Crystal structures of [Cu(phen)(HO)(F)]·HO ( = Ti, Zr, Hf) and [Cu(phen)(HO)F][HfF]·HO.

The crystal structures of three bridged bimetallic mol-ecular compounds, namely, tri-aqua-2κ -μ-fluorido-penta-fluorido-1κ -(1,10-phenanthroline-2κ ,')copper(II)titanium(IV) monohydrate, [Cu(TiF)(phen)(HO)]·HO (phen is 1,10-phenanthroline, CHN), (I), tri-aqua-2κ -μ-fluorido-penta-fluorido-1κ -(1,10-phenanthroline-2κ ,')copper(II)zirconium(IV) monohydrate, [Cu(ZrF)(phen)(HO)]·HO, (II), and tri-aqua-2κ -μ-fluorido-penta-fluorido-1κ -(1,10-phenanthroline-2κ ,')copper(II)hafnium(IV) monohydrate, [Cu(HfF)(phen)(HO)]·HO, (III), and one mol-ecular salt, bis-[diaqua-fluorido-(1,10-phenanthroline-κ ,')copper(II)] hexa-fluorido-hafnate(IV) dihydrate, [CuF(phen)(HO)][HfF]·2HO, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octa-hedrally coordinated copper(II) center linked to the fluorinated early transition metal a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and inter-molecular hydrogen bonds and inter-molecular π-π stacking. The salt compound [Cu(phen)(HO)F][HfF]·HO displays an isolated square-pyramidal Cu(phen)(HO)F complex linked to other cationic complexes and isolated HfF anions through inter-molecular hydrogen-bonding inter-actions.