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 in a 4-coordinate geometry to one O(24), one O(3), one O(6), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(12), one O(17), one O(21), and one O(22) atom. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(1), one O(14), one O(17), and one O(19) atom. 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(12), one O(14), one O(17), one O(23), one O(7), 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. In the second V site, V(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 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(10), one O(19), one O(20), one O(24), one O(3), and one O(4) 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(15), one O(21), one O(22), one O(5), and one O(6) 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(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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-48°. 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-46°. 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-48°. 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. 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(3), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) 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 distorted bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Mn(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(1), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the fourteenth O site, O(14) is bonded to one Li(3), one Li(4), one V(1), and one P(4) atom to form distorted OLi2VP tetrahedra that share  a cornercorner with one O(24)Li2MnP tetrahedra and  an edgeedge with one O(17)Li2VP trigonal pyramid. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the seventeenth O site, O(17) is bonded to one Li(2), one Li(3), one V(1), and one P(5) atom to form edge-sharing OLi2VP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a linear geometry to one V(2) and one P(6) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(5) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded to one Li(1), one Li(4), one Mn(1), and one P(6) atom to form distorted corner-sharing OLi2MnP tetrahedra.
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 in a 4-coordinate geometry to one O(24), one O(3), one O(6), and one O(8) atom. The Li(1)-O(24) bond length is 2.16 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(8) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(12), one O(17), one O(21), and one O(22) atom. The Li(2)-O(12) bond length is 2.05 Å. The Li(2)-O(17) bond length is 2.15 Å. The Li(2)-O(21) bond length is 2.51 Å. The Li(2)-O(22) bond length is 1.97 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(1), one O(14), one O(17), and one O(19) atom. The Li(3)-O(1) bond length is 2.06 Å. The Li(3)-O(14) bond length is 2.44 Å. The Li(3)-O(17) bond length is 2.02 Å. The Li(3)-O(19) bond length is 2.05 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 2.05 Å. The Li(4)-O(21) bond length is 2.14 Å. The Li(4)-O(24) bond length is 2.12 Å. The Li(4)-O(5) bond length is 1.97 Å. There are two inequivalent V sites. In the first V site, V(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 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(12) bond length is 1.98 Å. The V(1)-O(14) bond length is 2.00 Å. The V(1)-O(17) bond length is 2.11 Å. The V(1)-O(23) bond length is 1.96 Å. The V(1)-O(7) bond length is 1.90 Å. The V(1)-O(9) bond length is 1.83 Å. In the second V site, V(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 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(11) bond length is 1.91 Å. The V(2)-O(13) bond length is 1.98 Å. The V(2)-O(16) bond length is 1.85 Å. The V(2)-O(18) bond length is 1.94 Å. The V(2)-O(2) bond length is 1.97 Å. The V(2)-O(8) bond length is 2.02 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(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 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 1.95 Å. The Mn(1)-O(19) bond length is 1.96 Å. The Mn(1)-O(20) bond length is 2.12 Å. The Mn(1)-O(24) bond length is 2.03 Å. The Mn(1)-O(3) bond length is 2.32 Å. The Mn(1)-O(4) bond length is 1.95 Å. In the second Mn site, Mn(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 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 1.94 Å. The Mn(2)-O(15) bond length is 1.94 Å. The Mn(2)-O(21) bond length is 2.03 Å. The Mn(2)-O(22) bond length is 2.35 Å. The Mn(2)-O(5) bond length is 2.16 Å. The Mn(2)-O(6) bond length is 1.96 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-48°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(7) bond length is 1.54 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-46°. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.57 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.56 Å. The P(3)-O(6) bond length is 1.55 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. The P(4)-O(13) bond length is 1.52 Å. The P(4)-O(14) bond length is 1.58 Å. The P(4)-O(15) bond length is 1.53 Å. The P(4)-O(19) bond length is 1.57 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-48°. The P(5)-O(16) bond length is 1.57 Å. The P(5)-O(17) bond length is 1.57 Å. The P(5)-O(20) bond length is 1.50 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, and  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. The P(6)-O(18) bond length is 1.53 Å. The P(6)-O(22) bond length is 1.53 Å. The P(6)-O(23) bond length is 1.56 Å. The P(6)-O(24) bond length is 1.59 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(3), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) 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 distorted bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Mn(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(1), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the fourteenth O site, O(14) is bonded to one Li(3), one Li(4), one V(1), and one P(4) atom to form distorted OLi2VP tetrahedra that share  a cornercorner with one O(24)Li2MnP tetrahedra and  an edgeedge with one O(17)Li2VP trigonal pyramid. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the seventeenth O site, O(17) is bonded to one Li(2), one Li(3), one V(1), and one P(5) atom to form edge-sharing OLi2VP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a linear geometry to one V(2) and one P(6) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(5) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded to one Li(1), one Li(4), one Mn(1), and one P(6) atom to form distorted corner-sharing OLi2MnP tetrahedra.