The design of molecular crystals with specific optical properties, which are thought to arise from constituent molecules’ polarizability properties, is a desirable but currently unachievable goal. One can partially achieve this goal by choosing compounds with specific molecular attributes and empirically determining the manner in which these are translated into crystal properties. Besides the fact that there are no certain rules for prediction of crystal packing arrangements, there is also a problem in specifying molecular properties from what are today incomplete polarizability structure-property relationships. We have, realizing these limitations, identified new molecular crystals by a nonlinear optical (powder-SHG) scouting-screening program from lists of compounds chosen because of desirable molecular properties. Examination of successful materials has revealed interesting, new alignment motifs. Some of these materials, a set of halogen and cyano derivatives of aromatic compounds, are described relating properties and structures of molecules and crystals. In particular, the orientation directing influence of intermolecular halogen-cyano interactions and the use of heterocyclic compounds to improve transparency in the near infrared and in the blue and near ultraviolet spectral regions are demonstrated.