Li3VMn(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded to one O(12), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(7), one O(8), and two equivalent O(9) atoms. V(1) is bonded to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. In the third P site, P(3) is bonded to one O(1), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. In the fourth P site, P(4) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-48°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the third O site, O(3) is bonded in a linear geometry to one Mn(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and one P(1) atom to form distorted OLi3MnP trigonal bipyramids that share  a cornercorner with one O(9)Li3VP trigonal bipyramid and corners with two equivalent O(6)Li3MnP trigonal bipyramids. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(4) atom. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(3), one V(1), and one P(3) atom to form distorted OLi3VP trigonal bipyramids that share  a cornercorner with one O(6)Li3MnP trigonal bipyramid and corners with two equivalent O(9)Li3VP trigonal bipyramids. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(1), and one P(3) atom.
Li3VMn(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and two equivalent O(6) atoms. The Li(1)-O(1) bond length is 2.27 Å. The Li(1)-O(2) bond length is 2.17 Å. The Li(1)-O(4) bond length is 2.54 Å. The Li(1)-O(5) bond length is 2.01 Å. There is one shorter (2.28 Å) and one longer (2.46 Å) Li(1)-O(6) bond length. In the second Li site, Li(2) is bonded to one O(12), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The Li(2)-O(12) bond length is 2.30 Å. The Li(2)-O(4) bond length is 2.21 Å. The Li(2)-O(5) bond length is 2.17 Å. The Li(2)-O(6) bond length is 2.29 Å. The Li(2)-O(8) bond length is 2.22 Å. The Li(2)-O(9) bond length is 2.32 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(7), one O(8), and two equivalent O(9) atoms. The Li(3)-O(10) bond length is 2.28 Å. The Li(3)-O(12) bond length is 2.02 Å. The Li(3)-O(7) bond length is 2.24 Å. The Li(3)-O(8) bond length is 2.63 Å. There is one shorter (2.32 Å) and one longer (2.43 Å) Li(3)-O(9) bond length. V(1) is bonded to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. The V(1)-O(10) bond length is 1.99 Å. The V(1)-O(11) bond length is 1.94 Å. The V(1)-O(12) bond length is 2.06 Å. The V(1)-O(7) bond length is 2.05 Å. The V(1)-O(8) bond length is 2.01 Å. The V(1)-O(9) bond length is 2.05 Å. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. The Mn(1)-O(1) bond length is 2.01 Å. The Mn(1)-O(2) bond length is 2.11 Å. The Mn(1)-O(3) bond length is 1.91 Å. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(5) bond length is 2.19 Å. The Mn(1)-O(6) bond length is 2.01 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. The P(1)-O(10) bond length is 1.54 Å. The P(1)-O(11) bond length is 1.51 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.59 Å. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. Both P(2)-O(4) bond lengths are 1.56 Å. Both P(2)-O(7) bond lengths are 1.55 Å. In the third P site, P(3) is bonded to one O(1), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. The P(3)-O(1) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(3) bond length is 1.53 Å. The P(3)-O(9) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-48°. Both P(4)-O(2) bond lengths are 1.54 Å. Both P(4)-O(8) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(4) atom. In the third O site, O(3) is bonded in a linear geometry to one Mn(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and one P(1) atom to form distorted OLi3MnP trigonal bipyramids that share  a cornercorner with one O(9)Li3VP trigonal bipyramid and corners with two equivalent O(6)Li3MnP trigonal bipyramids. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(4) atom. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(3), one V(1), and one P(3) atom to form distorted OLi3VP trigonal bipyramids that share  a cornercorner with one O(6)Li3MnP trigonal bipyramid and corners with two equivalent O(9)Li3VP trigonal bipyramids. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(1) and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(1), and one P(3) atom.