3,6,9,16,19,22-Hexaazatricyclo

Area of Science:

• Supramolecular Chemistry
• Crystal Engineering
• Organic Chemistry

Background:

• Hexaaza macrocycles are versatile ligands with applications in host-guest chemistry.
• Phenolic compounds like diphenols can form salts and hydrogen-bonded networks.
• Understanding adduct formation is key to designing functional supramolecular materials.

Purpose of the Study:

• To characterize the crystal structures of adducts formed between a specific hexaaza macrocycle and 4,4'-sulfonyldiphenol or 4,4'-biphenol.
• To investigate the role of hydrogen bonding and cation conformation in the assembly of these supramolecular adducts.
• To elucidate the packing arrangements and intermolecular interactions within the crystalline solids.

Main Methods:

• Single-crystal X-ray diffraction was employed to determine the three-dimensional structures of the adducts.
• Analysis of hydrogen bonding (N-H...O and O-H...O) and cation conformations was performed.
• Comparison of structural features between the two distinct adducts.

Main Results:

• Adduct (1) is a salt [(C24H40N6)2+].2[(HOC6H4SO2C6H4O)-] with two distinct cation sites and conformations.
• Adduct (2) is an aquated salt [(C24H40N6)2+].2[(HOC6H4C6H4O)-].(HOC6H4C6H4OH).2H2O with a conformationally disordered cation.
• In (1), cations link anion chains into sheets; in (2), cations and biphenol units form a 3D framework with anion/water sheets.

Conclusions:

• The study highlights the influence of the diphenol guest on the supramolecular assembly.
• Cation conformation and hydrogen bonding patterns are critical determinants of the final crystal packing.
• These findings contribute to the understanding of macrocycle-arene interactions and crystal engineering.