NaCdF3 is Ilmenite-like structured and crystallizes in the trigonal R3c space group. Na(1) is bonded to six equivalent F(1) atoms to form distorted NaF6 octahedra that share corners with three equivalent Cd(1)F6 octahedra, corners with six equivalent Na(1)F6 octahedra, edges with three equivalent Cd(1)F6 octahedra, and  a faceface with one Cd(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. Cd(1) is bonded to six equivalent F(1) atoms to form CdF6 octahedra that share corners with three equivalent Na(1)F6 octahedra, corners with six equivalent Cd(1)F6 octahedra, edges with three equivalent Na(1)F6 octahedra, and  a faceface with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-64°. F(1) is bonded to two equivalent Na(1) and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing FNa2Cd2 trigonal pyramids.
NaCdF3 is Ilmenite-like structured and crystallizes in the trigonal R3c space group. Na(1) is bonded to six equivalent F(1) atoms to form distorted NaF6 octahedra that share corners with three equivalent Cd(1)F6 octahedra, corners with six equivalent Na(1)F6 octahedra, edges with three equivalent Cd(1)F6 octahedra, and  a faceface with one Cd(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. There are three shorter (2.24 Å) and three longer (2.35 Å) Na(1)-F(1) bond lengths. Cd(1) is bonded to six equivalent F(1) atoms to form CdF6 octahedra that share corners with three equivalent Na(1)F6 octahedra, corners with six equivalent Cd(1)F6 octahedra, edges with three equivalent Na(1)F6 octahedra, and  a faceface with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-64°. There are three shorter (2.21 Å) and three longer (2.28 Å) Cd(1)-F(1) bond lengths. F(1) is bonded to two equivalent Na(1) and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing FNa2Cd2 trigonal pyramids.