An experimental charge density study of the effect of the noncentric crystal field on the molecular properties of organic NLO materials.

The structure, packing, and charge distribution in molecules of nonlinear optical materials have been analysed with reference to their counterparts in centrosymmetric structures based on low temperature X-ray measurements. The systems studied are the centric and noncentric polymorphs of 5-nitrouracil as well as the diamino, dithio, and thioamino derivatives of 1,1-ethylenedicarbonitrile; the latter possesses a noncentric structure. The molecular structure of 5-nitrouracil is invariant between the two forms, while the crystal packing is considerably different, leading to dimeric N-H·∙∙O rings in the centric polymorph and linear chains in noncentric one. There is an additional C-H·∙∙O contact in the centric form with a significant overlap of the electrostatic potentials between the alkenyl hydrogen atom and an oxygen atom of the nitro group. The dipole moment of 5-nitrouracil in the noncentric form is much higher (μ=9 D) than in the centric form (≈6 D). Among the 1,1-ethylenedicarbonitriles, there is an increased charge separation in the noncentric thioamino derivative, leading to an enhanced dipole of 15 D compared to the centric diamino (5 D) and dithio (6 D) derivatives. The effect of the crystal field is borne out by semiempirical AM1 calculations on the two systems. Dipole moments calculated for the molecules in the frozen geometries match closely with those obtained for centric crystals from the experimental charge densities. The calculated values of the dipole moment in the frozen or optimized geometries in the noncentric structures are, however, considerably lower than the observed value. Furthermore, the conformation of the S-CH(3) group in the noncentric crystal is anti with respect to the central C=C bond while the syn conformation is predicted for the free molecule in the optimized geometry.