Dihalomethanes as Bent Bifunctional XB/XB-Donating Building Blocks
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 of 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 the estimated strengths in the range 1.3–3.2 kcal/mol. CCDC search reveals that
hexagon-like arrays are rather common, but previously overlooked structural
motives for adducts of trans-bis(halide)
complexes and halomethanes.
