RESUMEN
The synthesis and structural characterization of α-haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles with various counterions is reported herein, demonstrating a strategy for directed supramolecular dimerization in the solid state. The compounds were obtained through a recently discovered 1,3-dipolar cycloaddition reaction between nitriles and bifunctional 2-pyridylselenyl reagents, and their structures were confirmed by the X-ray crystallography. α-Haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles exclusively formed supramolecular dimers via four-center Se···N chalcogen bonding, supported by additional halogen bonding involving α-haloalkyl substituents. The introduction of halogens at the α-position of the substituent R in the selenadiazole core proved effective in promoting supramolecular dimerization, which was unaffected by variation of counterions. Additionally, the impact of cocrystallization with a classical halogen bond donor C6F3I3 on the supramolecular assembly was investigated. Non-covalent interactions were studied using density functional theory calculations and topological analysis of the electron density distribution, which indicated that all ChB, XB and HB interactions are purely non-covalent and attractive in nature. This study underscores the potential of halogen and chalcogen bonding in directing the self-assembly of functional supramolecular materials employing 1,2,4-selenadiazoles derived from recently discovered cycloaddition between nitriles and bifunctional 2-pyridylselenyl reagents.
Asunto(s)
Calcógenos , Halógenos , Dimerización , Reactivos de Enlaces Cruzados , NitrilosRESUMEN
In the crystal of the title compound, C6H9ClN2O, mol-ecular pairs form dimers with an R 2 2(8) motif through N-Hâ¯O hydrogen bonds. These dimers are connect into ribbons parallel to the (100) plane with R 4 4(10) motifs by N-Hâ¯O hydrogen bonds along the c-axis direction. In addition, π-π [centroid-to-centroid distance = 3.4635â (9)â Å] and C-Clâ¯π inter-actions between the ribbons form layers parallel to the (100) plane. The three-dimensional consolidation of the crystal structure is also ensured by Clâ¯H and Clâ¯Cl inter-actions between these layers. According to a Hirshfeld surface study, Hâ¯H (43.3%), Clâ¯H/Hâ¯Cl (22.1%) and Oâ¯H/Hâ¯O (18.7%) inter-actions are the most significant contributors to the crystal packing.