Structure and Vibrational Spectra of Pyridine Solvated Solid Bis(Pyridine)silver(I) Perchlorate, [Agpy₂ClO₄]·0.5py

Abstract

A hemipyridine solvate of bis(pyridine)silver(I) perchlorate, [Agpy2ClO4]·0.5py (compound 1) was prepared and characterized by single crystal X-ray analysis and vibrational spectroscopy (R and low-temperature Raman). Compound 1 was prepared via the trituration of [Agpy2ClO4] and 4[Agpy2ClO4]·[Agpy4]ClO4 (as the source of the solvate pyridine) in a mixed solvent of acetone:benzene =1:1 (v = v) at room temperature. The monoclinic crystals of compound 1 were found to be isomorphic with the analogous permanganate complex (a = 19.1093(16) Å, b = 7.7016(8) Å, c = 20.6915(19) Å, β = 105.515(7)°; space group: C2/c). Two [Agpy2]+ cations formed a dimeric unit [Agpy2ClO4]2, and each silver ion was connected to two ClO4− anions via oxygen atoms. The Ag∙∙∙Ag distance was 3.3873(5) Å, the perchlorate ions were coordinated to silver ions, and the Ag∙∙∙O distances were 2.840(2) Å and 2.8749(16) Å in the centrosymmetric rectangle of Ag-O-Ag-O. The stoichiometric ratio of the monomer [Agpy2ClO4] and the solvent pyridine was 1:0.5. The guest pyridine occupied 527.2 Å3, which was 18.0% of the volume of the unit cell. There was no additional residual solvent-accessible void in the crystal lattice. The solvate pyridine was connected via its a-CH to one of the O atoms of the perchlorate anion. Correlation analysis, as well as IR and low-temperature Raman studies, were performed to assign all perchlorate and pyridine vibrational modes. The solvate and coordinated pyridine bands in the IR and Raman spectra were not distinguishable. A perchlorate contribution via Ag-O coordination to low-frequency Raman bands was also assigned.

Keywords

• pyridine complexes
• silver perchlorate
• vibrational spectroscopy
• single crystal structure
• hydrogen bond