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

• DOI: 10.1021/ic970694l
• Publication Date: 2002-07-26T05:19:54Z
• Authors: Mohammad A. Omary; Thomas R. Webb; Zerihun Assefa; George E. Shankle; Howard H. Patterson
• Keywords: Monoclinic crystal system; Thallium; Crystal (programming language)

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