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The title compound was prepared crystallizing together the co-formers namely, 2,4-diamino-6-phenyl-1,3,5-triazine (DAPT) and phenylthioacetic acid (PTAA) in methanol. The compound crystallized in the orthorhombic space group Pca21 with a = 12.384(2) Å, b = 18.698 (3) Å, c = 7.0428(11) Å, V = 1630.8(5) Å3, and Z = 4. The compound existed as a 1:1 cocrystal. The dihedral angle between the two formers is 50.89(9)°. The primary and secondary interactions between DAPT and PTAA form two different discrete chains C(3) that link the DAPT ribbons in adjacent layer. Mass spectra indicate the transfer of a carboxylic acid proton to form PTAA to the nitrogen of DAPT.