Li4NbCr2Mn3(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 5-coordinate geometry to one O(10), one O(14), one O(20), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(15), one O(17), and one O(21) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(22), and one O(23) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(24) atom. Nb(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 distorted NbO6 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 Cr sites. In the first Cr site, Cr(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 Cr site, Cr(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 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. There are three inequivalent Mn sites. In the first Mn site, Mn(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 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 second Mn site, Mn(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 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 Cr(2)O6 octahedra. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom. There are six inequivalent P sites. In the first P site, P(1) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-56°. In the second P site, P(2) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-45°. In the third P site, P(3) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-48°. In the fourth P site, P(4) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-52°. In the fifth P site, P(5) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-58°. In the sixth P site, P(6) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Cr(1), one Mn(1), and one P(5) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Mn(2), and one P(5) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Mn(1), and one P(6) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), one Mn(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Mn(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Nb(1), one Cr(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(6) atom. In the fourteenth O site, O(14) is bonded to one Li(1), one Cr(1), one Mn(1), and one P(1) atom to form distorted corner-sharing OLiMnCrP trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Cr(2), one Mn(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Cr(2), one Mn(3), and one P(3) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Nb(1), one Cr(1), and one P(3) atom to form distorted OLiNbCrP trigonal pyramids that share  a cornercorner with one O(14)LiMnCrP trigonal pyramid and  an edgeedge with one O(22)LiNbCrP trigonal pyramid. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(2), one Mn(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded to one Li(3), one Nb(1), one Cr(1), and one P(4) atom to form distorted OLiNbCrP trigonal pyramids that share  a cornercorner with one O(14)LiMnCrP trigonal pyramid and  an edgeedge with one O(18)LiNbCrP trigonal pyramid. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Mn(3), and one P(5) atom.
Li4NbCr2Mn3(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 5-coordinate geometry to one O(10), one O(14), one O(20), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.14 Å. The Li(1)-O(14) bond length is 2.08 Å. The Li(1)-O(20) bond length is 2.09 Å. The Li(1)-O(4) bond length is 2.09 Å. The Li(1)-O(8) bond length is 2.43 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(15), one O(17), and one O(21) atom. The Li(2)-O(11) bond length is 2.18 Å. The Li(2)-O(15) bond length is 2.05 Å. The Li(2)-O(17) bond length is 2.37 Å. The Li(2)-O(21) bond length is 1.94 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(22), and one O(23) atom. The Li(3)-O(15) bond length is 2.39 Å. The Li(3)-O(19) bond length is 2.05 Å. The Li(3)-O(22) bond length is 2.33 Å. The Li(3)-O(23) bond length is 1.96 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(24) atom. The Li(4)-O(17) bond length is 2.06 Å. The Li(4)-O(18) bond length is 2.20 Å. The Li(4)-O(19) bond length is 2.52 Å. The Li(4)-O(24) bond length is 1.93 Å. Nb(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 distorted NbO6 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 Nb(1)-O(11) bond length is 2.09 Å. The Nb(1)-O(13) bond length is 1.97 Å. The Nb(1)-O(16) bond length is 2.04 Å. The Nb(1)-O(18) bond length is 2.19 Å. The Nb(1)-O(22) bond length is 2.21 Å. The Nb(1)-O(5) bond length is 2.01 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(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 Cr(1)-O(11) bond length is 2.52 Å. The Cr(1)-O(14) bond length is 2.39 Å. The Cr(1)-O(18) bond