Dihalomethanes as Bent Bifunctional XB/XB‐Donating Building Blocks for Construction of Metal‐involving Halogen Bonded Hexagons

The dihalomethanes CH2X2 (X=Cl, Br, I) were co‐crystallized with the isocyanide complexes trans‐[MXM2(CNC6H4‐4‐XC)2] (M=Pd, Pt; XM=Br, I; XC=F, Cl, Br) to give an extended series comprising 15 X‐ray structures of isostructural adducts featuring 1D metal‐involving hexagon‐like arrays. In these structures, CH2X2 behave as bent bifunctional XB/XB‐donating building blocks, whereas trans‐[MXM2(CNC6H4‐4‐XC)2] act as a linear XB/XB acceptors. Results of DFT calculations indicate that all XCH2–X⋅⋅⋅XM–M contacts are typical noncovalent interactions with estimated strengths in the range of 1.3–3.2 kcal mol−1. A CCDC search reveals that hexagon‐like arrays are rather common but previously overlooked structural motives for adducts of trans‐bis(halide) complexes and halomethanes. Assembly of a series of trans‐[MXM2(CNC6H4‐4‐XC)2] (M=Pd, Pt) complexes in the presence CH2X2 (X=Cl, Br, I) systematically led to adducts featuring metal‐involving hexagon‐like structures. In these isostructural adducts, CH2X2 behave as bent XB/XB‐donating building blocks. The forming hexagon‐like arrays are a cohesive structural motive for adducts of halomethanes with trans‐bis(halide) complexes.