A comparison of electron density from Hirshfeld-atom refinement, X-ray wavefunction refinement and multipole refinement on three urea derivatives

Abstract

Electron density distributions of three urea derivatives N-methylurea, N-phenylurea and N,N′-diphenylurea were determined by single-crystal X-ray diffraction. High-resolution data were measured with synchrotron radiation. Data were subjected to a multipole refinement using the Hansen–Coppens multipole model, to Hirshfeld-atom refinement with and without a surrounding cluster of point charges/dipoles and to X-ray wavefunction refinement. Electron density distributions were evaluated in terms of deformation and residual electron density plots as well as bond critical points, atomic volumes and charges as defined in Bader's Theory of Atoms In Molecules. Given a sufficiently extended basis-set Hirshfeld-atom refinement yields results superior to multipole model refinements; best figures of merit were achieved by X-ray wavefunction refinement. Results indicate how conventional crystallographic studies can be systematically improved.