Copper(I) thiocyanate networks with aliphatic sulfide ligands

A total of five new CuSCN-L compounds with alkyl sulfide ligands, L = methyl sulfide (Me2S), ethyl sulfide (Et2S), isopropyl sulfide (Pri2S) or tetrahydrothiophene (THT) have been prepared and characterized. X-ray crystal structures for four of the compounds were obtained. Two compounds were collected from solutions of CuSCN in Me2S: {[Cu(SCN)(Me2S)2]}n (1a) in the form of colorless blocks and (CuSCN)(Me2S) (1b) as a white powder. Neat mixtures of CuSCN in the other alkyl sulfide ligands yielded only one product each: {[Cu(SCN)(Et2S)]}n (2); {[Cu(SCN)(Pri2S)]}n (3); and {[Cu(SCN)(THT)2]}n (4). Crystals of 2 and 4 underwent destructive phase changes at lower temperatures. Two networks types were observed: 1:2 decorated 1-D chains (1a and 4) and 1:2 decorated 1-D ladders (2 and 3). Further network formation through bridging of the organic sulfide ligands was not observed.

Copper(I) thiocyanate forms complexes {[Cu(SCN)(Me2S)2]}n, {[Cu(SCN)(Me2S)]}n, {[CuSCN)(Et2S)]}n, {[(CuSCN)(Pri2S)]}n, and {[(CuSCN)(THT)2]}n (THT = tetrahydrothiophene). In the Me2S and THT complexes the zigzag chains are formed. In the Et2S and Pri2S complexes ladders are formed. Alkyl sulfide ligands are monodentate in all cases.Figure optionsDownload as PowerPoint slide