Studies of Nature of Uncommon Bifurcated I–I···(I–M) Metal-Involving Noncovalent Interaction in Palladium(II) and Platinum(II) Isocyanide Cocrystals

[Image: see text] Two isostructural trans-[MI(2)(CNXyl)(2)]·I(2) (M = Pd or Pt; CNXyl = 2,6-dimethylphenyl isocyanide) metallopolymeric cocrystals containing uncommon bifurcated iodine···(metal–iodide) contact were obtained. In addition to classical halogen bonding, single-crystal X-ray diffraction analysis revealed a rare type of metal-involved stabilizing contact in both cocrystals. The nature of the noncovalent contact was studied computationally (via DFT, electrostatic surface potential, electron localization function, quantum theory of atoms in molecules, and noncovalent interactions plot methods). Studies confirmed that the I···I halogen bond is the strongest noncovalent interaction in the systems, followed by weaker I···M interaction. The electrophilic and nucleophilic nature of atoms participating in I···M interaction was studied with ED/ESP minima analysis. In trans-[PtI(2)(CNXyl)(2)]·I(2) cocrystal, Pt atoms act as weak nucleophiles in I···Pt interaction. In the case of trans-[PdI(2)(CNXyl)(2)]·I(2) cocrystal, electrophilic/nucleophilic roles of Pd and I are not clear, and thus the quasimetallophilic nature of the I···Pd interaction was suggested.