Li4CrFe3Cu2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(3), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(17), one O(21), one O(22), and one O(5) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(18), one O(19), one O(22), and one O(23) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(16), one O(17), one O(18), one O(19), and one O(24) atom. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom to form CrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(20), one O(3), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-43°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Cu(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Cu(1), 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(1), one Fe(2), one Cu(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), one Cu(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Cr(1), one Cu(1), and one P(4) atom to form distorted OLi2CrCuP trigonal bipyramids that share corners with two equivalent O(17)Li2FeCuP trigonal bipyramids,  an edgeedge with one O(15)Li2FeCuP trigonal bipyramid, and  a faceface with one O(22)Li2CrCuP trigonal bipyramid. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(3), one Cr(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Cu(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Li(3), one Fe(3), one Cu(2), and one P(4) atom to form distorted OLi2FeCuP trigonal bipyramids that share corners with two equivalent O(22)Li2CrCuP trigonal bipyramids,  an edgeedge with one O(11)Li2CrCuP trigonal bipyramid, and  a faceface with one O(17)Li2FeCuP trigonal bipyramid. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Cr(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded to one Li(2), one Li(4), one Fe(3), one Cu(2), and one P(5) atom to form distorted OLi2FeCuP trigonal bipyramids that share  a cornercorner with one O(22)Li2CrCuP trigonal bipyramid, corners with two equivalent O(11)Li2CrCuP trigonal bipyramids, and  a faceface with one O(15)Li2FeCuP trigonal bipyramid. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(3), one Cu(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded to one Li(2), one Li(3), one Cr(1), one Cu(1), and one P(6) atom to form distorted OLi2CrCuP trigonal bipyramids that share  a cornercorner with one O(17)Li2FeCuP trigonal bipyramid, corners with two equivalent O(15)Li2FeCuP trigonal bipyramids, and  a faceface with one O(11)Li2CrCuP trigonal bipyramid. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Fe(3), and one P(1) atom.
Li4CrFe3Cu2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(3), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.10 Å. The Li(1)-O(14) bond length is 2.10 Å. The Li(1)-O(20) bond length is 2.29 Å. The Li(1)-O(3) bond length is 2.37 Å. The Li(1)-O(4) bond length is 2.30 Å. The Li(1)-O(8) bond length is 2.37 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(17), one O(21), one O(22), and one O(5) atom. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(15) bond length is 2.13 Å. The Li(2)-O(17) bond length is 2.51 Å. The Li(2)-O(21) bond length is 2.42 Å. The Li(2)-O(22) bond length is 2.52 Å. The Li(2)-O(5) bond length is 2.36 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(18), one O(19), one O(22), and one O(23) atom. The Li(3)-O(13) bond length is 2.41 Å. The Li(3)-O(15) bond length is 2.51 Å. The Li(3)-O(18) bond length is 2.56 Å. The Li(3)-O(19) bond length is 2.10 Å. The Li(3)-O(22) bond length is 2.15 Å. The Li(3)-O(23) bond length is 2.44 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(16), one O(17), one O(18), one O(19), and one O(24) atom. The Li(4)-O(11) bond length is 2.54 Å. The Li(4)-O(16) bond length is 2.38 Å. The Li(4)-O(17) bond length is 2.13 Å. The Li(4)-O(18) bond length is 2.13 Å. The Li(4)-O(19) bond length is 2.55 Å. The Li(4)-O(24) bond length is 2.47 Å. