Li4Cu7(PO4)6 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(10) atoms. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(5), one O(7), and one O(9) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(8) atoms. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(12), one O(13), one O(14), one O(3), one O(8), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Cu(4)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(5), one O(6), and one O(9) atom. In the third Cu site, Cu(3) is bonded to one O(11), one O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-64°. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(10), one O(12), one O(3), one O(4), and one O(5) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. In the second P site, P(2) is bonded to one O(2), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra and corners with two equivalent Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. In the third P site, P(3) is bonded to one O(11), one O(7), and two equivalent O(13) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra and corners with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(4), and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Cu(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(3), one Cu(3), one Cu(4), and one P(1) atom to form distorted edge-sharing OLiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Cu(2), one Cu(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one Cu(1), one Cu(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(2), one Cu(1), one Cu(2), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(4), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Cu(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one Cu(1) and one P(1) atom.
Li4Cu7(PO4)6 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(10) atoms. The Li(1)-O(2) bond length is 1.99 Å. Both Li(1)-O(10) bond lengths are 2.33 Å. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(5), one O(7), and one O(9) atom. The Li(2)-O(5) bond length is 2.23 Å. The Li(2)-O(7) bond length is 2.21 Å. The Li(2)-O(9) bond length is 1.96 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(8) atoms. Both Li(3)-O(4) bond lengths are 2.12 Å. Both Li(3)-O(8) bond lengths are 2.53 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(12), one O(13), one O(14), one O(3), one O(8), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Cu(4)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. The Cu(1)-O(12) bond length is 2.19 Å. The Cu(1)-O(13) bond length is 2.14 Å. The Cu(1)-O(14) bond length is 1.93 Å. The Cu(1)-O(3) bond length is 1.96 Å. The Cu(1)-O(8) bond length is 2.15 Å. The Cu(1)-O(9) bond length is 2.48 Å. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(5), one O(6), and one O(9) atom. The Cu(2)-O(1) bond length is 1.97 Å. The Cu(2)-O(13) bond length is 1.93 Å. The Cu(2)-O(5) bond length is 2.13 Å. The Cu(2)-O(6) bond length is 2.30 Å. The Cu(2)-O(9) bond length is 2.25 Å. In the third Cu site, Cu(3) is bonded to one O(11), one O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-64°. The Cu(3)-O(11) bond length is 2.17 Å. The Cu(3)-O(2) bond length is 2.62 Å. Both Cu(3)-O(4) bond lengths are 2.02 Å. Both Cu(3)-O(8) bond lengths are 1.99 Å. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(10), one O(12), one O(3), one O(4), and one O(5) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The Cu(4)-O(1) bond length is 2.05 Å. The Cu(4)-O(10) bond length is 1.94 Å. The Cu(4)-O(12) bond length is 1.96 Å. The Cu(4)-O(3) bond length is 2.25 Å. The Cu(4)-O(4) bond length is 2.16 Å. The Cu(4)-O(5) bond length is 2.34 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The P(1)-O(14) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(2), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra and corners with two equivalent Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. The P(2)-O(2) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.56 Å. Both P(2)-O(1) bond lengths are 1.58 Å. In the third P site, P(3) is bonded to one O(11), one O(7), and two equivalent O(13) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(3)O6 octahedra and corners with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The P(3)-O(11) bond length is 1.51 Å. The P(3)-O(7) bond length is 1.55 Å. Both P(3)-O(13) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. The P(4)-O(10) bond length is 1.54 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(8) bond length is 1.59 Å. The P(4)-O(9) bond length is 1.55 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(4), and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Cu(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(3), one Cu(3), one Cu(4), and one P(1) atom to form distorted edge-sharing OLiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Cu(2), one Cu(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Cu(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one Cu(1), one Cu(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(2), one Cu(1), one Cu(2), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(4), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Cu(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one Cu(1) and one P(1) atom.