A simple procedure, with an available program, may readily be used to establish the three-dimensional relationships between a mother and daughter phase, where mother and daughter are either two different phases of a material or a reactant and product in a solid-state transformation. The only requirements are that (i) the process involves a crystal-to-crystal transformation, and (ii) the experiment must be carried out without changing the alignment of the mother crystal. Application of the method supports the inferred alignment of mother and daughter phases in the published structures of two polymorphs of 4-cyanopyridinium perchlorate monohydrate 1. A new low-temperature, monoclinic polymorph of ferrocenium tetrafluoroborate 2 is produced when the known orthorhombic polymorph is cooled from 173 to 120 K. The major features of the transformation include "conservative twinning" and a modulation of the structure along the crystallographic b direction upon cooling. Redetermination of the structure of the low-temperature polymorph of ferrocenium hexafluorophosphate 3 reveals that the phase change is accompanied by reproducible four-component twinning, providing a proper explanation for the previously reported, very high R-factor of 12.4%. Included tutorial information on the process will assist the reader in obtaining topotactic relationships, as well as in preparing figures and animations describing phase transitions or reactions.
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