Inorganic Chemistry 2001-01-01

Crystal Structure, Electronic Structure, and Temperature-Dependent Raman Spectra of Tl[Ag(CN)(2)]: Evidence for Ligand-Unsupported Argentophilic Interactions.

MohammadA. Omary, ThomasR. Webb, Zerihun Assefa, GeorgeE. Shankle, HowardH. Patterson

Index: Inorg. Chem. 37 , 1380, (1998)

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Abstract

The structure of thallium dicyanoargentate(I) has been determined crystallographically. The crystal structure shows an Ag-Ag distance of 3.11 _. This is the shortest Ag-Ag distance reported for any silver dicyanide salt whose crystal structure has been determined. Raman spectra of the compound show four nu(C)(-)(N) peaks that are well-resolved in the 10-80 K temperature range. This result agrees well with group theory analysis. Extended H_ckel calculations using relativistic wave functions have been carried out for two models which describe the interactions between the Ag(CN)(2)(-) ions within the crystal structure of Tl[Ag(CN)(2)]. The results of these calculations indicate the formation of potential wells at short Ag-Ag distances. The data in this study suggest the significance of ligand-unsupported silver-silver interactions (argentophilicity) in Tl[Ag(CN)(2)]. Tl-Ag interactions are determined to be insignificant in the compound. Tl[Ag(CN)(2)] crystallizes in the monoclinic space group P2(1)/c (No. 14), with a = 7.798(1) _, b = 14.685(3) _, c = 8.566(2) _, beta = 91.66(2) degrees, Z = 8, R = 0.0643, and R(w) = 0.0899.