LiMnF3 is Ilmenite structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to six equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with nine equivalent Mn(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. Mn(1) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent Mn(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. F(1) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing FLi2Mn2 trigonal pyramids.
LiMnF3 is Ilmenite structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to six equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with nine equivalent Mn(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. There are three shorter (2.03 Å) and three longer (2.23 Å) Li(1)-F(1) bond lengths. Mn(1) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent Mn(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. There are three shorter (2.10 Å) and three longer (2.20 Å) Mn(1)-F(1) bond lengths. F(1) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing FLi2Mn2 trigonal pyramids.