Crystal structures of [Cu(phen)(H(2)O)(3)(MF(6))]·H(2)O (M = Ti, Zr, Hf) and [Cu(phen)(H(2)O)(2)F](2)[HfF(6)]·H(2)O.

The crystal structures of three bridged bimetallic mol-ecular compounds, namely, tri-aqua-2κ(3) O-μ-fluorido-penta-fluorido-1κ(5) F-(1,10-phenanthroline-2κ(2) N,N')copper(II)titanium(IV) monohydrate, [Cu(TiF(6))(phen)(H(2)O)(3)]·H(2)O (phen is 1,10-phenanthroline, C(12)H(8)N(2)), (I), tri-aqua-2κ(3) O-μ-fluorido-penta-fluorido-1κ(5) F-(1,10-phenanthroline-2κ(2) N,N')copper(II)zirconium(IV) monohydrate, [Cu(ZrF(6))(phen)(H(2)O)(3)]·H(2)O, (II), and tri-aqua-2κ(3) O-μ-fluorido-penta-fluorido-1κ(5) F-(1,10-phenanthroline-2κ(2) N,N')copper(II)hafnium(IV) monohydrate, [Cu(HfF(6))(phen)(H(2)O)(3)]·H(2)O, (III), and one mol-ecular salt, bis-[diaqua-fluorido-(1,10-phenanthroline-κ(2) N,N')copper(II)] hexa-fluorido-hafnate(IV) dihydrate, [CuF(phen)(H(2)O)(2)](2)[HfF(6)]·2H(2)O, (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 via 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)(H(2)O)(2)F](2)[HfF(6)]·H(2)O displays an isolated square-pyramidal Cu(phen)(H(2)O)(2)F(+) complex linked to other cationic complexes and isolated HfF(6) (2-) anions through inter-molecular hydrogen-bonding inter-actions.