By slow reaction between colorless AgWOF and elemental F in liquid anhydrous HF, violet platelike single crystals of Ag(WOF) were grown. The crystal structure of Ag(WOF) consists of layers built from Ag cations bridged by [WOF] anions and not, as previously assumed, from infinite [Ag-F] chains and [WOF] anions. A majority (97%) of the disordered Ag cations are found with square-planar coordination of F/O ligands within the same layer, and they form additional long contacts with O/F atoms originating from the neighboring layers. The remaining 3% the of Ag(II) ions are coordinated only by F atoms in a square-planar fashion. The magnetic moments of Ag from the same layer are almost perfectly antiferromagnetically aligned. Weak ferromagnetic interlayer interactions cause a small tilt (∼1.5°) of the magnetic moments, resulting in canted antiferromagnetism. Because of the lowering of the symmetry of [WOF] in the solid state, the vibrational spectra show more bands than expected for regular C symmetry. The electronic spectrum of Ag(WOF) is reported and analyzed.
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