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

Reactions of CuI 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]·1/3(C6H6)}∞, (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]}∞, (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]4·3C6H6}∞, (3), is based on unique extended [Cu4(HAT)3]∞ “nanotubules” filled with solvent molecules and [SbF6]− anions.