LiVF3 is Ilmenite-like structured and crystallizes in the orthorhombic Pccn space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids.
LiVF3 is Ilmenite-like structured and crystallizes in the orthorhombic Pccn space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 2.22 Å. The Li(1)-F(4) bond length is 2.04 Å. There is one shorter (1.91 Å) and one longer (2.48 Å) Li(1)-F(1) bond length. There is one shorter (1.93 Å) and one longer (2.04 Å) Li(1)-F(2) bond length. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. The V(1)-F(3) bond length is 2.13 Å. The V(1)-F(4) bond length is 2.17 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) V(1)-F(1) bond length. There is one shorter (2.14 Å) and one longer (2.15 Å) V(1)-F(2) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids.