Li6WCr3P6O24 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(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 Li site, Li(2) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(3), one O(4), one O(8), and one O(9) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(11), one O(16), one O(17), one O(21), and one O(6) atom. In the fifth Li site, Li(5) is bonded in a distorted pentagonal planar geometry to one O(13), one O(16), one O(20), one O(22), and one O(23) atom. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(15), one O(17), one O(18), one O(20), and one O(24) atom. W(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), and one O(6) atom to form WO6 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 three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(12), one O(14), one O(19), one O(3), 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(2), one O(4), one O(5), one O(8), 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. In the third Cr site, Cr(3) is bonded to one O(16), one O(17), one O(20), one O(21), one O(23), and one O(24) 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(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-44°. 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. In the third P site, P(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-43°. 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(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 Li(2), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one Cr(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one W(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one W(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(5), one W(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal pyramidal geometry to one Li(1), one Li(2), one Cr(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(6), one W(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded to one Li(3), one Li(4), one Li(5), one Cr(3), and one P(4) atom to form distorted face-sharing OLi3CrP trigonal bipyramids. In the seventeenth O site, O(17) is bonded to one Li(3), one Li(4), one Li(6), one Cr(3), and one P(5) atom to form distorted face-sharing OLi3CrP trigonal bipyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one W(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 5-coordinate geometry to one Li(3), one Li(5), one Li(6), one Cr(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(4), one Cr(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one W(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Cr(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(6), one Cr(3), and one P(1) atom.
Li6WCr3P6O24 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(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 Li(1)-O(11) bond length is 2.46 Å. The Li(1)-O(14) bond length is 2.12 Å. The Li(1)-O(18) bond length is 2.64 Å. The Li(1)-O(22) bond length is 2.55 Å. The Li(1)-O(3) bond length is 2.09 Å. The Li(1)-O(7) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(3), one O(4), one O(8), and one O(9) atom. The Li(2)-O(14) bond length is 2.12 Å. The Li(2)-O(19) bond length is 2.28 Å. The Li(2)-O(3) bond length is 2.40 Å. The Li(2)-O(4) bond length is 2.26 Å. The Li(2)-O(8) bond length is 2.50 Å. The Li(2)-O(9) bond length is 2.10 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) atom. The Li(3)-O(16) bond length is 2.40 Å. The Li(3)-O(17) bond length is 2.47 Å. The Li(3)-O(20) bond length is 2.59 Å. The Li(3)-O(5) bond length is 2.03 Å. The Li(3)-O(8) bond length is 2.15 Å. The Li(3)-O(9) bond length is 2.23 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(11), one O(16), one O(17), one O(21), and one O(6) atom. The Li(4)-O(11) bond length is 2.12 Å. The Li(4)-O(16) bond length is 2.17 Å. The Li(4)-O(17) bond length is 2.23 Å. The Li(4)-O(21) bond length is 2.26 Å. The Li(4)-O(6) bond length is 2.47 Å. In the fifth Li site, Li(5) is bonded in a distorted pentagonal planar geometry to one O(13), one O(16), one O(20), one O(22), and one O(23) atom. The Li(5)-O(13) bond length is 2.46 Å. The Li(5)-O(16) bond length is 2.25 Å. The Li(5)-O(20) bond length is 2.16 Å. The Li(5)-O(22) bond length is 2.11 Å. The Li(5)-O(23) bond length is 2.28 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(15), one O(17), one O(18), one O(20), and one O(24) atom. The Li(6)-O(15) bond length is 2.50 Å. The Li(6)-O(17) bond length is 2.19 Å. The Li(6)-O(18) bond length is 2.09 Å. The Li(6)-O(20) bond length is 2.25 Å. The Li(6)-O(24) bond length is 2.26 Å. W(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), and one O(6) atom to form WO6 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 W(1)-O(11) bond length is 2.15 Å. The W(1)-O(13) bond length is 2.11 Å. The W(1)-O(15) bond length is 2.11 Å. The W(1)-O(18) bond length is 2.15 Å. The W(1)-O(22) bond length is 2.16 Å. The W(1)-O(6) bond length is 2.12 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(12), one O(14), one O(19), one O(3), 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(10) bond length is 1.98 Å. The Cr(1)-O(12) bond length is 1.98 Å. The Cr(1)-O(14) bond length is 2.02 Å. The Cr(1)-O(19) bond length is 2.03 Å. The Cr(1)-O(3) bond length is 2.04 Å. The Cr(1)-O(7) bond length is 2.01 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(8), 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(2)-O(1) bond length is 1.96 Å. The Cr(2)-O(2) bond length is 1.96 Å. The Cr(2)-O(4) bond length is 2.01 Å. The Cr(2)-O(5) bond length is 2.01 Å. The Cr(2)-O(8) bond length is 2.03 Å. The Cr(2)-O(9) bond length is 2.01 Å. In the third Cr site, Cr(3) is bonded to one O(16), one O(17), one O(20), one O(21), one O(23), and one O(24) 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(16) bond length is 2.05 Å. The Cr(3)-O(17) bond length is 2.06 Å. The Cr(3)-O(20) bond length is 2.05 Å. The Cr(3)-O(21) bond length is 2.00 Å. The Cr(3)-O(23) bond length is 1.99 Å. The Cr(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(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-44°. The P(1)-O(24) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.54 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(21) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(15) bond length is 1.53 Å. The P(3)-O(23) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. The P(4)-O(10) bond length is 1.52 Å. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(16) bond length is 1.59 Å. The P(4)-O(2) bond length is 1.51 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. The P(5)-O(12) bond length is 1.51 Å. The P(5)-O(17) bond length is 1.58 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(4) bond length is 1.54 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 W(1)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra, and  a cornercorner with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-43°. The P(6)-O(1) bond length is 1.51 Å. The P(6)-O(19) bond length is 1.54 Å. The P(6)-O(20) bond length is 1.58 Å. The P(6)-O(22) bond length is 1.57 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(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 Li(2), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Cr(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one Cr(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one W(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one W(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(5), one W(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a trigonal pyramidal geometry to one Li(1), one Li(2), one Cr(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(6), one W(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded to one Li(3), one Li(4), one Li(5), one Cr(3), and one P(4) atom to form distorted face-sharing OLi3CrP trigonal bipyramids. In the seventeenth O site, O(17) is bonded to one Li(3), one Li(4), one Li(6), one Cr(3), and one P(5) atom to form distorted face-sharing OLi3CrP trigonal bipyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one W(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 5-coordinate geometry to one Li(3), one Li(5), one Li(6), one Cr(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(4), one Cr(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one W(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Cr(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(6), one Cr(3), and one P(1) atom.