Multi-component crystals-salts, co-crystals, or solvates-are usually designed based on the analysis of the complementarity of functional groups and intermolecular interactions of the components. However, no crystal design can do without a practical method of crystal growth. Not all compounds that should be expected to exist based on the "synthon approach" can be prepared in real experiments. This paper aims to illustrate that, in addition to the synthon approach, it is equally important to take into account phase diagrams when searching for practical methods of crystallising multi-component crystals, either as single crystals or as fine particles. Here, we describe the crystallization of a bis(paracetamol) pyridine solvate from a glass-like metastable phase produced by quench-freezing of a paracetamol-pyridine solution with subsequent low-temperature annealing. These procedures must be carried out strictly within the boundaries of the two-phase region "solid solvate + liquor", which was found only as a result of modelling the phase diagram. The crystal structure was solved by single-crystal X-ray diffraction and compared with co-crystals of paracetamol found in the Cambridge Structural Database. The structure-forming role of the intermolecular interactions and their characteristics were studied by variable-temperature experiments over the range of 100-275 K. This was compared with the structures of pure paracetamol polymorphs and other solvates and co-crystals at ambient and non-ambient conditions.