Arylamine-solvated copper(I)/iodide coordination polymers cooperatively formed by the amination of aryl iodides and the assembly of [Cu2I2] species with 1,2-bis(4-pyridyl)ethane

► Reaction of Cu2(OH)2CO3 with bpe and PhI in MeCN and aqueous NH3 gave compound 1. ► Compound 1 has a [Cu2I2]-based 2D (4,4) topological network. ► The aniline molecule was in situ formed through Ullmann reactions of PhI with NH3.