Li3Cr4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(20), one O(5), one O(7), and one O(9) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(17), one O(4), one O(5), and one O(7) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(19), one O(21), one O(4), and one O(6) atom. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(12), one O(16), one O(2), one O(3), one O(5), and one O(7) 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. In the second Cr site, Cr(2) is bonded to one O(1), one O(10), one O(14), one O(17), one O(4), and one O(6) 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. In the third Cr site, Cr(3) is bonded to one O(11), one O(15), one O(19), one O(21), one O(24), and one O(8) 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. In the fourth Cr site, Cr(4) is bonded to one O(13), one O(18), one O(20), one O(22), one O(23), and one O(9) 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 six inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(23), one O(24), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-48°. In the second P site, P(2) is bonded to one O(16), one O(22), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. In the third P site, P(3) is bonded to one O(13), one O(15), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(18), and one O(19) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-47°. In the fifth P site, P(5) is bonded to one O(17), one O(21), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-40°. In the sixth P site, P(6) is bonded to one O(1), one O(11), one O(2), and one O(20) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(6) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), 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 Li(3), one Cr(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and one P(5) atom. In the tenth O site, O(10) is bonded in a linear geometry to one Cr(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Cr(3), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Cr(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(3), one Cr(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 Cr(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(3), one Cr(3), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(2) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(1) atom.
Li3Cr4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(20), one O(5), one O(7), and one O(9) atom. The Li(1)-O(16) bond length is 2.18 Å. The Li(1)-O(18) bond length is 2.19 Å. The Li(1)-O(20) bond length is 2.16 Å. The Li(1)-O(5) bond length is 2.23 Å. The Li(1)-O(7) bond length is 2.33 Å. The Li(1)-O(9) bond length is 2.30 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(17), one O(4), one O(5), and one O(7) atom. The Li(2)-O(12) bond length is 2.26 Å. The Li(2)-O(14) bond length is 2.18 Å. The Li(2)-O(17) bond length is 2.20 Å. The Li(2)-O(4) bond length is 2.35 Å. The Li(2)-O(5) bond length is 2.11 Å. The Li(2)-O(7) bond length is 2.25 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(19), one O(21), one O(4), and one O(6) atom. The Li(3)-O(11) bond length is 2.22 Å. The Li(3)-O(14) bond length is 2.25 Å. The Li(3)-O(19) bond length is 2.23 Å. The Li(3)-O(21) bond length is 2.21 Å. The Li(3)-O(4) bond length is 2.32 Å. The Li(3)-O(6) bond length is 2.15 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(12), one O(16), one O(2), one O(3), one O(5), and one O(7) 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(12) bond length is 1.99 Å. The Cr(1)-O(16) bond length is 1.99 Å. The Cr(1)-O(2) bond length is 1.93 Å. The Cr(1)-O(3) bond length is 1.94 Å. The Cr(1)-O(5) bond length is 2.01 Å. The Cr(1)-O(7) bond length is 2.02 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(10), one O(14), one O(17), one O(4), and one O(6) 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(2)-O(1) bond length is 1.93 Å. The Cr(2)-O(10) bond length is 1.93 Å. The Cr(2)-O(14) bond length is 2.00 Å. The Cr(2)-O(17) bond length is 2.00 Å. The Cr(2)-O(4) bond length is 2.01 Å. The Cr(2)-O(6) bond length is 1.99 Å. In the third Cr site, Cr(3) is bonded to one O(11), one O(15), one O(19), one O(21), one O(24), and one O(8) 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(3)-O(11) bond length is 1.94 Å. The Cr(3)-O(15) bond length is 1.92 Å. The Cr(3)-O(19) bond length is 1.95 Å. The Cr(3)-O(21) bond length is 1.99 Å. The Cr(3)-O(24) bond length is 1.92 Å. The Cr(3)-O(8) bond length is 1.92 Å. In the fourth Cr site, Cr(4) is bonded to one O(13), one O(18), one O(20), one O(22), one O(23), and one O(9) 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(4)-O(13) bond length is 1.92 Å. The Cr(4)-O(18) bond length is 1.99 Å. The Cr(4)-O(20) bond length is 1.98 Å. The Cr(4)-O(22) bond length is 1.92 Å. The Cr(4)-O(23) bond length is 1.92 Å. The Cr(4)-O(9) bond length is 1.94 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(23), one O(24), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-48°. The P(1)-O(14) bond length is 1.56 Å. The P(1)-O(23) bond length is 1.52 Å. The P(1)-O(24) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(16), one O(22), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. The P(2)-O(16) bond length is 1.54 Å. The P(2)-O(22) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(13), one O(15), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. The P(3)-O(13) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(18), and one O(19) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-47°. The P(4)-O(10) bond length is 1.53 Å. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(18) bond length is 1.55 Å. The P(4)-O(19) bond length is 1.56 Å. In the fifth P site, P(5) is bonded to one O(17), one O(21), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-40°. The P(5)-O(17) bond length is 1.54 Å. The P(5)-O(21) bond length is 1.55 Å. The P(5)-O(3) bond length is 1.52 Å. The P(5)-O(9) bond length is 1.57 Å. In the sixth P site, P(6) is bonded to one O(1), one O(11), one O(2), and one O(20) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, and  a cornercorner with one Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. The P(6)-O(1) bond length is 1.53 Å. The P(6)-O(11) bond length is 1.56 Å. The P(6)-O(2) bond length is 1.52 Å. The P(6)-O(20) bond length is 1.55 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 Cr(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(6) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), 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 Li(3), one Cr(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and one P(5) atom. In the tenth O site, O(10) is bonded in a linear geometry to one Cr(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Cr(3), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Cr(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one Cr(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(3), one Cr(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 Cr(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(3), one Cr(3), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(2) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Cr(4) and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(1) atom.