Li4CrMn5(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(24), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(17), one O(18), and one O(3) atom. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), 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 five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. In the second Mn site, Mn(2) is bonded to one O(10), one O(22), one O(23), one O(24), one O(6), and one O(8) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(3)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) atom to form distorted MnO6 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 fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), 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 Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. In the second P site, P(2) is bonded to one O(1), one O(13), 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 Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-53°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-48°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Mn(5), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(5), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Mn(5), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(4), 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 Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(4) 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 Mn(2), one Mn(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Cr(1), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(4) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to 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 Mn(1), one Mn(4), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Mn(3), one Mn(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Mn(3), one Mn(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Cr(1), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Li(3), one Mn(3), one Mn(5), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Cr(1), one Mn(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(5) atom.
Li4CrMn5(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(24), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.07 Å. The Li(1)-O(14) bond length is 2.21 Å. The Li(1)-O(20) bond length is 2.12 Å. The Li(1)-O(24) bond length is 2.12 Å. The Li(1)-O(4) bond length is 2.58 Å. The Li(1)-O(8) bond length is 2.39 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(11) bond length is 2.17 Å. The Li(2)-O(15) bond length is 2.07 Å. The Li(2)-O(17) bond length is 2.60 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. The Li(3)-O(15) bond length is 2.61 Å. The Li(3)-O(19) bond length is 2.06 Å. The Li(3)-O(2) bond length is 2.11 Å. The Li(3)-O(21) bond length is 2.18 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(17), one O(18), and one O(3) atom. The Li(4)-O(17) bond length is 2.09 Å. The Li(4)-O(18) bond length is 2.16 Å. The Li(4)-O(3) bond length is 2.08 Å. Cr(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), 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 2.06 Å. The Cr(1)-O(13) bond length is 1.96 Å. The Cr(1)-O(16) bond length is 1.97 Å. The Cr(1)-O(18) bond length is 2.09 Å. The Cr(1)-O(21) bond length is 2.06 Å. The Cr(1)-O(5) bond length is 2.01 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. The Mn(1)-O(11) bond length is 2.30 Å. The Mn(1)-O(14) bond length is 2.26 Å. The Mn(1)-O(18) bond length is 2.34 Å. The Mn(1)-O(21) bond length is 2.30 Å. The Mn(1)-O(4) bond length is 2.28 Å. The Mn(1)-O(7) bond length is 2.11 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(22), one O(23), one O(24), one O(6), and one O(8) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(3)O6 octahedra. The Mn(2)-O(10) bond length is 2.24 Å. The Mn(2)-O(22) bond length is 2.06 Å. The Mn(2)-O(23) bond length is 2.07 Å. The Mn(2)-O(24) bond length is 2.20 Å. The Mn(2)-O(6) bond length is 2.26 Å. The Mn(2)-O(8) bond length is 2.23 Å. In the third Mn site, Mn(3) is bonded to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. The Mn(3)-O(10) bond length is 2.25 Å. The Mn(3)-O(15) bond length is 2.26 Å. The Mn(3)-O(17) bond length is 2.26 Å. The Mn(3)-O(19) bond length is 2.26 Å. The Mn(3)-O(6) bond length is 2.12 Å. The Mn(3)-O(8) bond length is 2.20 Å. In the fourth Mn site, Mn(4) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) atom to form distorted MnO6 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 Mn(4)-O(12) bond length is 1.97 Å. The Mn(4)-O(14) bond length is 2.04 Å. The Mn(4)-O(20) bond length is 2.16 Å. The Mn(4)-O(4) bond length is 2.04 Å. The Mn(4)-O(7) bond length is 2.22 Å. The Mn(4)-O(9) bond length is 1.94 Å. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom. The Mn(5)-O(1) bond length is 2.08 Å. The Mn(5)-O(15) bond length is 2.30 Å. The Mn(5)-O(17) bond length is 2.35 Å. The Mn(5)-O(19) bond length is 2.25 Å. The Mn(5)-O(2) bond length is 2.09 Å. The Mn(5)-O(3) bond length is 2.09 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), 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 Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(1), one O(13), 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 Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(13) 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 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-53°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(14) bond length is 1.59 Å. The P(3)-O(16) bond length is 1.53 Å. The P(3)-O(2) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. The P(4)-O(11) bond length is 1.60 Å. The P(4)-O(15) bond length is 1.57 Å. The P(4)-O(23) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. The P(5)-O(12) bond length is 1.53 Å. The P(5)-O(17) bond length is 1.57 Å. The P(5)-O(18) bond length is 1.60 Å. The P(5)-O(24) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-48°. The P(6)-O(19) bond length is 1.57 Å. The P(6)-O(20) bond length is 1.52 Å. The P(6)-O(21) bond length is 1.60 Å. The P(6)-O(22) bond length is 1.51 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Mn(5), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(5), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Mn(5), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(4), 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 Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(4) 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 Mn(2), one Mn(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Cr(1), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(4) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to 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 Mn(1), one Mn(4), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Mn(3), one Mn(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Mn(3), one Mn(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Cr(1), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Li(3), one Mn(3), one Mn(5), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Cr(1), one Mn(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(5) atom.