Synthesis and Halogen Bonding in the Crystal Structures of the New 2,3‐Diiodo Indenone and 1‐Ethoxy‐2,3‐diiodo Indene

The CuI‐catalyzed addition of iodine to the C≡C triple bond of 3,3‐diethoxy‐1‐phenyl propyne ( 1 ) unexpectedly leads to the new cyclization products 2,3‐diiodo‐1H‐inden‐1‐one ( 2 ) and 1‐ethoxy‐2,3‐diiodo‐1H‐indene ( 3 ). Both compounds were isolated and characterized via ¹H, ¹³C NMR (Nuclear Magnetic Resonance) spectroscopy and HRMS (High Resolution Mass Spectrometry). The molecular and crystal structures of compounds 2 and 3 were determined by single crystal X‐ray diffraction. Their crystal structures are governed by extensive halogen bonding, involving I·I and I·O interactions.