Li3VMn(PO4)3 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(18), one O(5), and one O(9) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(2), one O(5), and one O(8) atom. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(10), one O(17), one O(20), and one O(7) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(19), one O(2), one O(21), and one O(24) atom. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(14), one O(23), one O(4), and one O(6) atom. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(16), one O(24), one O(6), and one O(7) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(13), one O(16), one O(20), and one O(21) 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. In the second V site, V(2) is bonded to one O(12), one O(14), one O(15), one O(4), one O(5), and one O(9) 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 two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(18), one O(23), one O(3), one O(6), and one O(8) 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(17), one O(19), one O(2), one O(22), one O(24), 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. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(2), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 22-52°. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 22-47°. In the third P site, P(3) is bonded to one O(14), one O(16), one O(17), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 27-47°. In the fourth P site, P(4) is bonded to one O(15), one O(18), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 30-46°. In the fifth P site, P(5) is bonded to one O(11), one O(19), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 30-45°. In the sixth P site, P(6) is bonded to one O(12), one O(20), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 26-50°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(5), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Li(5), one Li(6), one Mn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Mn(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(5) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(5) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(4), one V(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(6), one V(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Mn(2), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a distorted T-shaped geometry to one Li(4), one Mn(2), and one P(5) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), 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 V(1), and one P(4) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Mn(1), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Li(4), one Li(6), one Mn(2), and one P(6) atom.
Li3VMn(PO4)3 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(18), one O(5), and one O(9) atom. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(18) bond length is 1.98 Å. The Li(1)-O(5) bond length is 2.53 Å. The Li(1)-O(9) bond length is 2.08 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(2), one O(5), and one O(8) atom. The Li(2)-O(11) bond length is 2.09 Å. The Li(2)-O(15) bond length is 2.02 Å. The Li(2)-O(2) bond length is 2.56 Å. The Li(2)-O(5) bond length is 2.06 Å. The Li(2)-O(8) bond length is 2.41 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(10), one O(17), one O(20), and one O(7) atom. The Li(3)-O(10) bond length is 1.99 Å. The Li(3)-O(17) bond length is 2.06 Å. The Li(3)-O(20) bond length is 2.07 Å. The Li(3)-O(7) bond length is 2.58 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(19), one O(2), one O(21), and one O(24) atom. The Li(4)-O(11) bond length is 2.28 Å. The Li(4)-O(12) bond length is 2.51 Å. The Li(4)-O(19) bond length is 2.36 Å. The Li(4)-O(2) bond length is 2.15 Å. The Li(4)-O(21) bond length is 2.11 Å. The Li(4)-O(24) bond length is 2.54 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(14), one O(23), one O(4), and one O(6) atom. The Li(5)-O(14) bond length is 2.26 Å. The Li(5)-O(23) bond length is 2.02 Å. The Li(5)-O(4) bond length is 2.23 Å. The Li(5)-O(6) bond length is 2.29 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(16), one O(24), one O(6), and one O(7) atom. The Li(6)-O(16) bond length is 2.40 Å. The Li(6)-O(24) bond length is 2.00 Å. The Li(6)-O(6) bond length is 2.12 Å. The Li(6)-O(7) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(13), one O(16), one O(20), and one O(21) 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(10) bond length is 2.03 Å. The V(1)-O(11) bond length is 2.13 Å. The V(1)-O(13) bond length is 2.00 Å. The V(1)-O(16) bond length is 2.02 Å. The V(1)-O(20) bond length is 2.04 Å. The V(1)-O(21) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(12), one O(14), one O(15), one O(4), one O(5), and one O(9) 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(2)-O(12) bond length is 1.96 Å. The V(2)-O(14) bond length is 2.06 Å. The V(2)-O(15) bond length is 2.06 Å. The V(2)-O(4) bond length is 2.03 Å. The V(2)-O(5) bond length is 2.03 Å. The V(2)-O(9) bond length is 2.07 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(18), one O(23), one O(3), one O(6), and one O(8) 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(1) bond length is 1.98 Å. The Mn(1)-O(18) bond length is 2.22 Å. The Mn(1)-O(23) bond length is 2.20 Å. The Mn(1)-O(3) bond length is 1.91 Å. The Mn(1)-O(6) bond length is 2.02 Å. The Mn(1)-O(8) bond length is 1.95 Å. In the second Mn site, Mn(2) is bonded to one O(17), one O(19), one O(2), one O(22), one O(24), 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(2)-O(17) bond length is 2.01 Å. The Mn(2)-O(19) bond length is 1.96 Å. The Mn(2)-O(2) bond length is 2.16 Å. The Mn(2)-O(22) bond length is 1.90 Å. The Mn(2)-O(24) bond length is 2.05 Å. The Mn(2)-O(7) bond length is 2.19 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(2), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 22-52°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(13) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 22-47°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(14), one O(16), one O(17), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 27-47°. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(16) bond length is 1.54 Å. The P(3)-O(17) bond length is 1.55 Å. The P(3)-O(6) bond length is 1.58 Å. In the fourth P site, P(4) is bonded to one O(15), one O(18), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 30-46°. The P(4)-O(15) bond length is 1.56 Å. The P(4)-O(18) bond length is 1.52 Å. The P(4)-O(21) bond length is 1.56 Å. The P(4)-O(22) bond length is 1.55 Å. In the fifth P site, P(5) is bonded to one O(11), one O(19), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 30-45°. The P(5)-O(11) bond length is 1.56 Å. The P(5)-O(19) bond length is 1.57 Å. The P(5)-O(8) bond length is 1.55 Å. The P(5)-O(9) bond length is 1.54 Å. In the sixth P site, P(6) is bonded to one O(12), one O(20), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)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 26-50°. The P(6)-O(12) bond length is 1.55 Å. The P(6)-O(20) bond length is 1.55 Å. The P(6)-O(23) bond length is 1.54 Å. The P(6)-O(24) bond length is 1.56 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(5), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Li(5), one Li(6), one Mn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Mn(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(5) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(5) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(4), one V(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(6), one V(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Mn(2), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a distorted T-shaped geometry to one Li(4), one Mn(2), and one P(5) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), 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 V(1), and one P(4) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Mn(1), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Li(4), one Li(6), one Mn(2), and one P(6) atom.