Na2W(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form distorted NaF6 octahedra that share corners with two equivalent Na(2)O4F2 octahedra, corners with two equivalent W(1)O2F4 octahedra, corners with four equivalent Na(1)F6 octahedra, and edges with two equivalent W(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. In the second Na site, Na(2) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with six equivalent W(1)O2F4 octahedra, and edges with two equivalent Na(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. W(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form WO2F4 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with six equivalent Na(2)O4F2 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. O(1) is bonded in a 3-coordinate geometry to two equivalent Na(2) and one W(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one W(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Na(1) and one W(1) atom.
Na2W(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form distorted NaF6 octahedra that share corners with two equivalent Na(2)O4F2 octahedra, corners with two equivalent W(1)O2F4 octahedra, corners with four equivalent Na(1)F6 octahedra, and edges with two equivalent W(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. Both Na(1)-F(1) bond lengths are 2.50 Å. There are two shorter (2.26 Å) and two longer (2.31 Å) Na(1)-F(2) bond lengths. In the second Na site, Na(2) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with six equivalent W(1)O2F4 octahedra, and edges with two equivalent Na(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. There are two shorter (2.44 Å) and two longer (2.46 Å) Na(2)-O(1) bond lengths. Both Na(2)-F(1) bond lengths are 2.35 Å. W(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form WO2F4 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with six equivalent Na(2)O4F2 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. Both W(1)-O(1) bond lengths are 1.78 Å. Both W(1)-F(1) bond lengths are 1.97 Å. Both W(1)-F(2) bond lengths are 2.08 Å. O(1) is bonded in a 3-coordinate geometry to two equivalent Na(2) and one W(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one W(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Na(1) and one W(1) atom.