Li2VMn(PO4)3 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(19), one O(2), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra,  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, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-69°. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(15), one O(20), one O(23), and one O(6) atom. In the third Li site, Li(3) is bonded to one O(1), one O(17), one O(19), and one O(22) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)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 V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-70°. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(14), one O(21), one O(24), and one O(5) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(19), one O(20), one O(24), one O(3), and one O(4) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  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(1)O4 tetrahedra. In the second V site, V(2) is bonded to one O(1), one O(15), one O(21), one O(22), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  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(3)O4 tetrahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(14), one O(17), one O(23), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  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(11), one O(13), one O(16), one O(18), one O(2), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  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(2), one O(3), 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,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-49°. In the second P site, P(2) is bonded to one O(4), one O(5), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-48°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-50°. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(19) 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,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-52°. In the fifth P site, P(5) is bonded to one O(16), one O(17), one O(20), and one O(21) 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-47°. In the sixth P site, P(6) is bonded to one O(18), one O(22), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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 V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one V(2), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one Mn(1), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(5) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(6) atom. In the nineteenth O site, O(19) is bonded to one Li(1), one Li(3), one V(1), and one P(4) atom to form distorted corner-sharing OLi2VP tetrahedra. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one P(6) atom.
Li2VMn(PO4)3 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(19), one O(2), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra,  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, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-69°. The Li(1)-O(10) bond length is 1.98 Å. The Li(1)-O(19) bond length is 2.18 Å. The Li(1)-O(2) bond length is 1.89 Å. The Li(1)-O(5) bond length is 2.01 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(15), one O(20), one O(23), and one O(6) atom. The Li(2)-O(15) bond length is 2.09 Å. The Li(2)-O(20) bond length is 2.00 Å. The Li(2)-O(23) bond length is 1.90 Å. The Li(2)-O(6) bond length is 2.27 Å. In the third Li site, Li(3) is bonded to one O(1), one O(17), one O(19), and one O(22) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)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 V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-70°. The Li(3)-O(1) bond length is 2.11 Å. The Li(3)-O(17) bond length is 1.98 Å. The Li(3)-O(19) bond length is 2.00 Å. The Li(3)-O(22) bond length is 2.03 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(14), one O(21), one O(24), and one O(5) atom. The Li(4)-O(14) bond length is 1.97 Å. The Li(4)-O(21) bond length is 2.09 Å. The Li(4)-O(24) bond length is 1.99 Å. The Li(4)-O(5) bond length is 2.21 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(19), one O(20), one O(24), one O(3), and one O(4) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  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(1)O4 tetrahedra. The V(1)-O(10) bond length is 1.99 Å. The V(1)-O(19) bond length is 2.08 Å. The V(1)-O(20) bond length is 1.98 Å. The V(1)-O(24) bond length is 1.97 Å. The V(1)-O(3) bond length is 1.86 Å. The V(1)-O(4) bond length is 1.91 Å. In the second V site, V(2) is bonded to one O(1), one O(15), one O(21), one O(22), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  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(3)O4 tetrahedra. The V(2)-O(1) bond length is 1.95 Å. The V(2)-O(15) bond length is 1.98 Å. The V(2)-O(21) bond length is 1.98 Å. The V(2)-O(22) bond length is 1.97 Å. The V(2)-O(5) bond length is 2.01 Å. The V(2)-O(6) bond length is 1.87 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(14), one O(17), one O(23), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  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(12) bond length is 2.11 Å. The Mn(1)-O(14) bond length is 2.00 Å. The Mn(1)-O(17) bond length is 2.07 Å. The Mn(1)-O(23) bond length is 2.32 Å. The Mn(1)-O(7) bond length is 1.94 Å. The Mn(1)-O(9) bond length is 1.92 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(13), one O(16), one O(18), one O(2), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  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(11) bond length is 1.96 Å. The Mn(2)-O(13) bond length is 2.13 Å. The Mn(2)-O(16) bond length is 1.98 Å. The Mn(2)-O(18) bond length is 1.93 Å. The Mn(2)-O(2) bond length is 2.29 Å. The Mn(2)-O(8) bond length is 1.95 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), 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,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-49°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(7) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(4), one O(5), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-48°. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-50°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(12) bond length is 1.50 Å. The P(3)-O(6) bond length is 1.62 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(19) 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,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-52°. The P(4)-O(13) bond length is 1.49 Å. The P(4)-O(14) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.57 Å. The P(4)-O(19) bond length is 1.58 Å. In the fifth P site, P(5) is bonded to one O(16), one O(17), one O(20), and one O(21) 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-47°. The P(5)-O(16) bond length is 1.51 Å. The P(5)-O(17) bond length is 1.55 Å. The P(5)-O(20) bond length is 1.58 Å. The P(5)-O(21) bond length is 1.57 Å. In the sixth P site, P(6) is bonded to one O(18), one O(22), 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,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. The P(6)-O(18) bond length is 1.52 Å. The P(6)-O(22) bond length is 1.57 Å. The P(6)-O(23) bond length is 1.53 Å. The P(6)-O(24) 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 T-shaped geometry to one Li(3), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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 V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one V(2), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one Mn(1), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(5) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(6) atom. In the nineteenth O site, O(19) is bonded to one Li(1), one Li(3), one V(1), and one P(4) atom to form distorted corner-sharing OLi2VP tetrahedra. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one P(6) atom.