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 square co-planar geometry to two equivalent O(10) and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(7), one O(8), and two equivalent O(4) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(6), one O(7), one O(8), and one O(9) atom. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(10), one O(12), one O(13), one O(14), one O(2), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Cu(3)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 65°. In the second Cu site, Cu(2) is bonded to one O(11), one O(3), two equivalent O(10), and two equivalent O(5) atoms to form 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 65-67°. In the third Cu site, Cu(3) is bonded to one O(13), one O(4), one O(6), and one O(9) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-86°. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Cu(3)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 67°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O4 tetrahedra, and  an edgeedge with one Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-61°. In the second P site, P(2) is bonded to one O(3), one O(7), and two equivalent O(4) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra, and corners with two equivalent Cu(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-61°. In the third P site, P(3) is bonded to one O(11), one O(8), and two equivalent O(13) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent Cu(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-60°. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one Cu(3)O4 tetrahedra, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-61°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(4) and one P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Cu(3), one Cu(4), and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Cu(2), one Cu(4), and one P(1) atom to form a mixture of edge and corner-sharing OLiCu2P tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one Cu(3), one Cu(4), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(3), one Cu(1), one Cu(3), and one P(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Cu(1), one Cu(2), and one P(4) atom to form a mixture of edge and corner-sharing OLiCu2P tetrahedra. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Cu(2) 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 trigonal planar geometry to one Cu(1), one Cu(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees 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 square co-planar geometry to two equivalent O(10) and two equivalent O(5) atoms. Both Li(1)-O(10) bond lengths are 2.23 Å. Both Li(1)-O(5) bond lengths are 2.29 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(7), one O(8), and two equivalent O(4) atoms. The Li(2)-O(7) bond length is 2.12 Å. The Li(2)-O(8) bond length is 2.19 Å. Both Li(2)-O(4) bond lengths are 2.56 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(6), one O(7), one O(8), and one O(9) atom. The Li(3)-O(6) bond length is 2.36 Å. The Li(3)-O(7) bond length is 2.29 Å. The Li(3)-O(8) bond length is 2.04 Å. The Li(3)-O(9) bond length is 1.94 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(10), one O(12), one O(13), one O(14), one O(2), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Cu(3)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 65°. The Cu(1)-O(10) bond length is 2.06 Å. The Cu(1)-O(12) bond length is 2.17 Å. The Cu(1)-O(13) bond length is 2.12 Å. The Cu(1)-O(14) bond length is 1.94 Å. The Cu(1)-O(2) bond length is 2.00 Å. The Cu(1)-O(9) bond length is 2.57 Å. In the second Cu site, Cu(2) is bonded to one O(11), one O(3), two equivalent O(10), and two equivalent O(5) atoms to form 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 65-67°. The Cu(2)-O(11) bond length is 1.96 Å. The Cu(2)-O(3) bond length is 1.98 Å. Both Cu(2)-O(10) bond lengths are 2.15 Å. Both Cu(2)-O(5) bond lengths are 2.17 Å. In the third Cu site, Cu(3) is bonded to one O(13), one O(4), one O(6), and one O(9) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-86°. The Cu(3)-O(13) bond length is 1.95 Å. The Cu(3)-O(4) bond length is 1.96 Å. The Cu(3)-O(6) bond length is 2.01 Å. The Cu(3)-O(9) bond length is 2.05 Å. In the fourth Cu site, Cu(4) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), and one O(6) atom to form distorted CuO6 octahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Cu(3)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 67°. The Cu(4)-O(1) bond length is 1.95 Å. The Cu(4)-O(12) bond length is 1.99 Å. The Cu(4)-O(2) bond length is 2.16 Å. The Cu(4)-O(4) bond length is 2.12 Å. The Cu(4)-O(5) bond length is 2.05 Å. The Cu(4)-O(6) bond length is 2.53 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra,  a cornercorner with one Cu(4)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O4 tetrahedra, and  an edgeedge with one Cu(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-61°. The P(1)-O(14) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.59 Å. The P(1)-O(6) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(3), one O(7), and two equivalent O(4) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra, and corners with two equivalent Cu(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-61°. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.54 Å. Both P(2)-O(4) bond lengths are 1.58 Å. In the third P site, P(3) is bonded to one O(11), one O(8), and two equivalent O(13) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent Cu(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-60°. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(8) bond length is 1.55 Å. Both P(3)-O(13) bond lengths are 1.57 Å. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(4)O6 octahedra,  a cornercorner with one Cu(3)O4 tetrahedra, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-61°. The P(4)-O(1) bond length is 1.54 Å. The P(4)-O(10) bond length is 1.59 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(9) bond length is 1.56 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(4) and one P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(4), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Cu(3), one Cu(4), and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Cu(2), one Cu(4), and one P(1) atom to form a mixture of edge and corner-sharing OLiCu2P tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one Cu(3), one Cu(4), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(3), one Cu(1), one Cu(3), and one P(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Cu(1), one Cu(2), and one P(4) atom to form a mixture of edge and corner-sharing OLiCu2P tetrahedra. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Cu(2) 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 trigonal planar geometry to one Cu(1), one Cu(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(1) atom.