6533b7d0fe1ef96bd125a5a8
RESEARCH PRODUCT
Tunable Interaction Strength and Nature of the S···Br Halogen Bonds in [(Thione)Br2] Systems
Pipsa HirvaLaura KoskinenMatti HaukkaSirpa Jääskeläinensubject
thionessynthesis010405 organic chemistryChemistryLigandStereochemistryCharge densityElectron donorGeneral ChemistryInteraction energy010402 general chemistryCondensed Matter Physics01 natural sciencesHeterolysis0104 chemical sciences3. Good healthCrystallographychemistry.chemical_compoundhalogen bondingCovalent bondHalogenMoleculeGeneral Materials Scienceta116bromidedescription
The strength and nature of the S···Br and Br···Br interactions were systematically tuned by altering the electron donor properties of the thione group. Three new halogen-bonded compounds, [(N-methylbenzothiazole-2-thione)Br2]·0.5CH2Cl2 (1), [(2(3H)-benzothiazolethione)Br2] (2), and [(2-benzimidazolethione)Br]·[Br3] (3), were synthesized and studied structurally by using X-ray crystallography and computationally by using charge density analysis based on QTAIM calculations. Analysis of the interaction strength indicated a formation of surprisingly strong S···Br halogen bonds in 1 (−104 kJ mol–1, and RBrS = 0.64) and 2 (−116 kJ mol–1, and RBrS = 0.63) with a substantial covalent contribution. The strong electron donor character of the thione ligand in 3 induced a heterolytic cleavage of the dibromine molecule and a change in the S···Br interaction nature to form a covalent bond with a high interaction energy (−147 kJ mol–1, and RBrS = 0.60).
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2015-02-19 | Crystal Growth & Design |