(Isocyano group)⋯lone pair interactions involving coordinated isocyanides: experimental, theoretical and CSD studies.

Inspection of the X-ray structure of the newly prepared trans-[PdCl(CNXyl)ADC] (ADC = XylNH–C_;＝N–[5-iodo-2,6-dimethylpyrimidin-4-yl]) complex made it possible to identify for the first time the π-hole interaction involving the nitrogen atom of a coordinated isocyano group with a lone pair. Processing of available CSD data and results of DFT calculations revealed the possibility of two different sites for π-hole interaction involving isocyanides, i.e. both isocyano carbon and nitrogen centers are capable of acting as the π-hole donor toward lone pairs. [ABSTRACT FROM AUTHOR]