Computational study of the hydrogen bonding interactions in the [CH2XNO2•H2O] clusters (X = H, F, Cl, Br, I)

Two kinds of structures are identified for the [CH2XNO2 center dot H2O] (X = H, F, Cl, Br, I) clusters, using ab initio and DFT computational techniques. The configurations of the resulting water complexes arise from the two different ways of possible hydrogen bonding interaction. Both types of complexes present cyclic geometries formed through either the interaction of a methylic H with the O atom of the water molecule, type (a), or via the symmetric coupling of each H atom of the water molecule with each O atom of the nitro group, type (b). The examination of the stereochemistry of the complexes shows a dependence on the halogen atom involved. The type (a) complexes are more stable and assumingly, those are primarily involved in the degradation mechanism of halogenated nitromethanes in water solvated surroundings. (C) 2017 Elsevier B.V. All rights reserved.