Li4VCr2Ni3(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 5-coordinate geometry to one O(1), one O(11), one O(15), one O(17), and one O(5) atom. In the third Li site, Li(3) is bonded in a 4-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 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(3) atom. V(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 distorted VO6 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(21), one O(4), 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,  a faceface with one Ni(1)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(10), one O(22), one O(23), one O(24), one O(6), and one O(8) 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 Cr(2)O6 octahedra. In the second Ni site, Ni(2) 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 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 third Ni site, Ni(3) is bonded to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) 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 Cr(2)O6 octahedra. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 29-51°. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 27-52°. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 25-53°. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 31-53°. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 20-52°. 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 17-51°. 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 Ni(3), 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 Ni(3), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Ni(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Ni(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Ni(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), one Ni(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(2) 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 Cr(2), one Ni(1), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one V(1), one Cr(1), and one P(4) atom to form distorted OLiVCrP trigonal pyramids that share  an edgeedge with one O(15)Li2CrNiP square pyramid and  an edgeedge with one O(21)LiVCrP trigonal pyramid. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Cr(1), one Ni(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Li(3), one Cr(2), one Ni(3), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLi2CrNiP square pyramids. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(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 Cr(2), one Ni(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one Cr(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 Cr(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(2), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(3), one V(1), one Cr(1), and one P(6) atom to form distorted OLiVCrP trigonal pyramids that share  a cornercorner with one O(15)Li2CrNiP square pyramid and  an edgeedge with one O(11)LiVCrP trigonal pyramid. In the twenty-second O site, O(22) is bonded in a distorted linear geometry to one Ni(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Ni(1) 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 Ni(1), and one P(5) atom.
Li4VCr2Ni3(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 2.11 Å. The Li(1)-O(20) bond length is 2.05 Å. The Li(1)-O(24) bond length is 2.07 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 5-coordinate geometry to one O(1), one O(11), one O(15), one O(17), and one O(5) atom. The Li(2)-O(1) bond length is 1.95 Å. The Li(2)-O(11) bond length is 2.11 Å. The Li(2)-O(15) bond length is 2.08 Å. The Li(2)-O(17) bond length is 2.37 Å. The Li(2)-O(5) bond length is 2.62 Å. In the third Li site, Li(3) is bonded in a 4-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 2.34 Å. The Li(3)-O(19) bond length is 2.10 Å. The Li(3)-O(2) bond length is 1.95 Å. The Li(3)-O(21) bond length is 2.16 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(3) atom. The Li(4)-O(17) bond length is 2.13 Å. The Li(4)-O(18) bond length is 2.20 Å. The Li(4)-O(19) bond length is 2.31 Å. The Li(4)-O(3) bond length is 1.93 Å. V(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 distorted VO6 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 V(1)-O(11) bond length is 2.10 Å. The V(1)-O(13) bond length is 1.95 Å. The V(1)-O(16) bond length is 1.95 Å. The V(1)-O(18) bond length is 2.17 Å. The V(1)-O(21) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.02 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(21), one O(4), and one O(7) atom. The Cr(1)-O(11) bond length is 2.16 Å. The Cr(1)-O(14) bond length is 2.10 Å. The Cr(1)-O(18) bond length is 2.15 Å. The Cr(1)-O(21) bond length is 2.37 Å. The Cr(1)-O(4) bond length is 2.15 Å. The Cr(1)-O(7) bond length is 2.04 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,  a faceface with one Ni(1)O6 octahedra, and  a faceface with one Ni(3)O6 octahedra. The Cr(2)-O(10) bond length is 2.25 Å. The Cr(2)-O(15) bond length is 2.29 Å. The Cr(2)-O(17) bond length is 2.21 Å. The Cr(2)-O(19) bond length is 2.15 Å. The Cr(2)-O(6) bond length is 2.05 Å. The Cr(2)-O(8) bond length is 2.14 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) 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 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 Cr(2)O6 octahedra. The Ni(1)-O(10) bond length is 2.08 Å. The Ni(1)-O(22) bond length is 2.00 Å. The Ni(1)-O(23) bond length is 2.00 Å. The Ni(1)-O(24) bond length is 2.08 Å. The Ni(1)-O(6) bond length is 2.12 Å. The Ni(1)-O(8) bond length is 2.19 Å. In the second Ni site, Ni(2) 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 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(2)-O(12) bond length is 1.99 Å. The Ni(2)-O(14) bond length is 2.11 Å. The Ni(2)-O(20) bond length is 2.08 Å. The Ni(2)-O(4) bond length is 2.10 Å. The Ni(2)-O(7) bond length is 2.16 Å. The Ni(2)-O(9) bond length is 1.98 Å. In the third Ni site, Ni(3) is bonded to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) 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 Cr(2)O6 octahedra. The Ni(3)-O(1) bond length is 2.01 Å. The Ni(3)-O(15) bond length is 2.09 Å. The Ni(3)-O(17) bond length is 2.18 Å. The Ni(3)-O(19) bond length is 2.17 Å. The Ni(3)-O(2) bond length is 2.00 Å. The Ni(3)-O(3) bond length is 2.00 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 29-51°. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.56 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 27-52°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.56 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(2) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cr(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 25-53°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.58 Å. The P(3)-O(16) bond length is 1.53 Å. The P(3)-O(2) bond length is 1.52 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 31-53°. The P(4)-O(11) bond length is 1.63 Å. The P(4)-O(15) bond length is 1.59 Å. The P(4)-O(23) bond length is 1.50 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(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Cr(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 20-52°. 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 1.62 Å. The P(5)-O(24) bond length is 1.52 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 V(1)O6 octahedra,  a cornercorner with one Cr(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 17-51°. The P(6)-O(19) bond length is 1.60 Å. The P(6)-O(20) bond length is 1.52 Å. The P(6)-O(21) bond length is 1.61 Å. The P(6)-O(22) bond length is 1.50 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 Ni(3), 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 Ni(3), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Ni(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Ni(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Ni(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), one Ni(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(2) 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 Cr(2), one Ni(1), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one V(1), one Cr(1), and one P(4) atom to form distorted OLiVCrP trigonal pyramids that share  an edgeedge with one O(15)Li2CrNiP square pyramid and  an edgeedge with one O(21)LiVCrP trigonal pyramid. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Cr(1), one Ni(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Li(3), one Cr(2), one Ni(3), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLi2CrNiP square pyramids. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(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 Cr(2), one Ni(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one Cr(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 Cr(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(2), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(3), one V(1), one Cr(1), and one P(6) atom to form distorted OLiVCrP trigonal pyramids that share  a cornercorner with one O(15)Li2CrNiP square pyramid and  an edgeedge with one O(11)LiVCrP trigonal pyramid. In the twenty-second O site, O(22) is bonded in a distorted linear geometry to one Ni(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Ni(1) 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 Ni(1), and one P(5) atom.