The synthesis of a series of supramolecular double sulfate salts using transition metals and the aromatic amine alpha-methylbenzylamine afforded an unexpected hybrid lamellar structure type. (C8H12N)(2)[M(H2O)(4)(SO4)(2)]center dot 2H(2)O (M = Fe to Zn) crystallizes with a monoclinic structure (S.G. P2(1)/n), with a significant interlamellar distance of more than 16 angstrom. While comparable to common clay materials, the crystal structure is actually supramolecular; in particular, the mineral layer is built from hydrogen bonds only. The interlayer space is filled with aromatic amines that form chains through C-H center dot center dot center dot pi interactions. The thermal study of all metal compounds revealed good stability of the filled compounds up to 200 degrees C. The dehydration proceeds differently according to the metal incorporated into the structure. In particular, the stepped release of water drastically modifies the interlayer space, which is able to vary from 14.8 to 18.8 angstrom, in an opposite way for the Zn-related compound compared to other metals.