NaFeF3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1) and six equivalent F(2) atoms. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form a mixture of corner and edge-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form distorted FNa2Fe2 tetrahedra that share corners with four equivalent F(1)Na2Fe2 tetrahedra, corners with eight equivalent F(2)Na3Fe2 trigonal bipyramids, and edges with six equivalent F(2)Na3Fe2 trigonal bipyramids. In the second F site, F(2) is bonded to three equivalent Na(1) and two equivalent Fe(1) atoms to form distorted FNa3Fe2 trigonal bipyramids that share corners with four equivalent F(1)Na2Fe2 tetrahedra, corners with nine equivalent F(2)Na3Fe2 trigonal bipyramids, edges with three equivalent F(1)Na2Fe2 tetrahedra, and edges with six equivalent F(2)Na3Fe2 trigonal bipyramids.
NaFeF3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1) and six equivalent F(2) atoms. Both Na(1)-F(1) bond lengths are 2.29 Å. There are four shorter (2.40 Å) and two longer (2.56 Å) Na(1)-F(2) bond lengths. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form a mixture of corner and edge-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Fe(1)-F(1) bond lengths are 2.02 Å. All Fe(1)-F(2) bond lengths are 2.09 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form distorted FNa2Fe2 tetrahedra that share corners with four equivalent F(1)Na2Fe2 tetrahedra, corners with eight equivalent F(2)Na3Fe2 trigonal bipyramids, and edges with six equivalent F(2)Na3Fe2 trigonal bipyramids. In the second F site, F(2) is bonded to three equivalent Na(1) and two equivalent Fe(1) atoms to form distorted FNa3Fe2 trigonal bipyramids that share corners with four equivalent F(1)Na2Fe2 tetrahedra, corners with nine equivalent F(2)Na3Fe2 trigonal bipyramids, edges with three equivalent F(1)Na2Fe2 tetrahedra, and edges with six equivalent F(2)Na3Fe2 trigonal bipyramids.