X-ray molecular orbital analysis. II. Application to diformohydrazide, (NHCHO)2

The molecular orbitals (MOs) of diformohydrazide have been determined from the electron density measured by X-ray diffraction. The experimental and refinement procedures are explained in detail and the validity of the obtained MOs is assessed from the crystallographic point of view. The X-ray structure factors were measured at 100   K by a four-circle diffractometer avoiding multiple diffraction, the effect of which on the structure factors is comparable to two-centre structure factors. There remained no significant peaks on the residual density map and the R factors reduced significantly. Among the 788 MO coefficients, 731 converged, of which 694 were statistically significant. The C — H and N — H bond distances are 1.032   (2) and 1.033   (3)   Å , respectively. The electron densities of theoretical and experimental MOs and the differences between them are illustrated. The overall features of the electron density obtained by X-ray molecular orbital (XMO) analysis are in good agreement with the canonical orbitals calculated by the restricted Hartree Fock (RHF) method. The bonding-electron distribution around the middle of each bond is well represented and the relative phase relationships of the π orbitals are reflected clearly in the electron densities on the plane perpendicular to the molecular plane. However, differences are noticeable around the O atom on the molecular plane. The orbital energies obtained by XMO analysis are about 0.3   a.u. higher than th...

Source: Acta Crystallographica Section A - October 4, 2021 Category: Chemistry Authors: Tanaka, K. Wasada-Tsutsui, Y. Tags: X-ray molecular orbital analysis XMO analysis electron density molecular orbitals diformohydrazide multiple diffraction hydrogen bonds research papers Source Type: research