Li6Co5(P2O7)4 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. In the second Li site, Li(2) is bonded to one O(10), one O(3), one O(8), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and edges with two equivalent Co(1)O5 trigonal bipyramids. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), and two equivalent O(5) atoms. In the fourth Li site, Li(4) is bonded to two equivalent O(14), two equivalent O(6), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with two equivalent Co(1)O5 trigonal bipyramids, and edges with two equivalent P(3)O4 tetrahedra. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(13), one O(2), one O(7), and one O(8) atom to form CoO5 trigonal bipyramids that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-73°. In the second Co site, Co(2) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Co(3)O6 octahedra. In the third Co site, Co(3) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-59°. In the second P site, P(2) is bonded to one O(13), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-63°. In the third P site, P(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Co(1)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-63°. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-57°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one Co(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(3), one Co(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Co(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Co(2), one Co(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the twelfth O site, O(12) is bonded to one Li(3), one Co(2), one Co(3), and one P(4) atom to form distorted corner-sharing OLiCo2P trigonal pyramids. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one P(3), and one P(4) atom.
Li6Co5(P2O7)4 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. Both Li(1)-O(3) bond lengths are 2.55 Å. Both Li(1)-O(6) bond lengths are 2.04 Å. Both Li(1)-O(7) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to one O(10), one O(3), one O(8), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and edges with two equivalent Co(1)O5 trigonal bipyramids. The Li(2)-O(10) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.17 Å. The Li(2)-O(8) bond length is 2.09 Å. There is one shorter (2.17 Å) and one longer (2.29 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), and two equivalent O(5) atoms. The Li(3)-O(1) bond length is 2.19 Å. The Li(3)-O(12) bond length is 2.04 Å. The Li(3)-O(3) bond length is 1.93 Å. There is one shorter (2.04 Å) and one longer (2.53 Å) Li(3)-O(5) bond length. In the fourth Li site, Li(4) is bonded to two equivalent O(14), two equivalent O(6), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with two equivalent Co(1)O5 trigonal bipyramids, and edges with two equivalent P(3)O4 tetrahedra. Both Li(4)-O(14) bond lengths are 2.01 Å. Both Li(4)-O(6) bond lengths are 2.06 Å. Both Li(4)-O(7) bond lengths are 2.26 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(13), one O(2), one O(7), and one O(8) atom to form CoO5 trigonal bipyramids that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-73°. The Co(1)-O(10) bond length is 2.04 Å. The Co(1)-O(13) bond length is 2.12 Å. The Co(1)-O(2) bond length is 2.12 Å. The Co(1)-O(7) bond length is 2.02 Å. The Co(1)-O(8) bond length is 2.11 Å. In the second Co site, Co(2) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Co(3)O6 octahedra. The Co(2)-O(1) bond length is 2.03 Å. The Co(2)-O(12) bond length is 2.08 Å. The Co(2)-O(13) bond length is 2.19 Å. The Co(2)-O(9) bond length is 2.27 Å. There is one shorter (2.06 Å) and one longer (2.16 Å) Co(2)-O(11) bond length. In the third Co site, Co(3) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. Both Co(3)-O(12) bond lengths are 2.18 Å. Both Co(3)-O(5) bond lengths are 2.03 Å. Both Co(3)-O(9) bond lengths are 2.12 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-59°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(11) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(5) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(13), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-63°. The P(2)-O(13) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.65 Å. The P(2)-O(6) bond length is 1.51 Å. In the third P site, P(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Co(1)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-63°. The P(3)-O(14) bond length is 1.65 Å. The P(3)-O(3) bond length is 1.52 Å. The P(3)-O(7) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-57°. The P(4)-O(10) bond length is 1.53 Å. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(14) bond length is 1.61 Å. The P(4)-O(8) bond length is 1.52 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one Co(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(3), one Co(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Co(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Co(2), one Co(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the twelfth O site, O(12) is bonded to one Li(3), one Co(2), one Co(3), and one P(4) atom to form distorted corner-sharing OLiCo2P trigonal pyramids. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one P(3), and one P(4) atom.