Li4CrMn2Ni3(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 two 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(22), one O(3), and one O(7) atom. In the second Mn site, Mn(2) 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,  a faceface with one Ni(2)O6 octahedra, and  a faceface with one Ni(3)O6 octahedra. There are three inequivalent Ni sites. In the first Ni site, Ni(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 NiO6 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 Ni site, Ni(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 NiO6 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 third Ni site, Ni(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 distorted NiO6 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. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-48°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-49°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-50°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-48°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-47°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ni(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 Mn(1), one Ni(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 Ni(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 Mn(2), one Ni(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Ni(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 Mn(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), one Ni(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Cr(1), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ni(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 Mn(1), one Ni(1), 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(2), one Ni(3), and one P(4) atom. 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 in a distorted trigonal bipyramidal geometry to one Li(2), one Li(4), one Mn(2), one Ni(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(3), 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 5-coordinate geometry to one Li(3), one Li(4), one Mn(2), one Ni(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Ni(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 Ni(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Cr(1), one Mn(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Li(3), one Ni(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 Ni(3), and one P(1) atom.
Li4CrMn2Ni3(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 2.13 Å. The Li(1)-O(14) bond length is 2.12 Å. The Li(1)-O(20) bond length is 2.23 Å. The Li(1)-O(3) bond length is 2.42 Å. The Li(1)-O(4) bond length is 2.21 Å. The Li(1)-O(8) bond length is 2.38 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 2.23 Å. The Li(2)-O(15) bond length is 2.14 Å. The Li(2)-O(17) bond length is 2.48 Å. The Li(2)-O(21) bond length is 2.19 Å. The Li(2)-O(22) bond length is 2.61 Å. The Li(2)-O(5) bond length is 2.48 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 2.50 Å. The Li(3)-O(15) bond length is 2.49 Å. The Li(3)-O(18) bond length is 2.63 Å. The Li(3)-O(19) bond length is 2.12 Å. The Li(3)-O(22) bond length is 2.23 Å. The Li(3)-O(23) bond length is 2.21 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 2.62 Å. The Li(4)-O(16) bond length is 2.49 Å. The Li(4)-O(17) bond length is 2.14 Å. The Li(4)-O(18) bond length is 2.21 Å. The Li(4)-O(19) bond length is 2.50 Å. The Li(4)-O(24) bond length is 2.21 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 2.04 Å. The Cr(1)-O(13) bond length is 1.95 Å. The Cr(1)-O(16) bond length is 1.96 Å. The Cr(1)-O(18) bond length is 2.06 Å. The Cr(1)-O(22) bond length is 2.06 Å. The Cr(1)-O(5) bond length is 1.97 Å. There are two 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(22), one O(3), and one O(7) atom. The Mn(1)-O(11) bond length is 2.29 Å. The Mn(1)-O(14) bond length is 2.19 Å. The Mn(1)-O(18) bond length is 2.33 Å. The Mn(1)-O(22) bond length is 2.29 Å. The Mn(1)-O(3) bond length is 2.19 Å. The Mn(1)-O(7) bond length is 2.10 Å. In the second Mn site, Mn(2) 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,  a faceface with one Ni(2)O6 octahedra, and  a faceface with one Ni(3)O6 octahedra. The Mn(2)-O(10) bond length is 2.19 Å. The Mn(2)-O(15) bond length is 2.24 Å. The Mn(2)-O(17) bond length is 2.25 Å. The Mn(2)-O(19) bond length is 2.28 Å. The Mn(2)-O(6) bond length is 2.11 Å. The Mn(2)-O(8) bond length is 2.19 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(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 NiO6 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 Ni(1)-O(12) bond length is 1.96 Å. The Ni(1)-O(14) bond length is 2.07 Å. The Ni(1)-O(20) bond length is 2.03 Å. The Ni(1)-O(3) bond length is 2.09 Å. The Ni(1)-O(7) bond length is 2.09 Å. The Ni(1)-O(9) bond length is 1.97 Å. In the second Ni site, Ni(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 NiO6 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 Ni(2)-O(1) bond length is 1.98 Å. The Ni(2)-O(10) bond length is 2.09 Å. The Ni(2)-O(2) bond length is 1.99 Å. The Ni(2)-O(4) bond length is 2.06 Å. The Ni(2)-O(6) bond length is 2.11 Å. The Ni(2)-O(8) bond length is 2.11 Å. In the third Ni site, Ni(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 distorted NiO6 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 Ni(3)-O(15) bond length is 2.11 Å. The Ni(3)-O(17) bond length is 2.14 Å. The Ni(3)-O(19) bond length is 2.13 Å. The Ni(3)-O(21) bond length is 2.00 Å. The Ni(3)-O(23) bond length is 1.99 Å. The Ni(3)-O(24) bond length is 1.98 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-48°. The P(1)-O(24) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.56 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-49°. The P(2)-O(13) bond length is 1.55 Å. The P(2)-O(21) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.57 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-50°. The P(3)-O(10) bond length is 1.57 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 1.53 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-48°. The P(4)-O(11) bond length is 1.61 Å. The P(4)-O(15) bond length is 1.59 Å. The P(4)-O(2) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.50 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. The P(5)-O(12) bond length is 1.50 Å. The P(5)-O(17) bond length is 1.59 Å. The P(5)-O(18) bond length is 1.60 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-47°. The P(6)-O(1) bond length is 1.51 Å. The P(6)-O(19) bond length is 1.59 Å. The P(6)-O(20) bond length is 1.52 Å. The P(6)-O(22) bond length is 1.61 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 Ni(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ni(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 Mn(1), one Ni(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 Ni(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 Mn(2), one Ni(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Ni(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 Mn(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), one Ni(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Cr(1), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ni(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 Mn(1), one Ni(1), 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(2), one Ni(3), and one P(4) atom. 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 in a distorted trigonal bipyramidal geometry to one Li(2), one Li(4), one Mn(2), one Ni(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(3), 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 5-coordinate geometry to one Li(3), one Li(4), one Mn(2), one Ni(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Ni(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 Ni(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Cr(1), one Mn(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Li(3), one Ni(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 Ni(3), and one P(1) atom.