Synthesis, structure, and characterization of Cu4S10(4-methylpyridine)4

Abstract

The title compound, Cu4S10(4-methylpyridine)4 · 4-methylpyridine was prepared by three different reactions: the oxidation of copper power by sulfur and the reaction of copper (I) sulfide (or CuBr-SMe2) with cues sulfur, both in the coordinating solvent, 4-methylpyridine. Red crystals of the compound obtained by layering with hexans were subjected to single crystal X-ray diffraction. The structure was refined toR=0.026 and R w =0.036 in a space groupP1bar (No. 2), withZ=2,a=13.983 (2) A,b=15.384( 2) Å,c=9.660 (1) Å, α = 93.87 (1)°,β=93.38 =γ=(1)°,V=2037.9 (9) Å3. The commpound has approximate S4 symmetry and consists of two pentasuffide chains linking four Cu(I) ions, each with a coordinating 2-methylpyridine. The infrared spectrum was dominated by absorption due to coodinated 4-methylpyridine with several low-energy peaks attributable to S-S stretches, which were also observed by Raman spectroscopy. A featureless electronic absorption spectrum yielded a single peak in the mar ultraviolet upon computer enhancement (λ=334 nm, ε = 10,000), most likely an intraligand transition. Cyclic voltammetry indicates that the polysulfide complex undergoes irreversible oxidation and reduction at +0.04 and −0.34 V vs. SCR respectively, at NS K in 4-methylpyridine when swept at 20 mV/sec. The electrochemical behavior was unvaried even at sweep rates as high as 100 V/sec.