Polymorphism and versatile solvate formation of thiophanate-methyl

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

“…The structures exhibit a complicated array of single and bifurcated hydrogen bonds (Fig. 1), unlike in the other TE structures [3,5], where a pairing of two donors and acceptors is often seen. The two N-H hydrogen atoms that participate in a S(6) intramolecular motif [12] are not further hydrogen bonded.…”

“…4). Hydrogen bonding wise the co-crystal (TE4) is expected to be similar to the TE co-crystal with 4,4'-bipyridine [5], which only uses one of the pyridine functional groups for hydrogen bonding to TE. The PXRD patterns of these were compared, but they are not similar (Fig.…”

“…Molecular structures of TE, di(2-pyridyl)ketone (1), 2-benzoylpyridine (2), 3-benzoylpyridine (3), 4-phenylpyridine (4) and biphenyl (5) Piotrowska et al [6] found dithiooxamide, a simpler compound that has some of the same functionalities as TE and TM, to be a convenient substrate for construction of two component supramolecular structures with azaheterocycles. Ellis et al [7] used the same approach for a number of thiocarbamide derivatives and found that they formed many 2:1 co-crystals with bipyridine-type molecules.…”

“…TE and an analogous thiophanate-methyl [4] both have a hydrogen bonded pyridine solvate. They have also been found to make co-crystals [5] with 2,2'-bipyridine, 4,4'-bipyridine and 1,2-bis(4-pyridyl)ethane.…”

“…TE and an analogous thiophanate-methyl [4] both have a hydrogen bonded pyridine solvate. They have also been found to make co-crystals [5] with 2,2'-bipyridine, 4,4'-bipyridine and 1,2-bis(4-pyridyl)ethane. Inspired by the success, we wanted to investigate whether the N-H···N hydrogen bond could be used further for co-crystal design and screened with a series of azaheterocycles (1-4) (Scheme 1) containing a pyridine moiety.…”