Li6V3Mn(PO4)6 crystallizes in the trigonal R3 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. In the second Li site, Li(2) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 63-71°. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 tetrahedra. In the second V site, V(2) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. Mn(1) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with three equivalent Li(2)O4 trigonal pyramids. There are two inequivalent P sites. In the first P site, P(2) is bonded to one O(5), one O(6), 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 V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 25-48°. In the second P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-49°. There are eight inequivalent O sites. In the first O site, O(8) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and one P(1) atom to form distorted corner-sharing OLi2VP tetrahedra. In the third O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the seventh O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one P(2) atom.
Li6V3Mn(PO4)6 crystallizes in the trigonal R3 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(4) bond length is 1.98 Å. The Li(1)-O(8) bond length is 2.24 Å. In the second Li site, Li(2) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 63-71°. The Li(2)-O(1) bond length is 2.24 Å. The Li(2)-O(5) bond length is 1.95 Å. The Li(2)-O(7) bond length is 1.98 Å. The Li(2)-O(8) bond length is 2.05 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 tetrahedra. All V(1)-O(2) bond lengths are 2.01 Å. All V(1)-O(8) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. All V(2)-O(4) bond lengths are 2.08 Å. All V(2)-O(6) bond lengths are 1.96 Å. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. All V(3)-O(1) bond lengths are 2.08 Å. All V(3)-O(7) bond lengths are 2.05 Å. Mn(1) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with three equivalent Li(2)O4 trigonal pyramids. All Mn(1)-O(3) bond lengths are 2.04 Å. All Mn(1)-O(5) bond lengths are 2.16 Å. There are two inequivalent P sites. In the first P site, P(2) is bonded to one O(5), one O(6), 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 V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 25-48°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.58 Å. In the second P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-49°. The P(1)-O(1) bond length is 1.59 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.57 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and one P(1) atom to form distorted corner-sharing OLi2VP tetrahedra. In the third O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the seventh O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one P(2) atom.