Li6WMn3P6O24 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(14), one O(3), and one O(7) atom. In the second Li site, Li(2) is bonded to one O(14), one O(19), one O(4), one O(8), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(16), one O(17), one O(5), one O(8), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(11), one O(16), one O(17), and one O(21) atom. In the fifth Li site, Li(5) is bonded in a rectangular see-saw-like geometry to 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 distorted rectangular see-saw-like geometry to 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 Mn sites. In the first Mn site, Mn(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 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  an edgeedge with one Li(2)O5 square pyramid. In the second Mn site, Mn(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 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 Li(2)O5 square pyramid. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), 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(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 Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-56°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 20-56°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 21-56°. 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 Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-40°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-50°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 31-40°. 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(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Mn(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 Mn(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 Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to 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 Mn(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 Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(4), one W(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one W(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Mn(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one W(1) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(5), one Mn(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(6), one Mn(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted T-shaped geometry to 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 Mn(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Li(5), one Li(6), one Mn(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 Mn(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a distorted T-shaped geometry to 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 Mn(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 Mn(3), and one P(1) atom.
Li6WMn3P6O24 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(14), one O(3), and one O(7) atom. The Li(1)-O(14) bond length is 1.98 Å. The Li(1)-O(3) bond length is 2.09 Å. The Li(1)-O(7) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(14), one O(19), one O(4), one O(8), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. The Li(2)-O(14) bond length is 2.15 Å. The Li(2)-O(19) bond length is 2.43 Å. The Li(2)-O(4) bond length is 2.11 Å. The Li(2)-O(8) bond length is 2.15 Å. The Li(2)-O(9) bond length is 2.09 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(16), one O(17), one O(5), one O(8), and one O(9) atom. The Li(3)-O(16) bond length is 2.45 Å. The Li(3)-O(17) bond length is 2.52 Å. The Li(3)-O(5) bond length is 2.03 Å. The Li(3)-O(8) bond length is 2.18 Å. The Li(3)-O(9) bond length is 2.16 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(11), one O(16), one O(17), and one O(21) atom. The Li(4)-O(11) bond length is 2.19 Å. The Li(4)-O(16) bond length is 2.17 Å. The Li(4)-O(17) bond length is 2.09 Å. The Li(4)-O(21) bond length is 1.96 Å. In the fifth Li site, Li(5) is bonded in a rectangular see-saw-like geometry to one O(16), one O(20), one O(22), and one O(23) atom. The Li(5)-O(16) bond length is 2.08 Å. The Li(5)-O(20) bond length is 2.08 Å. The Li(5)-O(22) bond length is 2.25 Å. The Li(5)-O(23) bond length is 1.97 Å. In the sixth Li site, Li(6) is bonded in a distorted rectangular see-saw-like geometry to one O(17), one O(18), one O(20), and one O(24) atom. The Li(6)-O(17) bond length is 2.15 Å. The Li(6)-O(18) bond length is 2.25 Å. The Li(6)-O(20) bond length is 2.08 Å. The Li(6)-O(24) bond length is 1.97 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 2.04 Å. The W(1)-O(13) bond length is 1.96 Å. The W(1)-O(15) bond length is 1.96 Å. The W(1)-O(18) bond length is 2.02 Å. The W(1)-O(22) bond length is 2.04 Å. The W(1)-O(6) bond length is 1.95 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(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 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  an edgeedge with one Li(2)O5 square pyramid. The Mn(1)-O(10) bond length is 1.94 Å. The Mn(1)-O(12) bond length is 2.06 Å. The Mn(1)-O(14) bond length is 2.23 Å. The Mn(1)-O(19) bond length is 1.99 Å. The Mn(1)-O(3) bond length is 2.01 Å. The Mn(1)-O(7) bond length is 2.02 Å. In the second Mn site, Mn(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 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 Li(2)O5 square pyramid. The Mn(2)-O(1) bond length is 2.12 Å. The Mn(2)-O(2) bond length is 2.13 Å. The Mn(2)-O(4) bond length is 2.28 Å. The Mn(2)-O(5) bond length is 2.22 Å. The Mn(2)-O(8) bond length is 2.41 Å. The Mn(2)-O(9) bond length is 2.22 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), one O(21), one O(23), and one O(24) atom. The Mn(3)-O(16) bond length is 2.34 Å. The Mn(3)-O(17) bond length is 2.25 Å. The Mn(3)-O(20) bond length is 2.25 Å. The Mn(3)-O(21) bond length is 2.07 Å. The Mn(3)-O(23) bond length is 2.05 Å. The Mn(3)-O(24) bond length is 2.09 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 Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-56°. The P(1)-O(24) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.60 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 20-56°. The P(2)-O(13) bond length is 1.59 Å. The P(2)-O(21) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.53 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 21-56°. The P(3)-O(14) bond length is 1.53 Å. The P(3)-O(15) bond length is 1.58 Å. The P(3)-O(23) bond length is 1.53 Å. The P(3)-O(9) bond length is 1.54 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 Mn(1)O6 octahedra, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-40°. The P(4)-O(10) bond length is 1.53 Å. The P(4)-O(11) bond length is 1.62 Å. The P(4)-O(16) bond length is 1.55 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-50°. The P(5)-O(12) bond length is 1.51 Å. The P(5)-O(17) bond length is 1.56 Å. The P(5)-O(18) bond length is 1.63 Å. The P(5)-O(4) bond length is 1.53 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 31-40°. The P(6)-O(1) bond length is 1.51 Å. The P(6)-O(19) bond length is 1.55 Å. The P(6)-O(20) bond length is 1.55 Å. The P(6)-O(22) bond length is 1.61 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(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Mn(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 Mn(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 Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to 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 Mn(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 Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(4), one W(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one W(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Mn(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one W(1) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(5), one Mn(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(6), one Mn(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted T-shaped geometry to 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 Mn(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Li(5), one Li(6), one Mn(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 Mn(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a distorted T-shaped geometry to 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 Mn(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 Mn(3), and one P(1) atom.