Modeling the effect of H-bonding interactions and molecular packing on the molecular structure of [Ag(ethylnicotinate)(2)]NO (3) complex.

The gas phase molecular structure of a single isolated molecule of [Ag(Etnic)(2)NO(3)];1 where Etnic = Ethylnicotinate was calculated using B3LYP method. The H-bonding interaction between 1 with one (complex 2) and two (complex 3) water molecules together with the dimeric formula [Ag(Etnic)(2)NO(3)](2);4 and the tetrameric formula [Ag(Etnic)(2)NO(3)](4);5 were calculated using the same level of theory to model the effect of intermolecular interactions and molecular packing on the molecular structure of the titled complex. The H-bond dissociation energies of complexes 2 and 3 were calculated to be in the range of 12.220-14.253 and 30.106-31.055 kcal mol(-1), respectively, indicating the formation of relatively strong H-bonds between 1 and water molecules. The calculations predict bidentate nitrate ligand in the case of 1 and 2, leading to distorted tetrahedral geometry around the silver ion with longer Ag-O distances in case of 2 compared to 1, while 3 has a unidentate nitrate ligand leading to a distorted trigonal planar geometry. The packing of two [Ag(Etnic)(2)NO(3)] complex units; 4 does not affect the molecular geometry around Ag(I) ion compared to 1. In the case of 5, the two asymmetric units of the formula [Ag(Etnic)(2)NO(3)] differ in the bonding mode of the nitrate group, where the geometry around the silver ion is distorted tetrahedral in one unit and trigonal planar in the other. The calculations predicted almost no change in the charge densities at the different atomic sites except at the sites involved in the C-H⋯O interactions as well as at the coordinated nitrogen of the pyridine ring.