Na3InF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent In(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent F(1), two equivalent F(2), and three equivalent F(3) atoms. In(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form InF6 octahedra that share corners with six equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one In(1) atom to form a mixture of distorted corner and edge-sharing FNa3In trigonal pyramids. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one In(1) atom to form a mixture of distorted corner and edge-sharing FNa3In trigonal pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(1), three equivalent Na(2), and one In(1) atom.
Na3InF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent In(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. Both Na(1)-F(1) bond lengths are 2.26 Å. Both Na(1)-F(2) bond lengths are 2.31 Å. Both Na(1)-F(3) bond lengths are 2.20 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent F(1), two equivalent F(2), and three equivalent F(3) atoms. There is one shorter (2.29 Å) and one longer (2.53 Å) Na(2)-F(1) bond length. There is one shorter (2.28 Å) and one longer (2.30 Å) Na(2)-F(2) bond length. There are a spread of Na(2)-F(3) bond distances ranging from 2.27-2.73 Å. In(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form InF6 octahedra that share corners with six equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. Both In(1)-F(1) bond lengths are 2.09 Å. Both In(1)-F(2) bond lengths are 2.09 Å. Both In(1)-F(3) bond lengths are 2.07 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one In(1) atom to form a mixture of distorted corner and edge-sharing FNa3In trigonal pyramids. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one In(1) atom to form a mixture of distorted corner and edge-sharing FNa3In trigonal pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(1), three equivalent Na(2), and one In(1) atom.