Abstract
A di(μ-phenoxo)CoIICuI complex, [CoCu(L)]ClO4·0.5DMF, has been prepared where (L)2- is a macrocyclic dinucleating compartmental ligand derived from the 2:1:1 condensation of 2,6-diformyl-4-methylphenol, ethylenediamine, and 3-thia-1,5-pentanediamine, having a salen-like N2O2 metal-binding site (salen = N,N‘-ethylenedisalicylideneaminate) and an N2O2S site sharing the phenolic oxygens. It crystallizes in the monoclinic space group P21/n, a = 7.087(1) A, b = 19.593(6) A, c = 19.447(3) A, β = 96.29(1)°, V = 2684(1) A3, and Z = 4. The CoII resides in the salen-like site and assumes a planar geometry. The CuI in the N2O2S site has a planar four-coordinate geometry with two phenolic oxygens and two imine nitrogens; the thioether sulfur on the lateral chain is situated at an axial site of the CuI, but the Cu--S separation is very large (3.08 A). In the {CuN2O2} chromophore, the two Cu−O bond distances (2.333(5) and 2.385(5) A) are significantly long relative to the two Cu−N bond distances (1.984(6) and 1.929(4) ...
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