Influence of anions on the dimensionality of extended networks based on Cu I cations and 1,4,5,8,9,12-hexaazatriphenylene (HAT) ligands

Reactions of Cu I salts with 1,4,5,8,9,12-hexaazatriphenylene (HAT) afford three types of cationic coordination polymers depending on the anion present in the reaction solution. In the crystal structure of {Cu(HAT)]BF4]x1/3(C6H6)}infinity, (1), Cu ions and HAT molecules form extended layers that are best described as strongly distorted honeycomb nets. The space between the layers is occupied by BF4]- anions and solvent molecules. {Cu(HAT)]PF6]}infinity, (2), crystallizes as a chiral (10,3)-a net with PF6]- anions residing in the cavities of the three-dimensional metal-organic framework. The crystal structure of {Cu4(HAT)3]SbF6]4x3C6H6}infinity, (3), is based on unique extended Cu4(HAT)3]infinity "nanotubules" filled with solvent molecules and SbF6]- anions.