LiCuF3 is Calcite structured and crystallizes in the trigonal R3c space group. Li(1) is bonded to six equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with three equivalent Cu(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and  a faceface with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent Cu(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. F(1) is bonded to two equivalent Li(1) and two equivalent Cu(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Cu2 trigonal pyramids.
LiCuF3 is Calcite structured and crystallizes in the trigonal R3c space group. Li(1) is bonded to six equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with three equivalent Cu(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and  a faceface with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. There are three shorter (1.92 Å) and three longer (2.20 Å) Li(1)-F(1) bond lengths. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent Cu(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. There are three shorter (1.99 Å) and three longer (2.02 Å) Cu(1)-F(1) bond lengths. F(1) is bonded to two equivalent Li(1) and two equivalent Cu(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Cu2 trigonal pyramids.