LiVF3 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 V(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent V(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 trigonal pyramids.
LiVF3 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 V(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. There are three shorter (2.00 Å) and three longer (2.30 Å) Li(1)-F(1) bond lengths. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with nine equivalent Li(1)F6 octahedra, edges with three equivalent V(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. All V(1)-F(1) bond lengths are 2.13 Å. F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 trigonal pyramids.