Multi-dimensional transition-metal coordination polymers of 4,4′-bipyridine-N,N′-dioxide:: 1D chains and 2D sheets

Reaction of 4,4'-bipyridine-N,N'-dioxide (L) with a variety of transition-metal salts in MeOH affords a range of coordination polymer products. For the complexes [FeCl3(mu-L)](infinity), 1, and ([Cu(L)(2)(OHMe)(2)(mu-L)]center dot 2PF(6)center dot n(solv))(infinity), 2, 1D chain structures are observed, whereas ([Mn(mu-L)(3)]center dot 2ClO(4))(infinity), 3, and ([Cu(mu-L)(3)]center dot 2BF(4))(infinity), 4, both show 2D sheet architectures incorporating an unusual 3(6)-hxl topology. The more common 4(4)-sql topology is observed in [Cd(ONO2)(2)(mu-L)(2)](infinity), 5, ([Cu(OHMe)(2)(mu-L)(2)]center dot 2ZrF(5))(infinity), 6, ([Cu(L)(2)(mu-L)(2)]center dot 2EF(6))(infinity) (7 E = P; 8 E = Sb), and ([Et4N][Cu(OHMe)(0.5)(mu-L)(2)(mu-FSiF4F)(0.5)]center dot 2SbF(6)center dot n(solv))(infinity), 9. In 6, the [ZrF5](-) anion, formed in situ from [ZrF6](2-), forms 1D anionic chains ([ZrF5]-)- of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated ([Cu(OHMe)(2)(mu-L)(2)](2+))(infinity) 4(4)-sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 4(4)-sql sheets of stoichiometry ([Cu(L)(2)](2+))(infinity) coordinatively linked by bridging [SiF6](2-) anions to give a structure of 5-c 4(4).6(6)-sqp topology. The mononuclear [Cu(L)(6)]center dot 2BF(4) (10) and [Cd(L)(6)]center dot 2NO(3) (11) and binuclear complexes [(Cu(L)(OH2))(2)(mu-L)(2))]center dot 2SiF(6)center dot n(solv), 12, are also reported. The majority of the coordination polymers are free of solvent and are nonporous. Thermal treatment of materials that do contain solvent results in structural disintegration of the complex structures giving no permanent porosity.