Crystal structures of [Cu(phen)(H2O)3(MF6)]•H2O (M = Ti, Zr, Hf) and [Cu(phen)(H2O)2F]2[HfF6]•H2O

The crystal structures of three bridged bimetallic molecular compounds, namely, triaqua-2 kappa O-3-mu-fluorido-pentafluorido-1 kappa F-5-(1,10-phenanthroline-2 kappa N-2,N')copper(II)titanium(IV) monohydrate, [Cu(TiF6)(phen)(H2O)(3)]center dot H2O (phen is 1,10-phenanthroline, C12H8N2), (I), triaqua-2 kappa O-3-mu-fluorido-pentafluorido-1 kappa(5) F-(1,10-phenanthroline-2 kappa N-2,N')copper( II)zirconium(IV) monohydrate, [Cu(ZrF6)(phen)(H2O)(3)]center dot H2O, (II), and triaqua-2 kappa O-3-mu-fluorido-pentafluorido-1 kappa(5) F-(1,10-phenanthroline-2 kappa N-2,N')copper(II)hafnium(IV) monohydrate, [Cu(HfF6)(phen)(H2O)(3)]center dot H2O, (III), and one molecular salt, bis[diaquafluorido(1,10-phenanthroline-kappa N-2,N0)copper(II)] hexafluoridohafnate(IV) dihydrate, [CuF(phen)(H2O)(2)](2)[HfF6]center dot 2H(2)O, (IV), are reported. The bridged bimetallic compounds adopt Lambda-shaped configurations, with the octahedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Lambda-shaped compounds are organized through both intra-and intermolecular hydrogen bonds and intermolecular pi-pi stacking. The salt compound [Cu(phen)(H2O)(2)F](2)[HfF6]center dot-H2O displays an isolated square-pyramidal Cu(phen)(H2O)(2)F+ complex linked to other cationic complexes and isolated HfF62- anions through intermolecular hydrogen-bonding interactions.