title: Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.
abstract: The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.
authors.affiliation: College of Physics Science and Information Engineering, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.|Huihua College, Hebei Normal University, Shijiazhuang, 050091, People's Republic of China.|College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
authors.forename: Lixin
authors.initials: L
authors.lastname: Mo
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.|Key Laboratory of Inorganic Nano-materials of Hebei Province, Shijiazhuang, 050024, People's Republic of China.
authors.forename: Yanli
authors.initials: Y
authors.lastname: Zeng
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.|Key Laboratory of Inorganic Nano-materials of Hebei Province, Shijiazhuang, 050024, People's Republic of China.
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Li
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.|Key Laboratory of Inorganic Nano-materials of Hebei Province, Shijiazhuang, 050024, People's Republic of China.
authors.forename: Xueying
authors.initials: X
authors.lastname: Zhang
authors.affiliation: College of Physics Science and Information Engineering, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China. menglp@mail.hebtu.edu.cn.|College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China. menglp@mail.hebtu.edu.cn.
authors.forename: Lingpeng
authors.initials: L
authors.lastname: Meng
mesh_terms: D001665:Binding Sites; D018011:Chalcogens / Q000737:chemistry*; D019295:Computational Biology / Q000379:methods; D005557:Formaldehyde / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D008958:Models, Molecular; D055672:Static Electricity; D013457:Sulfur Compounds / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D018011:Chalcogens; D006219:Halogens; D013457:Sulfur Compounds; D005557:Formaldehyde
keywords: Chalcogen bond; Cooperativity; Halogen bond; σ-hole interactions