Li6VMn3(PO4)6 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(11), one O(14), 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 5-coordinate 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 6-coordinate geometry to one O(11), one O(15), one O(17), one O(18), one O(20), and one O(24) atom. V(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 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 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 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, and  a cornercorner with one P(6)O4 tetrahedra. 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, and  a cornercorner with one P(6)O4 tetrahedra. In the third Mn site, Mn(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 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, 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-49°. 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-44°. 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-44°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear 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 4-coordinate geometry to one Li(1), one Li(2), 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 distorted T-shaped geometry to one Li(3), one Mn(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 V(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 to one Li(2), one Li(3), one Mn(2), and one P(3) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(17)Li3MnP trigonal bipyramid and  an edgeedge with one O(14)Li2MnP trigonal pyramid. 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 5-coordinate geometry to one Li(1), one Li(4), one Li(6), one V(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 distorted bent 150 degrees geometry to one Li(5), one V(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded to one Li(1), one Li(2), one Mn(1), and one P(3) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(22)Li2VP trigonal pyramid and  an edgeedge with one O(9)Li2MnP trigonal pyramid. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Li(6), one V(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 to one Li(3), one Li(4), one Li(6), one Mn(3), and one P(5) atom to form distorted corner-sharing OLi3MnP trigonal bipyramids. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(6), one V(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 5-coordinate geometry to one Li(3), 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 to one Li(1), one Li(5), one V(1), and one P(6) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the twenty-third O site, O(23) is bonded in a distorted T-shaped 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.
Li6VMn3(PO4)6 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(11), one O(14), one O(22), one O(3), and one O(7) atom. The Li(1)-O(11) bond length is 2.37 Å. The Li(1)-O(14) bond length is 2.07 Å. The Li(1)-O(22) bond length is 2.32 Å. The Li(1)-O(3) bond length is 2.20 Å. The Li(1)-O(7) bond length is 2.09 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 2.09 Å. The Li(2)-O(19) bond length is 2.16 Å. The Li(2)-O(3) bond length is 2.58 Å. The Li(2)-O(4) bond length is 2.23 Å. The Li(2)-O(8) bond length is 2.45 Å. The Li(2)-O(9) bond length is 2.07 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 2.26 Å. The Li(3)-O(17) bond length is 2.41 Å. The Li(3)-O(20) bond length is 2.54 Å. The Li(3)-O(5) bond length is 2.09 Å. The Li(3)-O(8) bond length is 2.19 Å. The Li(3)-O(9) bond length is 2.14 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 2.15 Å. The Li(4)-O(16) bond length is 2.13 Å. The Li(4)-O(17) bond length is 2.45 Å. The Li(4)-O(21) bond length is 2.31 Å. The Li(4)-O(6) bond length is 2.49 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate 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 2.59 Å. The Li(5)-O(16) bond length is 2.29 Å. The Li(5)-O(20) bond length is 2.13 Å. The Li(5)-O(22) bond length is 2.16 Å. The Li(5)-O(23) bond length is 2.19 Å. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(17), one O(18), one O(20), and one O(24) atom. The Li(6)-O(11) bond length is 2.57 Å. The Li(6)-O(15) bond length is 2.67 Å. The Li(6)-O(17) bond length is 2.23 Å. The Li(6)-O(18) bond length is 2.08 Å. The Li(6)-O(20) bond length is 2.43 Å. The Li(6)-O(24) bond length is 2.08 Å. V(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 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 2.12 Å. The V(1)-O(13) bond length is 2.03 Å. The V(1)-O(15) bond length is 1.94 Å. The V(1)-O(18) bond length is 2.05 Å. The V(1)-O(22) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.01 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 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, and  a cornercorner with one P(6)O4 tetrahedra. The Mn(1)-O(10) bond length is 1.90 Å. The Mn(1)-O(12) bond length is 2.03 Å. The Mn(1)-O(14) bond length is 2.18 Å. The Mn(1)-O(19) bond length is 2.04 Å. The Mn(1)-O(3) bond length is 1.95 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, and  a cornercorner with one P(6)O4 tetrahedra. The Mn(2)-O(1) bond length is 2.07 Å. The Mn(2)-O(2) bond length is 1.92 Å. The Mn(2)-O(4) bond length is 1.99 Å. The Mn(2)-O(5) bond length is 1.98 Å. The Mn(2)-O(8) bond length is 1.98 Å. The Mn(2)-O(9) bond length is 2.23 Å. In the third Mn site, Mn(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 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, and  a cornercorner with one P(6)O4 tetrahedra. The Mn(3)-O(16) bond length is 2.33 Å. The Mn(3)-O(17) bond length is 1.98 Å. The Mn(3)-O(20) bond length is 2.03 Å. The Mn(3)-O(21) bond length is 1.94 Å. The Mn(3)-O(23) bond length is 1.91 Å. The Mn(3)-O(24) bond length is 2.12 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. The P(1)-O(24) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.55 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. 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 1.57 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.54 Å. The P(3)-O(23) bond length is 1.56 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-49°. The P(4)-O(10) bond length is 1.53 Å. The P(4)-O(11) bond length is 1.58 Å. The P(4)-O(16) bond length is 1.56 Å. The P(4)-O(2) bond length is 1.53 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-44°. 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 1.55 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 V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-44°. 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 1.58 Å. The P(6)-O(22) bond length is 1.58 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear 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 4-coordinate geometry to one Li(1), one Li(2), 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 distorted T-shaped geometry to one Li(3), one Mn(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 V(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 to one Li(2), one Li(3), one Mn(2), and one P(3) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(17)Li3MnP trigonal bipyramid and  an edgeedge with one O(14)Li2MnP trigonal pyramid. 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 5-coordinate geometry to one Li(1), one Li(4), one Li(6), one V(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 distorted bent 150 degrees geometry to one Li(5), one V(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded to one Li(1), one Li(2), one Mn(1), and one P(3) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(22)Li2VP trigonal pyramid and  an edgeedge with one O(9)Li2MnP trigonal pyramid. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Li(6), one V(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 to one Li(3), one Li(4), one Li(6), one Mn(3), and one P(5) atom to form distorted corner-sharing OLi3MnP trigonal bipyramids. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(6), one V(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 5-coordinate geometry to one Li(3), 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 to one Li(1), one Li(5), one V(1), and one P(6) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the twenty-third O site, O(23) is bonded in a distorted T-shaped 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.