1:2 Complexes of chloranilic acid with pyrazole and imidazole, and the acetonitrile solvate of a 1:1 complex with imidazole.

2,5-Dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid) forms X-H.Y (X, Y = N or O) and C-H.Cl hydrogen bonds with pyrazole and imidazole to afford bis(pyrazolium) dichloroanilate and bis(imidazolium) dichloroanilate, (I) and (II), both 2C(3)H(5)N(2)(+).C(6)Cl(2)O(4)(2-), and imidazolium chloroanilate acetonitrile solvate, C(3)H(5)N(2)(+).C(6)HCl(2)O(4)(-).C(2)H(3)N, (III). Their crystal structures demonstrate three novel supramolecular architectures based on supramolecular synthons to build a ladder, (I), a two-dimensional network, (II), and a flat ribbon, (III).