Experimental and theoretical charge distribution in (Z)-N-methyl-C-phenylnitrone

Abstract

The total experimental charge density in (Z)-N-methyl-C-phenylnitrone (1) has been determined using high-resolution X-ray diffraction data in combination with neutron diffraction data measured at 100 K in terms of the rigid pseudoatom model. Multipole refinement converged at R = 0.03 for 7163 reflections with I > 2σ(I). Topological analysis of the total experimental charge density ρ(r) and its Laplacian, −▽²ρ(r) and a comparison with high level theoretical gas-phase calculations reveals an unexpected electron distribution in the N–O group, both atoms having negative atomic charges, contrary to that commonly assumed in nitrone species. This observation is confirmed on examination of both the theoretical charges and the molecular electrostatic potential. Compound 1 contains a large number of hydrogen bonds and these are analysed using the atoms in molecules approach leading to quantitative values for bond strength, ranging from medium to very weak.