The crystalline structures of carboxylic acid monolayers adsorbed on graphite.

X-ray and neutron diffraction have been used to investigate the formation of solid crystalline monolayers of all of the linear carboxylic acids from C(6) to C(14) at submonolayer coverage and from C(8) to C(14) at multilayer coverages, and to characterize their structures. X-rays and neutrons highlight different aspects of the monolayer structures, and their combination is therefore important in structural determination. For all of the acids with an odd number of carbon atoms, the unit cell is rectangular of plane group pgg containing four molecules. The members of the homologous series with an even number of carbon atoms have an oblique unit cell with two molecules per unit cell and plane group p2. This odd-even variation in crystal structure provides an explanation for the odd-even variation observed in monolayer melting points and mixing behavior. In all cases, the molecules are arranged in strongly hydrogen-bonded dimers with their extended axes parallel to the surface and the plane of the carbon skeleton essentially parallel to the graphite surface. The monolayer crystal structures have unit cell dimensions similar to certain close-packed planes of the bulk crystals, but the molecular arrangements are different. There is a 1-3% compression on increasing the coverage over a monolayer.