Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts

Beves, Jonathon E., Constable, Edwin C., Decurtins, Silvio, Dunphy, Emma L., Housecroft, Catherine E., Keene, Tony D., Neuburger, Markus, Schaffner, Silvia and Zampese, Jennifer A. (2009) Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts. CrystEngComm, 11 (11), 2406-2416. (doi:10.1039/b909639f).

Abstract

We have demonstrated that treatment of [Fe(1)(2)](2+) (1 = 4'-(4-pyridyl)-2,2':6',2 ''-terpyridine) with an excess of CuCl(2)center dot 2H(2)O leads to competition between coordination of copper(II) by the pendant pyridine donors in [Fe(1)(2)](2+), and transfer of ligand 1 from iron(II) to copper(II) to yield [{Cl(3)Cu(mu-1)Fe(mu-1)}(2)CuCl(2)(OH(2))(2)]Cl(2)center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4H(2)O, respectively. Direct reaction of 1 with CuCl(2)center dot 2H(2)O and variation in crystallization conditions results in the formation of either monomeric or polymeric complexes: [Cu(1)Cl(2)]center dot 4.75H(2)O, [Cu(1)Cl(2)]center dot H(2)O center dot MeOH and [Cu(1)Cl(2)center dot 2H(2)O](n). The reaction of 1 with Cu(NO(3))(2)center dot 3H(2)O gives the coordination polymer [Cu(1)(ONO(2))(2)center dot H(2)O](n). Magnetic data for [Cu(1)Cl(2)center dot 2H(2)O](n) and [Cu(1)(ONO(2))(2)center dot H(2)O](n) are consistent with antiferromagnetically- coupled chains. Reactions of CuCl(2)center dot 2H(2)O with ligands 2 and 3 (2 = 4'-(3-pyridyl)-2,2':6',2 ''-terpyridine, 3 = 4'-(2-pyridyl)-2,2':6',2 ''-terpyridine) lead to monomeric complexes. With the exception of [Cu(3)Cl(2)], the mononuclear complexes show a propensity for the incorporation of water into their crystal lattices; in the case of [Cu(H1)Cl(2)]Cl center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4.75H(2)O, the small change in water content leads to the assembly of (5.8(2))(2)(5.6.8)(4)(5(2).6)(2) or (4(2).6(2))(3)(4.6(2))(6) water-chloride ion nets.

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Contributors

Author: Tony D. Keene

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