Mechanistic insights into a gas-solid reaction in molecular crystals : the role of hydrogen bonding

Mínguez Espallargas, Guillermo and van de Streek, Jacco and Fernandes, Philippe and Florence, Alastair J and Brunelli, Michela and Shankland, Kenneth and Brammer, Lee (2010) Mechanistic insights into a gas-solid reaction in molecular crystals : the role of hydrogen bonding. Angewandte Chemie International Edition, 49 (47). pp. 8892-8896. (https://doi.org/10.1002/anie.201003265)

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Abstract

Hydrogen bonding leads the way: Reaction of nonporous crystalline coordination compound 1 with HCl gas results in conversion into the crystalline salt 2 (see picture) following chemisorption and insertion of HCl into CuN bonds. Powder diffraction studies show that [CuBr2Cl2]2− ions formed in 2 are reoriented to maximize the strength of hydrogen bonds and halogen bonds by preferentially involving Cl rather than Br ligands as acceptor sites.