Structure Analysis of Molecular Compounds with Z′ = 2 Using Laboratory X-ray Powder Diffraction Data: 3-Phenylpropionic Acid and Its Derivatives

Abstract

The structure determination of 3-phenylpropionic acid (1), 3-(3-methylphenyl) propionic acid (5), and 3-(3- methoxyphenyl) propionic acid (6), all three compounds crystallizing in the monoclinic space group P21/a (or P21/n) with Z′ = 2, has been accomplished from laboratory X-ray powder diffraction data following the direct space approach. The nature of intermolecular interactions in 1, 5, and 6 has been analyzed using the Hirshfeld surfaces and 2D fingerprint plots. While the two molecules (A and B) in the crystallographic asymmetric unit of 6 display almost identical conformation, those in 1 and 5 are significantly different due a rotation about the C–C bond linking the planar aromatic ring and propionic acid fragments. The presence of the COOH functional group in the compounds promotes the formation of cyclic R22(8) synthons via intermolecular O–H···O hydrogen bonds. Further linking of molecules through intermolecular C–H···O and C–H···π hydrogen bonds generates a three-dimensional supramolecular architecture in 1 and 5 and a two-dimensional molecular sheet in 6. Hirshfeld surface analyses of 1, 5, and 6 as well as a few substituted phenylpropionic acids retrieved from the Cambridge Structure Database (CSD) indicate that 94–99% of Hirshfeld surface areas in this class of compounds are due to H···H, O···H, and C···H contacts.