Alkali-metal-cyclotriveratrylene coordination polymers:: Inclusion of neutral C2B10H12 or anionic [CB11H12]- and DMF

The complexes [Cs(CTV)(2)(OH)(H2O)(2)(DMF)(2)](C2B10H12) (4), [Rb(CTV)(2)(OH)(H2O)(2)(DMF)(2)](C2B10H12) (5), [Cs(CTV)(2)(H2O)(3)(DMF)(2)](CB11H12) (6), [Rb(CTV)(2)(H2O)(3)(DMF)(2)](CB11H12) (7), [K(CTV)(DMF)](2)(OH)(H2O)(CB11H12) (8), and [Na(CTV)(2)(H2O)(3)(DMF)(2)](CB11H12) (9) (CTV = cyclotriveratrylene) all form as crystalline inclusion complexes from N,N'-dimethylformamide (=DMF) solutions. The overall structures of complexes 4-9 are strikingly similar, forming extended coordinate and hydrogen-bonding interactions, and all feature intracavity complexation of DMF by CTV and [CB11H12](-) or C2B10H12 as channel-type guest molecules. A pseudopolymorph of 9 can be formed from 2,2,2-trifluoroethanol solution.