The reaction of 1:1 stoichiometries (1:1.5 for the nitrate/tetraethylene glycol (EO4) and pentaethylene glycol (EO5) complexes) of PbX(2) (X = NO3, Br) with five- to eight-donor poly(ethylene glycols) (PEGs) in 3:1 CH3CN/CH3OH (CH3CN only for the nitrate/EO5 complex) followed by solvent evaporation resulted in six crystalline materials upon which X-ray structural analyses were carried out : [Pb(NO3)(2)(EO4)](n), [Pb(NO3)(2)(EO5)], [Pb(NO3)(2)(EO6)], [PbBr(EO5)(mu-Br)PbBr2]. H2O, [PbBr(NCMe)(EO6)](2)[PbBr2(EO6)][PbBr3](2), and [PbBr(EO7)][PbBr3]. The nitrates crystallize as tight ion pairs with the PEG ligands coordinating in an equatorial plane around the Pb2+ ions. Because EO4 has only five oxygen donors, this complex exhibits steric unsaturation which is overcome by a monodentate interaction with a third nitrate anion that is also coordinated to a neighboring Pb2+ ion. : [Pb(NO3)(2)(EO4)](n), [Pb(NO3)(2)(EO5)], [Pb(NO3)(2)(EO6)], [PbBr(EO5)(mu-Br)PbBr2]. H2O, [PbBr(NCMe)(EO6)](2)[PbBr2(EO6)][PbBr3](2), and [PbBr(EO7)][PbBr3]. The nitrates crystallize as tight ion pairs with the PEG ligands coordinating in an equatorial plane around the Pb2+ ions. Because EO4 has only five oxygen donors, this complex exhibits steric unsaturation which is overcome by a monodentate interaction with a third nitrate anion that is also coordinated to a neighboring Pb2+ ion. : [Pb(NO3)(2)(EO4)](n), [Pb(NO3)(2)(EO5)], [Pb(NO3)(2)(EO6)], [PbBr(EO5)(mu-Br)PbBr2]. H2O, [PbBr(NCMe)(EO6)](2)[PbBr2(EO6)][PbBr3](2), and [PbBr(EO7)][PbBr3]. The nitrates crystallize as tight ion pairs with the PEG ligands coordinating in an equatorial plane around the Pb2+ ions. Because EO4 has only five oxygen donors, this complex exhibits steric unsaturation which is overcome by a monodentate interaction with a third nitrate anion that is also coordinated to a neighboring Pb2+ ion.