Na2SbF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), two equivalent F(1), and two equivalent F(5) atoms. In the second Na site, Na(2) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms to form NaF6 octahedra that share corners with two equivalent Na(2)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, and edges with two equivalent Sb(1)F5 square pyramids. The corner-sharing octahedral tilt angles are 57°. Sb(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted SbF5 square pyramids that share corners with two equivalent Na(2)F6 octahedra and edges with two equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Sb(1) atom to form a mixture of edge and corner-sharing FNa3Sb tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Sb(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Sb(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Sb(1) atom to form a mixture of edge and corner-sharing FNa3Sb tetrahedra.
Na2SbF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), two equivalent F(1), and two equivalent F(5) atoms. The Na(1)-F(2) bond length is 2.23 Å. The Na(1)-F(3) bond length is 2.22 Å. There is one shorter (2.24 Å) and one longer (2.31 Å) Na(1)-F(1) bond length. There is one shorter (2.32 Å) and one longer (2.49 Å) Na(1)-F(5) bond length. In the second Na site, Na(2) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms to form NaF6 octahedra that share corners with two equivalent Na(2)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, and edges with two equivalent Sb(1)F5 square pyramids. The corner-sharing octahedral tilt angles are 57°. The Na(2)-F(1) bond length is 2.37 Å. The Na(2)-F(2) bond length is 2.27 Å. The Na(2)-F(3) bond length is 2.23 Å. The Na(2)-F(5) bond length is 2.32 Å. There is one shorter (2.25 Å) and one longer (2.31 Å) Na(2)-F(4) bond length. Sb(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted SbF5 square pyramids that share corners with two equivalent Na(2)F6 octahedra and edges with two equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Sb(1)-F(1) bond length is 2.11 Å. The Sb(1)-F(2) bond length is 2.07 Å. The Sb(1)-F(3) bond length is 2.09 Å. The Sb(1)-F(4) bond length is 2.09 Å. The Sb(1)-F(5) bond length is 2.01 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Sb(1) atom to form a mixture of edge and corner-sharing FNa3Sb tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Sb(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Sb(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Sb(1) atom to form a mixture of edge and corner-sharing FNa3Sb tetrahedra.