LiMnVO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-70°. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-54°. Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent V(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing OLiMn2V tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Mn(1) atom.
LiMnVO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-70°. Both Li(1)-O(1) bond lengths are 2.09 Å. Both Li(1)-O(2) bond lengths are 1.93 Å. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-54°. Both V(1)-O(1) bond lengths are 1.76 Å. Both V(1)-O(2) bond lengths are 1.71 Å. Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent V(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both Mn(1)-O(2) bond lengths are 2.09 Å. All Mn(1)-O(1) bond lengths are 2.17 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing OLiMn2V tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Mn(1) atom.