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom to form CrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Cr(1)-O(11) bond length is 2.05 Å. The Cr(1)-O(13) bond length is 1.97 Å. The Cr(1)-O(16) bond length is 1.97 Å. The Cr(1)-O(18) bond length is 2.05 Å. The Cr(1)-O(22) bond length is 2.06 Å. The Cr(1)-O(5) bond length is 1.98 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(20), one O(3), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(1)-O(12) bond length is 1.95 Å. The Fe(1)-O(14) bond length is 2.04 Å. The Fe(1)-O(20) bond length is 2.06 Å. The Fe(1)-O(3) bond length is 2.06 Å. The Fe(1)-O(7) bond length is 2.02 Å. The Fe(1)-O(9) bond length is 1.96 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(2)-O(1) bond length is 1.95 Å. The Fe(2)-O(10) bond length is 2.04 Å. The Fe(2)-O(2) bond length is 1.96 Å. The Fe(2)-O(4) bond length is 2.06 Å. The Fe(2)-O(6) bond length is 2.02 Å. The Fe(2)-O(8) bond length is 2.06 Å. In the third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(3)-O(15) bond length is 2.09 Å. The Fe(3)-O(17) bond length is 2.12 Å. The Fe(3)-O(19) bond length is 2.10 Å. The Fe(3)-O(21) bond length is 1.96 Å. The Fe(3)-O(23) bond length is 1.95 Å. The Fe(3)-O(24) bond length is 1.95 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. The Cu(1)-O(11) bond length is 2.34 Å. The Cu(1)-O(14) bond length is 2.29 Å. The Cu(1)-O(18) bond length is 2.46 Å. The Cu(1)-O(22) bond length is 2.37 Å. The Cu(1)-O(3) bond length is 2.30 Å. The Cu(1)-O(7) bond length is 2.12 Å. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. The Cu(2)-O(10) bond length is 2.29 Å. The Cu(2)-O(15) bond length is 2.32 Å. The Cu(2)-O(17) bond length is 2.34 Å. The Cu(2)-O(19) bond length is 2.44 Å. The Cu(2)-O(6) bond length is 2.13 Å. The Cu(2)-O(8) bond length is 2.31 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. The P(1)-O(24) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. The P(2)-O(13) bond length is 1.55 Å. The P(2)-O(21) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-43°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(16) bond length is 1.54 Å. The P(3)-O(23) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. The P(4)-O(11) bond length is 1.58 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(2) bond length is 1.52 Å. The P(4)-O(9) bond length is 1.52 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. The P(5)-O(12) bond length is 1.52 Å. The P(5)-O(17) bond length is 1.58 Å. The P(5)-O(18) bond length is 1.58 Å. The P(5)-O(4) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. The P(6)-O(1) bond length is 1.52 Å. The P(6)-O(19) bond length is 1.57 Å. The P(6)-O(20) bond length is 1.53 Å. The P(6)-O(22) bond length is 1.58 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Cu(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Cu(1), 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(1), one Fe(2), one Cu(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), one Cu(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Cr(1), one Cu(1), and one P(4) atom to form distorted OLi2CrCuP trigonal bipyramids that share corners with two equivalent O(17)Li2FeCuP trigonal bipyramids,  an edgeedge with one O(15)Li2FeCuP trigonal bipyramid, and  a faceface with one O(22)Li2CrCuP trigonal bipyramid. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(3), one Cr(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Cu(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Li(3), one Fe(3), one Cu(2), and one P(4) atom to form distorted OLi2FeCuP trigonal bipyramids that share corners with two equivalent O(22)Li2CrCuP trigonal bipyramids,  an edgeedge with one O(11)Li2CrCuP trigonal bipyramid, and  a faceface with one O(17)Li2FeCuP trigonal bipyramid. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Cr(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded to one Li(2), one Li(4), one Fe(3), one Cu(2), and one P(5) atom to form distorted OLi2FeCuP trigonal bipyramids that share  a cornercorner with one O(22)Li2CrCuP trigonal bipyramid, corners with two equivalent O(11)Li2CrCuP trigonal bipyramids, and  a faceface with one O(15)Li2FeCuP trigonal bipyramid. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(3), one Cu(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Fe(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded to one Li(2), one Li(3), one Cr(1), one Cu(1), and one P(6) atom to form distorted OLi2CrCuP trigonal bipyramids that share  a cornercorner with one O(17)Li2FeCuP trigonal bipyramid, corners with two equivalent O(15)Li2FeCuP trigonal bipyramids, and  a faceface with one O(11)Li2CrCuP trigonal bipyramid. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Fe(3), and one P(1) atom.