Crystal and molecular structure of the lithium p-nitrosophenolate dihydrate dimer: an example of a strong dependence of the π-electron cooperative substituent effect on the hydrogen-bonding network in the crystal lattice

Abstract

The crystal and molecular structure of lithium p -nitrosophenolate dihydrate dimer (LNP) is solved by X-ray diffraction with relatively high precision (the mean esd for the bond lengths is 0.002–0.003 Å; wR = 0.0433). NMR studies and ab initio (6-31G) calculations indicate that the free anions have primarily a quinoid structure, whose contribution to the crystal lattice strongly depends on hydrogen bonding. Comparison of the reported structure with sodium tri- and magnesium hexahydrate p -nitrosophenolate perchlorates indicates that LiO interactions somewhat resemble the hydrogen bond.