length is 2.22 Å. The Cr(1)-O(22) bond length is 2.31 Å. The Cr(1)-O(3) bond length is 2.14 Å. The Cr(1)-O(7) bond length is 2.10 Å. In the second Cr site, Cr(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 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. The Cr(2)-O(10) bond length is 2.17 Å. The Cr(2)-O(15) bond length is 2.19 Å. The Cr(2)-O(17) bond length is 2.47 Å. The Cr(2)-O(19) bond length is 2.17 Å. The Cr(2)-O(6) bond length is 2.09 Å. The Cr(2)-O(8) bond length is 2.40 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(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 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(1)-O(12) bond length is 2.05 Å. The Mn(1)-O(14) bond length is 2.17 Å. The Mn(1)-O(20) bond length is 2.19 Å. The Mn(1)-O(3) bond length is 2.32 Å. The Mn(1)-O(7) bond length is 2.25 Å. The Mn(1)-O(9) bond length is 2.07 Å. In the second Mn site, Mn(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 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 Cr(2)O6 octahedra. The Mn(2)-O(1) bond length is 2.08 Å. The Mn(2)-O(10) bond length is 2.27 Å. The Mn(2)-O(2) bond length is 2.09 Å. The Mn(2)-O(4) bond length is 2.27 Å. The Mn(2)-O(6) bond length is 2.36 Å. The Mn(2)-O(8) bond length is 2.22 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom. The Mn(3)-O(15) bond length is 2.32 Å. The Mn(3)-O(17) bond length is 2.23 Å. The Mn(3)-O(19) bond length is 2.45 Å. The Mn(3)-O(21) bond length is 2.10 Å. The Mn(3)-O(23) bond length is 2.06 Å. The Mn(3)-O(24) bond length is 2.08 Å. There are six inequivalent P sites. In the first P site, P(1) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-56°. The P(1)-O(10) bond length is 1.56 Å. The P(1)-O(14) bond length is 1.54 Å. The P(1)-O(16) bond length is 1.58 Å. The P(1)-O(23) bond length is 1.53 Å. In the second P site, P(2) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-45°. The P(2)-O(11) bond length is 1.61 Å. The P(2)-O(15) bond length is 1.58 Å. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(9) bond length is 1.51 Å. In the third P site, P(3) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-48°. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(17) bond length is 1.56 Å. The P(3)-O(18) bond length is 1.62 Å. The P(3)-O(4) bond length is 1.53 Å. In the fourth P site, P(4) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-52°. The P(4)-O(1) bond length is 1.52 Å. The P(4)-O(19) bond length is 1.58 Å. The P(4)-O(20) bond length is 1.52 Å. The P(4)-O(22) bond length is 1.61 Å. In the fifth P site, P(5) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-58°. The P(5)-O(24) bond length is 1.53 Å. The P(5)-O(3) bond length is 1.54 Å. The P(5)-O(5) bond length is 1.59 Å. The P(5)-O(6) bond length is 1.54 Å. In the sixth P site, P(6) 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 Nb(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. The P(6)-O(13) bond length is 1.60 Å. The P(6)-O(21) bond length is 1.53 Å. The P(6)-O(7) bond length is 1.54 Å. The P(6)-O(8) bond length is 1.53 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 Mn(2) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Cr(1), one Mn(1), and one P(5) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Mn(2), and one P(5) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Mn(1), and one P(6) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), one Mn(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Mn(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Nb(1), one Cr(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(6) atom. In the fourteenth O site, O(14) is bonded to one Li(1), one Cr(1), one Mn(1), and one P(1) atom to form distorted corner-sharing OLiMnCrP trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Cr(2), one Mn(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Cr(2), one Mn(3), and one P(3) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Nb(1), one Cr(1), and one P(3) atom to form distorted OLiNbCrP trigonal pyramids that share  a cornercorner with one O(14)LiMnCrP trigonal pyramid and  an edgeedge with one O(22)LiNbCrP trigonal pyramid. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(2), one Mn(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded to one Li(3), one Nb(1), one Cr(1), and one P(4) atom to form distorted OLiNbCrP trigonal pyramids that share  a cornercorner with one O(14)LiMnCrP trigonal pyramid and  an edgeedge with one O(18)LiNbCrP trigonal pyramid. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Mn(3), and one P(5) atom.