Di-μ-fluoro-bis[aqua-(dimethyl sulfoxide)-trifluorozirconium(IV)]

[Zr 2 F 8 (dmso) 2 (H 2 O) 2 ], a dehydration product of [ZrF 4 (dmso)(H 2 O) 2 ]⋅2H 2 O, crystallizes in the orthorhombic symmetry [space group C m c a , a =7.8266(3) Å, b =13.5847(5) Å, c =15.6119(6) Å, and Z =4]. The structure, solved ab initio in direct space from X-ray powder diffraction data, is built up from [Zr 2 F 8 O 4 ] bipolyhedra formed by edge sharing of [ZrF 5 O 2 ] pentagonal bipyramids (condensed from isolated [ZrF 4 O 3 ] pentagonal bipyramids in the precursor). Difficulties associated with a fortuitous hexagonal pseudosymmetry were surmounted. The dmso departure at 220 °C leads to an amorphous phase.