Li4TiCr2Ni3(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 distorted rectangular see-saw-like 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 distorted rectangular see-saw-like 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. Ti(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 TiO6 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 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 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 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 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(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-54°. In the second P site, P(2) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-48°. In the third P site, P(3) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-53°. In the fourth P site, P(4) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-49°. In the fifth P site, P(5) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. In the sixth P site, P(6) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. 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(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Ni(1), and one P(4) 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(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Ni(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Ni(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Ni(2), and one P(5) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(1) 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(2), and one P(6) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one Cr(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted linear geometry to one Ni(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(5) 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(1), and one P(6) atom. 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 Ni(3), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted square pyramidal geometry to one Li(2), one Li(4), one Cr(2), one Ni(3), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Ti(1), one Cr(1), and one P(2) 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(3) 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(3) 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(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Ti(1), one Cr(1), and one P(3) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Ni(3), and one P(6) 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(4) atom.
Li4TiCr2Ni3(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 2.18 Å. The Li(1)-O(14) bond length is 2.12 Å. The Li(1)-O(20) bond length is 2.20 Å. The Li(1)-O(3) bond length is 2.57 Å. The Li(1)-O(4) bond length is 2.22 Å. The Li(1)-O(8) bond length is 2.21 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(15), one O(17), and one O(21) atom. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(15) bond length is 2.24 Å. The Li(2)-O(17) bond length is 2.14 Å. The Li(2)-O(21) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(15), one O(19), one O(22), and one O(23) atom. The Li(3)-O(15) bond length is 2.19 Å. The Li(3)-O(19) bond length is 2.13 Å. The Li(3)-O(22) bond length is 2.16 Å. The Li(3)-O(23) bond length is 1.94 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 2.23 Å. The Li(4)-O(18) bond length is 2.10 Å. The Li(4)-O(19) bond length is 2.17 Å. The Li(4)-O(24) bond length is 1.96 Å. Ti(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 TiO6 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 Ti(1)-O(11) bond length is 2.19 Å. The Ti(1)-O(13) bond length is 1.86 Å. The Ti(1)-O(16) bond length is 1.87 Å. The Ti(1)-O(18) bond length is 2.04 Å. The Ti(1)-O(22) bond length is 2.11 Å. The Ti(1)-O(5) bond length is 1.87 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 2.19 Å. The Cr(1)-O(14) bond length is 2.13 Å. The Cr(1)-O(18) bond length is 2.53 Å. The Cr(1)-O(22) bond length is 2.24 Å. The Cr(1)-O(3) bond length is 2.16 Å. The Cr(1)-O(7) bond length is 2.30 Å. In the second Cr site, Cr(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 Cr(2)-O(10) bond length is 2.14 Å. The Cr(2)-O(15) bond length is 2.15 Å. The Cr(2)-O(17) bond length is 2.21 Å. The Cr(2)-O(19) bond length is 2.46 Å. The Cr(2)-O(6) bond length is 2.26 Å. The Cr(2)-O(8) bond length is 2.17 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 1.99 Å. The Ni(1)-O(14) bond length is 2.17 Å. The Ni(1)-O(20) bond length is 2.04 Å. The Ni(1)-O(3) bond length is 2.13 Å. The Ni(1)-O(7) bond length is 2.03 Å. The Ni(1)-O(9) bond length is 1.99 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 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(1) bond length is 2.05 Å. The Ni(2)-O(10) bond length is 2.24 Å. The Ni(2)-O(2) bond length is 2.01 Å. The Ni(2)-O(4) bond length is 2.09 Å. The Ni(2)-O(6) bond length is 2.06 Å. The Ni(2)-O(8) bond length is 2.21 Å. In the third Ni site, Ni(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 Ni(3)-O(15) bond length is 2.24 Å. The Ni(3)-O(17) bond length is 2.15 Å. The Ni(3)-O(19) bond length is 2.06 Å. The Ni(3)-O(21) bond length is 1.99 Å. The Ni(3)-O(23) bond length is 1.98 Å. The Ni(3)-O(24) bond length is 2.00 Å. There are six inequivalent P sites. In the first P site, P(1) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-54°. The P(1)-O(11) bond length is 1.63 Å. The P(1)-O(15) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(9) bond length is 1.50 Å. In the second P site, P(2) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-48°. The P(2)-O(12) bond length is 1.50 Å. The P(2)-O(17) bond length is 1.60 Å. The P(2)-O(18) bond length is 1.59 Å. The P(2)-O(4) bond length is 1.54 Å. In the third P site, P(3) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-53°. The P(3)-O(1) bond length is 1.52 Å. The P(3)-O(19) bond length is 1.57 Å. The P(3)-O(20) bond length is 1.53 Å. The P(3)-O(22) bond length is 1.63 Å. In the fourth P site, P(4) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-49°. The P(4)-O(24) bond length is 1.53 Å. The P(4)-O(3) bond length is 1.55 Å. The P(4)-O(5) bond length is 1.59 Å. The P(4)-O(6) bond length is 1.53 Å. In the fifth P site, P(5) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. The P(5)-O(13) bond length is 1.59 Å. The P(5)-O(21) bond length is 1.53 Å. The P(5)-O(7) bond length is 1.52 Å. The P(5)-O(8) bond length is 1.56 Å. In the sixth P site, P(6) 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 Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. The P(6)-O(10) bond length is 1.56 Å. The P(6)-O(14) bond length is 1.56 Å. The P(6)-O(16) bond length is 1.56 Å. The P(6)-O(23) bond length is 1.52 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(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Ni(1), and one P(4) 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(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Cr(2), one Ni(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cr(1), one Ni(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), one Ni(2), and one P(5) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(1) 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(2), and one P(6) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one Cr(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted linear geometry to one Ni(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(5) 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(1), and one P(6) atom. 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 Ni(3), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted square pyramidal geometry to one Li(2), one Li(4), one Cr(2), one Ni(3), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Ti(1), one Cr(1), and one P(2) 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(3) 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(3) 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(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Ti(1), one Cr(1), and one P(3) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Ni(3), and one P(6) 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(4) atom.