Group 1 Coordination Chains and Hexagonal Networks of Host Cyclotriveratrylene with Halogenated Monocarbaborane Anions

Halogenated carbaborane ions [CB 11 H 6 X 6 ] − in which X=Cl or Br have been combined with the host molecule cyclotriveratrylene (CTV) and Group 1 metal cations to give crystalline materials. The complexes [Na(ctv)(H 2 O)(CB 11 H 6 X 6 )](CF 3 CH 2 OH) feature chiral Na–CTV coordination chains with complexation of the [CB 11 H 6 X 6 ] − ion by the Na + ion, together with the CTV molecular cavity. The coordination chains are hydrogen bonded together to give a puckered two‐dimensional hexagonal grid structure. [K(ctv)(CB 11 H 6 Cl 6 )(CF 3 CH 2 OH) 0.5 ] is essentially isostructural. Complexes [Rb(ctv)(CB 11 H 6 Br 6 )(H 2 O)] and [Cs(ctv)(CB 11 H 6 X 6 )(CH 3 CN)] are coordination polymers with related distorted hexagonal grid structures. Use of N , N ′‐dimethylformamide (DMF) as a solvent results in an entirely different type of assembly, with [Na 2 (dmf) 4 (H 2 O) 2 (ctv)][(dmf) 0.5 (ctv)][CB 11 H 6 Br 6 ] 2 showing unusual {Na‐μ‐(dmf)‐Na} bridges, and once again forming a distorted hexagonal coordination polymer.