A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π interactions in the solid-state supramolecular assembly of 2- and 4-formylphenyl arylsulfonates

Abstract

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, CHOS, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, CHClOS, 3b, 2-formylphenyl 4-bromobenzenesulfonate, CHBrOS, 3c, 4-formylphenyl 4-methylbenzenesulfonate, CHOS, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, CHClOS, and 4-formylphenyl 4-bromobenzenesulfonate, CHBrOS, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

A long-chain based bromo and methyl substituted chalcone derivatives; experimental and theoretical approach on nonlinear optical single crystals

“…While the other angles are: S1-O3-C8 =118.1(2)°for 4M1PMS and S1-O3-C8 =119.7(2)°for 4BPMS. This indicated that S atoms in 4M1PMS and 4BPMS show distorted tetrahedral geometry and angle close to 120° [38]. Furthermore, the tosyloxy group in 4BPMS is twisted more from the enone group than that in 4M1PMS, which is confirmed by measuring mean plane angle between tosyloxy and enone group, which is 56.62°.…”

Synthesis, antioxidant, and anticholinesterase activities of novel N‐arylsulfonyl hydrazones bearing sulfonate ester scaffold

“…In this research, the antioxidant capacities of all tested molecules were determined using β-carotene bleaching, DPPH free radical scavenging, ABTS cation radical decolorization, and cupric-reducing antioxidant capacity assays. [49][50][51][52][53][54][55][56] butylated hydroxytoluene (BHT) and α-tocopherol (α-TOC) were employed as reference compounds to compare the activity. The antioxidant activity results of all tested molecules and reference compounds are presented in Table 1.…”

“…These compounds (2,8 [ 31 ] , 3,9 [ 11 ] , 4,10 [ 33 ] , 5,11 [ 50 ] , 6,12 [ 44 ] , and 7,13 [ 45 ] ) were re‐prepared according to the literature. Herein, the reaction of 4‐HBA with 4‐methoxybenzensulfonyl chloride (MBSC) to form compound 13 is given as an example.…”

Relevant π-hole tetrel bonding interactions in ethyl 2-triazolyl-2-oxoacetate derivatives: Hirshfeld surface analysis and DFT calculations

“…SHELX program was also used to solve all structures by direct method 35 .Positions and anisotropic parameters of all non-H atoms were refined on F 2 using the full matrix least-squares technique. The H atoms were added at geometrically calculated positions and refined using the riding model 36 .The details of crystallographic data and crystal refinement parameters for the compounds 1-4 are given in Table 1.…”