Au(CN)4]- as a supramolecular building block for heterobimetallic coordination polymers

A series of the first coordination polymers using the Au(CN)(4)](-) anion as a building block has been prepared. The planar tetracyanoaurate anion uses one, two, or four cyano groups to bridge to Ni(II) or Cu(II) centers and exhibits weak Au(III)-N(cyano) interactions between anions. Ni(en)(2)Au(CN)(4)](2).H(2)O (1, en = ethylenediamine) is a molecular compound with the two Au(CN)(4)](-) anions coordinating in a trans orientation to Ni(II) without further cyanide coordination. Cu(dien)Au(CN)(4)](2) (2, dien = diethylenetriamine) forms a similar molecular complex; however, the dimensionality is increased through weak intermolecular Au-N(cyano) interactions of 3.002(14) A to form a 1-D zigzag chain. Cu(en)(2)Au(CN)(4)](2) (3) also forms a molecular complex similar to 1, but with elongated axial bonds. The complex further aggregates through Au-N(cyano) interactions of 3.035(8) A to form a 2-D array. In Cu(dmeda)(2)Au(CN)(4)]Au(CN)(4)] (4, dmeda = N,N-dimethylethylenediamine) one Au(CN)(4)](-) anion coordinates via two cis-N(cyano) donors to the axial sites of two Cu(II) centers to form a 1-D zigzag chain of alternating Cu(dmeda)(2)](2+) and Au(CN)(2)](-) units; the other Au(CN)(4)](-) anion forms a 1-D chain via Au-N(cyano) interactions. In Cu(bipy)(H(2)O)(2)(Au(CN)(4))(0.5)]Au(CN)(4)](1.5) (5, bipy = 2,2'-bipyridine) one Au(CN)(4)](-) anion uses all four cyano moieties to bridge four different Cu(II) centers, creating a 1-D chain.