10 Å. Both Li(2)-O(3) bond lengths are 2.18 Å. Both Li(2)-O(5) bond lengths are 2.06 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Both Li(3)-O(1) bond lengths are 2.08 Å. Both Li(3)-O(3) bond lengths are 2.22 Å. Both Li(3)-O(6) bond lengths are 2.06 Å. Ti(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(1) atoms to form TiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Ti(1)-O(2) bond length is 1.87 Å. The Ti(1)-O(4) bond length is 1.97 Å. The Ti(1)-O(5) bond length is 2.18 Å. The Ti(1)-O(6) bond length is 2.11 Å. There is one shorter (1.87 Å) and one longer (2.26 Å) Ti(1)-O(1) bond length. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and three equivalent O(4) atoms to form distorted CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Co(1)-O(1) bond length is 2.19 Å. The Co(1)-O(2) bond length is 2.17 Å. The Co(1)-O(3) bond length is 1.98 Å. There are a spread of Co(1)-O(4) bond distances ranging from 2.06-2.48 Å. In the second Co site, Co(2) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. The Co(2)-O(2) bond length is 2.14 Å. The Co(2)-O(4) bond length is 2.15 Å. The Co(2)-O(5) bond length is 2.12 Å. The Co(2)-O(6) bond length is 2.10 Å. There is one shorter (2.06 Å) and one longer (2.08 Å) Co(2)-O(3) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), two equivalent Ti(1), and one Co(1) atom to form OLi3Ti2Co octahedra that share corners with two equivalent O(4)LiTiCo4 octahedra, corners with four equivalent O(1)Li3Ti2Co octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, and edges with three equivalent O(2)Li3TiCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to three equivalent Li(1), one Ti(1), one Co(1), and one Co(2) atom to form OLi3TiCo2 octahedra that share corners with two equivalent O(5)Li2Ti2Co2 octahedra, corners with two equivalent O(3)Li3Co3 octahedra, corners with two equivalent O(2)Li3TiCo2 octahedra,  an edgeedge with one O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with three equivalent O(1)Li3Ti2Co octahedra, and edges with four equivalent O(4)LiTiCo4 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(2)Li3TiCo2 octahedra, corners with four equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with three equivalent O(1)Li3Ti2Co octahedra, and edges with three equivalent O(4)LiTiCo4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), one Co(2), and three equivalent Co(1) atoms to form distorted OLiTiCo4 octahedra that share corners with two equivalent O(6)Li2Ti2Co2 octahedra, corners with two equivalent O(1)Li3Ti2Co octahedra, corners with two equivalent O(4)LiTiCo4 octahedra,  an edgeedge with one O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(1)Li3Ti2Co octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(2)Li3TiCo2 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the fifth O site, O(5) is bonded to two equivalent Li(2), two equivalent Ti(1), and two equivalent Co(2) atoms to form OLi2Ti2Co2 octahedra that share corners with two equivalent O(5)Li2Ti2Co2 octahedra, corners with four equivalent O(2)Li3TiCo2 octahedra, edges with two equivalent O(6)Li2Ti2Co2 octahedra, edges with two equivalent O(4)LiTiCo4 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(1)Li3Ti2Co octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the sixth O site, O(6) is bonded to two equivalent Li(3), two equivalent Ti(1), and two equivalent Co(2) atoms to form OLi2Ti2Co2 octahedra that share corners with two equivalent O(6)Li2Ti2Co2 octahedra, corners with four equivalent O(4)LiTiCo4 octahedra, edges with two equivalent O(5)Li2Ti2Co2 octahedra, edges with two equivalent O(2)Li3TiCo2 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with four equivalent O(1)Li3Ti2Co octahedra. The corner-sharing octahedral tilt angles range from 0-9°.