The design of supramolecular structures with using of crystal engineering principles, when molecular associates via noncovalent interactions act as the building blocks, opens the new possibility for modern chemistry and material sciences. 1,1`-Binaphtyl-2,2`-dicarboxylic acid (BNDA) is a versatile host capable to form the hostguest complexes with the large number (more than 30) of polar and apolar solvents [1]. On the example of BNDA such phenomenon as solvatomorphism or polymorphysm of the given clathrate exists (formation of different crystalline modifications of the same host-guest complex at different conditions of crystallization). Our investigations show that variation in the crystallization temperature for solutions of BNDA in 1,4-dioxane results in six crystalline forms of BNDA with different types of supramolecular association: 4 solvates - [2BNDA/dioxane] (1), [BNDA/dioxane] (2), [2BNDA/2dioxane] (3), [BNDA/2dioxane] (4), one mixed hydrate - [BNDA/3dioxane/H3O+] (5) and one unsolvated form. The framework structures form with participation of 0D-associates (1,3,4), containing (3,4) or not containing (1) guest molecules and 1D zigzag chains, also containing (5) or not containing (2) guest molecules. The 1,4-dioxane clathrates are formed in accordance with a rule formulated by B.T. Ibragimov [2] which may be summarized as follows: 1) The guest/host ratio decreases as the crystallization temperature increases. 2) The topology changes from low temperature to high temperature as intercalate→ tubulate→ cryptate→unsolvated form (apohost).