Li5Cu6(P2O7)4 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(10), one O(3), one O(8), and two equivalent O(2) atoms to form distorted 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(1)O5 trigonal bipyramid, and edges with two equivalent Cu(2)O5 trigonal bipyramids. In the second Li site, Li(2) 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 third Li site, Li(3) is bonded to two equivalent O(14), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with two equivalent Cu(2)O5 trigonal bipyramids, and edges with two equivalent P(3)O4 tetrahedra. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. In the second Cu site, Cu(2) is bonded to one O(10), one O(13), one O(2), one O(7), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Cu(3)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(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-72°. In the third Cu site, Cu(3) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form distorted CuO6 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 Cu(2)O5 trigonal bipyramid,  an edgeedge with one Cu(3)O6 octahedra, and  an edgeedge with one Cu(4)O6 octahedra. In the fourth Cu site, Cu(4) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CuO6 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 Cu(3)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 Cu(4)O6 octahedra, corners with three equivalent Cu(3)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-58°. 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(3)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. 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 Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Cu(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-59°. 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(3)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 53-56°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(2), one Cu(3), 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(1), one Cu(2), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Cu(1), 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(2), one Cu(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Cu(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(3), one Cu(1), one Cu(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cu(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(4), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Cu(3), one Cu(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(3), one P(3), and one P(4) atom.
Li5Cu6(P2O7)4 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(10), one O(3), one O(8), and two equivalent O(2) atoms to form distorted 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(1)O5 trigonal bipyramid, and edges with two equivalent Cu(2)O5 trigonal bipyramids. The Li(1)-O(10) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.20 Å. The Li(1)-O(8) bond length is 1.98 Å. There is one shorter (2.10 Å) and one longer (2.40 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) 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(2)-O(1) bond length is 2.15 Å. The Li(2)-O(12) bond length is 1.99 Å. The Li(2)-O(3) bond length is 1.91 Å. There is one shorter (2.09 Å) and one longer (2.53 Å) Li(2)-O(5) bond length. In the third Li site, Li(3) is bonded to two equivalent O(14), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with two equivalent Cu(2)O5 trigonal bipyramids, and edges with two equivalent P(3)O4 tetrahedra. Both Li(3)-O(14) bond lengths are 2.01 Å. Both Li(3)-O(6) bond lengths are 2.11 Å. Both Li(3)-O(7) bond lengths are 2.31 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. Both Cu(1)-O(3) bond lengths are 2.60 Å. Both Cu(1)-O(6) bond lengths are 1.97 Å. Both Cu(1)-O(7) bond lengths are 2.19 Å. In the second Cu site, Cu(2) is bonded to one O(10), one O(13), one O(2), one O(7), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Cu(3)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(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-72°. The Cu(2)-O(10) bond length is 1.98 Å. The Cu(2)-O(13) bond length is 1.99 Å. The Cu(2)-O(2) bond length is 2.05 Å. The Cu(2)-O(7) bond length is 2.02 Å. The Cu(2)-O(8) bond length is 2.29 Å. In the third Cu site, Cu(3) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form distorted CuO6 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 Cu(2)O5 trigonal bipyramid,  an edgeedge with one Cu(3)O6 octahedra, and  an edgeedge with one Cu(4)O6 octahedra. The Cu(3)-O(1) bond length is 1.97 Å. The Cu(3)-O(12) bond length is 2.00 Å. The Cu(3)-O(13) bond length is 2.52 Å. The Cu(3)-O(9) bond length is 2.46 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Cu(3)-O(11) bond length. In the fourth Cu site, Cu(4) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CuO6 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 Cu(3)O6 octahedra. Both Cu(4)-O(12) bond lengths are 2.34 Å. Both Cu(4)-O(5) bond lengths are 1.97 Å. Both Cu(4)-O(9) bond lengths are 2.04 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 Cu(4)O6 octahedra, corners with three equivalent Cu(3)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-58°. 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(3)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. The P(2)-O(13) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.64 Å. The P(2)-O(6) bond length is 1.54 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 Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Cu(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-59°. The P(3)-O(14) bond length is 1.64 Å. The P(3)-O(3) bond length is 1.51 Å. The P(3)-O(7) bond length is 1.56 Å. The P(3)-O(9) bond length is 1.53 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(3)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 53-56°. 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 1.64 Å. The P(4)-O(8) bond length is 1.51 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(2), one Cu(3), 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(1), one Cu(2), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Cu(1), 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(2), one Cu(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Cu(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(3), one Cu(1), one Cu(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cu(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(4), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Cu(3), one Cu(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(3), one P(3), and one P(4) atom.