Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

Abstract

The coupling of cis-[PdCl2(CNXyl)2] (Xyl = 2,6-Me2C6H3) with 4-phenylthiazol-2-amine in molar ratio 2:3 at RT in CH2Cl2 leads to binuclear (diaminocarbene)PdII complex 3c. The complex was characterized by HRESI+-MS, 1H NMR spectroscopy, and its structure was elucidated by single-crystal XRD. Inspection of the XRD data for 3c and for three relevant earlier obtained thiazole/thiadiazole derived binuclear diaminocarbene complexes (3a EYOVIZ; 3b: EYOWAS; 3d: EYOVOF) suggests that the structures of all these species exhibit intra-/intermolecular bifurcated chalcogen bonding (BCB). The obtained data indicate the presence of intramolecular S•••Cl chalcogen bonds in all of the structures, whereas varying of substituent in the 4th and 5th positions of the thiazaheterocyclic fragment leads to changes of the intermolecular chalcogen bonding type, viz. S•••π in 3a,b, S•••S in 3c, and S•••O in 3d. At the same time, the change of heterocyclic system (from 1,3-thiazole to 1,3,4-thiadiazole) does not affect the pattern of non-covalent interactions. Presence of such intermolecular chalcogen bonding leads to the formation of one-dimensional (1D) polymeric chains (for 3a,b), dimeric associates (for 3c), or the fixation of an acetone molecule in the hollow between two diaminocarbene complexes (for 3d) in the solid state. The Hirshfeld surface analysis for the studied X-ray structures estimated the contributions of intermolecular chalcogen bonds in crystal packing of 3a–d: S•••π (3a: 2.4%; 3b: 2.4%), S•••S (3c: less 1%), S•••O (3d: less 1%). The additionally performed DFT calculations, followed by the topological analysis of the electron density distribution within the framework of Bader’s theory (AIM method), confirm the presence of intra-/intermolecular BCB S•••Cl/S•••S in dimer of 3c taken as a model system (solid state geometry). The AIM analysis demonstrates the presence of appropriate bond critical points for these interactions and defines their strength from 0.9 to 2.8 kcal/mol indicating their attractive nature.

The competition and cooperativity of hydrogen/halogen bond and π‐hole bond involving the heteronuclear ethylene analogues

“…It has been demonstrated that cooperativity, either positive (synergy) or negative (anti‐synergy) is a very important phenomenon in many areas of chemistry 53–64 . Recently, Kukushkin and coworkers 57–64 have observed the existence of noncovalent interactions (hydrogen/halogen/chalcogen/π‐hole bonds) by X‐ray diffraction, investigated the cooperativity between them theoretically by DFT calculations followed by QTAIM analysis, and confirmed experimentally by combined FTIR, HRESI‐MS, 1 H NMR, and diffusion coefficient NMR measurements.…”

Electronic and Optical Properties of Atomic-Scale Heterostructure Based on MXene and MN (M = Al, Ga): A DFT Investigation

“…where that the framework of the quantum theory of atoms in molecules (QTAIM) functional is not considered here, which is also a popular method for simulations [90][91][92][93][94][95][96][97][98][99]. The results show that the Hf2CO2/MN heterostructure is formed by vdW interactions [100,101].…”

“…MXene/MN , E MXene and E MN show the total energy of the Hf 2 CO 2 /MN heterostructure, monolayered Hf 2 CO 2 and MN, respectively. The smaller the binding energy, the more stable the structure of the heterostructure[89], and thus the most stable structure of those six stacking configurations of the heterostructure is decided as the lowest binding energy, which is demonstrated in the AA stacking style of the Hf 2 CO It is worth not-ing that the framework of the quantum theory of atoms in molecules (QTAIM) functional is not considered here, which is also a popular method for simulations[90][91][92][93][94][95][96][97][98][99]. The results show that the Hf 2 CO 2 /MN heterostructure is formed by vdW interactions[100,101].…”

Monoprotonated Dimethyl Sulfoxide, [HOSMe2]+: Synthesis, Crystal Structure, Spectroscopic and Theoretical Studies of [HOSMe2]2[OsCl6] ⋅ 2H2O

“…in these BCPs are typical for non-covalent interactions involving a halogen atom in similar chemical systems [39][40][41] and chalcogen bonds. [42][43][44] Note that Table 2. Values of the density of all electrons -1(r), Laplacian of electron densityr 2 1(r) and appropriate λ 2 eigenvalues, energy density -H b , potential energy density -V(r), and Lagrangian kinetic energy -G(r) (a.u.)…”