Crystal structures of 2,3,8,9,14,15-hexa-methyl-5,6,11,12,17,18-hexa-aza-tri-naphthyl-ene and 2,3,8,9,14,15-hexa-phenyl-5,6,11,12,17,18-hexa-za-tri-naphthyl-ene di-chloro-methane disolvate.

The crystal structures of two substituted HATN (hexa-aza-tri-naphthyl-ene) derivatives, namely 2,3,8,9,14,15-hexa-methyl- and 2,3,8,9,14,15-hexa-phenyl-5,6,11,12,17,18- hexa-zatri-naphthyl-ene (HATNMe6 and HATNPh6), are reported. Whereas the structure of the methyl-substituted derivative (HATNMe6) contains no solvent mol-ecules (C30H24N6), the hexa-phenyl-substituted structure (HATNPh6) contains two mol-ecules of di-chloro-methane (C60H36N6·2CH2Cl2). This class of planar bridging ligands is known for its electron-deficient systems and its ability to form π-π stacking inter-actions. Indeed, in both crystal structures strong π-π stacking inter-actions are observed, but with different packing features. The di-chloro-methane mol-ecules in the crystal structure of HATNPh6 are situated in the voids and are involved in C-H⋯N contacts to the nitro-gen atoms of the pyrazine units.