A highly distorted hexacoordinated silver(I) complex: synthesis,crystal structure,and DFT studies

A new highly distorted hexacoordinated silver(I) complex AgL₂NO₃] with 2-(bis(methylthio)methylene)-1-phenylbutane-1,3-dione (L) as ligand is synthesized and characterized using elemental analysis, FTIR, NMR, and X-ray single-crystal structure analysis. The ligand (L) and the nitrate group act as bidentate ligands. The geometry around the silver ion has an intermediate configuration between a trigonal prism (TP) and an octahedron (OCT). Continuous shape measure (CShM) analysis indicated a closer configuration to TP than OCT. Experimentally and theoretically, the Ag–S bonds are shorter than any of the Ag–O bonds, indicating a stronger interaction between Ag⁺ (soft metal) and S-atom as a softer site than oxygen. Natural bond orbital (NBO) analyses showed higher interaction energies between the S-atom lone pairs and the Ag–antibonding NBO (8.61–31.39 kcal/mol) than LP(O)→Ag (3.48–11.46 kcal/mol). The acceptor antibonding NBO of the Ag atom has mainly s-orbital character. The Ag atom has a natural charge of +0.7579 e at the experimental structure, suggesting that negative charge was transferred from the ligand (0.0666 e) and nitrate (0.1090 e) to the Ag ion. Using Hirshfeld surface analysis, the important intermolecular interactions between molecular units within the crystal lattice of the ligand and its Ag-complex were analyzed and compared.