The dihalomethanes CH X (X=Cl, Br, I) were co-crystallized with the isocyanide complexes trans-[MX (CNC H -4-X ) ] (M=Pd, Pt; X =Br, I; X =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, CH X behave as bent bifunctional XB/XB-donating building blocks, whereas trans-[MX (CNC H -4-X ) ] act as a linear XB/XB acceptors. Results of DFT calculations indicate that all XCH -X⋅⋅⋅X -M contacts are typical noncovalent interactions with estimated strengths in the range of 1.3-3.2 kcal mol . 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.
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