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.