1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)S2C3H6 Substituent and Reaction Conditions on the Architecture of the 0D–3D Networks

The parent compound 1,3-dithiane (L1) was reacted with CuI providing the 1D coordination polymer [{Cu(μ2-I)2Cu}(μ2-L1)2]n (CP1), an isostructural compound [{Cu(μ2-Br)2Cu}(μ2-L1)2]n (CP2) was isolated upon treatment of CuBr with L1. In contrast, treatment of L1 with CuCl results in the formation of 2D polymeric [{Cu(μ2-Cl)2Cu}(μ2-L1)]n (CP3), in which each sulfur atom acts as a 4-electron donor. The 1D compounds [{Cu(μ2-X)2Cu}(μ2-L2)2]n (CP7, X = Br, and CP8, X = Cl) resulting from treatment of 2-methyl-1,3 dithiane (L2) with CuBr and CuCl are isostructural with their CuI homologue [{Cu(μ2-I)2Cu}(μ2-L2)2]n (CP5), reported previously. Using CuCN, a 2D CP of composition [{Cu(μ2-CN)2Cu}(μ2-L2)2]n (CP9) has been isolated. Complexation of 2-isobutyl-1,3-dithiane (L3) on CuI generates a 2D material [{Cu3(μ3-I)(μ2-I)2(μ2-L3)2}]n (CP10), incorporating the usual trinuclear μ3-I-capped Cu clusters as SBUs, whereas 2D-polymeric compounds [{Cu(μ2-Br)2Cu}(μ2-L3)2]n (CP11) and [{Cu(μ2-Cl)2Cu}(μ2-L3)2]n (CP12) were obtai...