LiFeF3 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 Fe(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. Fe(1) is bonded to six equivalent F(1) atoms to form FeF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. F(1) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Fe2 trigonal pyramids.
LiFeF3 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 Fe(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. There are three shorter (1.98 Å) and three longer (2.23 Å) Li(1)-F(1) bond lengths. Fe(1) is bonded to six equivalent F(1) atoms to form FeF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. There are three shorter (2.08 Å) and three longer (2.13 Å) Fe(1)-F(1) bond lengths. F(1) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Fe2 trigonal pyramids.