Exploring the structural landscape of 2-(thiophen-2-yl)-1,3-benzothiazole: high-Z′ packing polymorphism and cocrystallization with calix[4]tube

We report here for the first time a cocrystal of the so-called neutral calix[4]tube, which is two tail-to-tail-arranged and partially deprotonated tetrakis­(carb­oxy­meth­oxy)calix[4]arenes, including three sodium ions, with 2-(thio­phen-2-yl)-1,3-benzo­thia­zole, namely trisodium bis­(carb­oxy­meth­oxy)bis­(carboxyl­atometh­oxy)calix[4]arene tris­(carb­oxy­meth­oxy)(carboxyl­atometh­oxy)calix[4]arene–2-(thio­phen-2-yl)-1,3-benzo­thia­zole–dimethyl sulfoxide–water (1/1/2/2), 3Na+·C36H30O122−·C36H31O12−·C11H7NS2·2C2H6OS·2H2O, which provides a new approach into the host–guest chemistry of inclusion complexes. Three packing polymorphs of the same benzo­thia­zole with high Z′ (one with Z′ = 8 and two with Z′ = 4) were also discovered in the course of our desired cocrystallization. The inspection of these polymorphs and a previously known polymorph with Z′ = 2 revealed that Z′ increases as the strength of inter­molecular contacts decreases. Also, these results expand the frontier of invoking calixarenes as a host for non­solvent small mol­ecules, besides providing knowledge on the rare formation of high-Z′ packing polymorphs of simple mol­ecules, such as the target benzo­thia­zole.