Canted Antiferromagnetism in Two-Dimensional Silver(II) Bis[pentafluoridooxidotungstate(VI)].

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.

[Ag(OH ) ][Ag(SO ) ]: A Hydrate of a Silver(II) Salt.

When exposed to air at ambient conditions, AgSO slowly reacts with moisture, yielding AgSO ⋅H O. The crystal structure determination (powder data) shows that it may be described as [Ag(OH ) ][Ag(SO ) ], with some sulfate groups being shared between different Ag cations, resembling in that way its Cu analogue. [Ag(OH ) ][Ag(SO ) ], the first hydrate of a compound of Ag , was extensively characterized using many physicochemical methods.

AgSO meets AgSO: the second example of metal-ligand redox isomerism among inorganic systems.

Valence (redox) isomerism based on electron exchange between a metal and a ligand is immensely rare in purely inorganic systems, with only one documented case, that of PbS which adopts two polymorphic forms corresponding to Pb(iv)(S) and Pb(ii)(S). Here we have taken advantage of metathetic reactions using salts of weakly coordinating anions and we have prepared for the first time Ag(i)SO, silver(i) peroxydisulphate. The title compound crystallizes in the non-centrosymmetric Cc space group with partial disorder of the anionic sublattice.