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Perfluorinated mercury-containing anticrowns constitute an important class of anion receptors and catalysts but a rapid development of their chemistry is hampered by an insufficiently wide range of available compounds of such a type. Taking this into account, we have studied the interaction of o,o’-dilithiooctafluorobiphenyl with HgCl2 and found that this reaction gives two products, viz., threemercury anticrown (o,o'-C6F4C6F4Hg)3 (1) and a chloride complex of the previously unknown fourmercury anticrown (o,o'-C6F4C6F4Hg)4 (2), viz., Li{[(o,o'-C6F4C6F4Hg)4]Cl} (3). The latter could be easily converted to the free 2 by the reaction with boiling water. The complexes of these new mercury anticrowns with o-xylene and acetonitrile have been synthesized and structurally characterized. The structure of an adduct of 3 with 12-crown-4, viz., [Li(12-crown-4)2]{[(o,o'-C6F4C6F4Hg)4]Cl}, was also determined. It turned out that in this adduct, the chloride anion is η4-coordinated with the Hg-sites of 2. The complexing ability of the three-mercury anticrown 1 towards halide anions was studied as well.