In topochemical polymerization, little room is provided for the monomer to adjust their position. Thus, the reacting sites of the monomer should be pre-packed in a suitable manner. If [2+2] cycloaddition is involved in the polymerization, then the alignment of double bonds within the crystal should fulfill the aforementioned Schmidt's criteria. Sometimes multiple parameters should be considered. As shown in the figure, for example, the 1,4-polymerization of diacetylene requires the fine adjustment of angle as well as the monomer packing distance to achieve a satisfying reaction site distance d (distance between C1 and C4).
The method invented by Schmidt is still the most promising way to investigate the structural criteria of polymerization. In this approach, a series of monomers with different substituents are crystallized and characterized by single-crystal X-ray diffractometer. By comparing their polymerization reactivity and slightly different structure, the suitable range of lattice parameters can be derived.
Though Schmidts criteria are generally useful for predicting the topochemical reactivity, there are many instances of violation of these criteria. Many examples of smooth reaction of crystals that are not expected to be reactive based on Schmidts criteria are reported.