NaMgF3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent F(2) and six equivalent F(1) atoms. Mg(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form a mixture of corner and edge-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles are 43°. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Na(1) and two equivalent Mg(1) atoms to form distorted FNa3Mg2 trigonal bipyramids that share corners with four equivalent F(2)Na2Mg2 tetrahedra, corners with nine equivalent F(1)Na3Mg2 trigonal bipyramids, edges with three equivalent F(2)Na2Mg2 tetrahedra, and edges with six equivalent F(1)Na3Mg2 trigonal bipyramids. In the second F site, F(2) is bonded to two equivalent Na(1) and two equivalent Mg(1) atoms to form distorted FNa2Mg2 tetrahedra that share corners with four equivalent F(2)Na2Mg2 tetrahedra, corners with eight equivalent F(1)Na3Mg2 trigonal bipyramids, and edges with six equivalent F(1)Na3Mg2 trigonal bipyramids.
NaMgF3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent F(2) and six equivalent F(1) atoms. Both Na(1)-F(2) bond lengths are 2.26 Å. There are four shorter (2.40 Å) and two longer (2.52 Å) Na(1)-F(1) bond lengths. Mg(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form a mixture of corner and edge-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles are 43°. Both Mg(1)-F(2) bond lengths are 1.96 Å. All Mg(1)-F(1) bond lengths are 2.00 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Na(1) and two equivalent Mg(1) atoms to form distorted FNa3Mg2 trigonal bipyramids that share corners with four equivalent F(2)Na2Mg2 tetrahedra, corners with nine equivalent F(1)Na3Mg2 trigonal bipyramids, edges with three equivalent F(2)Na2Mg2 tetrahedra, and edges with six equivalent F(1)Na3Mg2 trigonal bipyramids. In the second F site, F(2) is bonded to two equivalent Na(1) and two equivalent Mg(1) atoms to form distorted FNa2Mg2 tetrahedra that share corners with four equivalent F(2)Na2Mg2 tetrahedra, corners with eight equivalent F(1)Na3Mg2 trigonal bipyramids, and edges with six equivalent F(1)Na3Mg2 trigonal bipyramids.