Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding

Abstract

Cocrystallization of the dimeric [Cu 2 (μ-I) 2 (CNXyl) 4 ] (Xyl = 2,6-Me 2 C 6 H 3 , 1) and polymeric catena-[Cu(μ-I)(CNC 6 H 3 -2-Cl-6-Me) 2 ] (2) complexes with I 2 at different molar ratios between the reactants resulted in a series of (RNC) 2 CuI-based crystal polyiodides formed along with gradual accumulation of iodine, namely the cocrystals [1The polyiodide 5•2I 2 exhibits a novel supramolecular motif�a purely inorganic halogen-bonded Cu 2 (μ 1,3 -I 3 ) 2 core in the chair conformation. The X-ray structure of 5•2I 2 featuring I•••I contacts was analyzed by a set of theoretical methods and attributed to moderately strong halogen bonding (from −3.2 to −3.9 kcal/mol); these interactions determine the supramolecular architecture of 5•2I 2 .