Simple quaternary ammonium ions R4N+ (R = nPr, nBu, nPen) as versatile structure directors for the synthesis of zeolite-like, heterobimetallic cyanide frameworks

The preparation of three new examples of water insoluble host/guest assembl ies of the general composition: [(R4N) (Me3Sn)(2)M(CN)(6) . zH(2)O] (R = n- propyl or n-pentyl, M = Fe or Co, 0 less than or equal to z less than or eq ual to 2) from likewise polymeric super-Prussian-blue derivatives [(Me3Sn)( 3)M(CN)(6)] and aqueous (R4N)X solutions are reported. According to combine d single-crystal X-ray (3a and 3a*: R = nPr, M = Co, z = 2; 5b: R = nPen, M = Fe, z = 0.5), powder X-ray diffraction (XRD), and multinuclear (C-13, N- 15, Co-59, Sn-119) CPMAS solid-state magnetic resonance studies, 3a and 3a* contain cis- and trans-isomeric [Co(CN)(4) (CNSnMe3OH2)(2)](-) building bl ocks, respectively, which are held together exclusively by Sn <-- OH2... NC -Co hydrogen bonds. In striking contrast, the building blocks of 5b and 5a are infinite [M-CN-Sn-NC] chains. in all these assemblies, also significant C-H ... NC hydrogen bonds between the encapsulated R4N+ guest ion and excl usively terminal cyanide ligands of the host seem to play a notable auxilia ry role. (C) 2000 Academic Press.