Co-crystals of an agrochemical active – A pyridine-amine synthon for a thioamide group

Five novel co-crystals of thiophanate-ethyl (TE), an agrochemical active, with di(2-pyridyl)ketone (1), 2-benzoylpyridine (2), 3-benzoylpyridine (3), 4-phenylpyridine (4) and biphenyl (5) were found and crystal structures of four of them (TE1–TE3, TE5) solved by single crystal X-ray diffraction. Three of the co-crystals (TE1–TE3) form by way of a reliable pyridine-amine hydrogen bond synthon and one (TE5) because of close packing effects. The fifth co-crystal was identified by X-ray powder diffraction. The work demonstrates the usage of a reliable supramolecular synthon for crystal engineering, while concurrently reminds that the close packing of even very similar molecules cannot be fully predicted.

► Five novel co-crystals for thiophanate-ethyl, an agrochemical active, were found.
► Crystal structures of four novel co-crystals were solved.
► A pyridine-amine synthon is useful even with a complicated agrochemical active.
► Close packing of even very similar molecules cannot be fully predicted.