Probing the Effect of Halogen Substituents (Br, Cl, and F) on the Non-covalent Interactions in 1-(Adamantan-1-yl)-3-arylthiourea Derivatives: A Theoretical Study

Abstract

The effect of halogen substituents (X = Br, Cl, and F) on the crystal packing and intra-and intermolecular interactions in four adamantane−thiourea hybrid derivatives is investigated using different theoretical tools. The bromo and chloro derivatives exhibit 3D isostructurality as evident from lattice parameters, molecular conformation, and crystal packing. The density functional theory study suggests that the molecular conformation of the parent (unsubstituted) and fluoro derivatives exhibits a stable low energy anti−syn conformation. In contrast, bromo and chloro derivatives adopt stable and relatively high energy minima on their potential energy surfaces. Hirshfeld surface analysis reveals the effect of halogen substituents on the intermolecular contacts. The halogen atoms mainly reduce the contribution of H•••H contacts toward crystal packing. PIXEL energy analysis indicates the strong dimer formed by N−H•••S hydrogen bonds in all four structures. It also revealed that a vast number of H•••H contacts observed in different dimers of these structures either presented along with other conventional interactions or solely stabilize the dimeric topology. The topological parameters for intermolecular interactions in these structures suggest an intermediate bonding character between shared and closed-shell interactions for N−H•••S hydrogen bonds in the parent and chloro derivatives. In contrast, the N−H•••S hydrogen bond in other structures is of a closed-shell interaction. Among four derivatives, the fluoro derivative is weakly packed in the solid state based on the PIXEL method's lattice energy calculation.

Novel Adamantane-Linked Isothiourea Derivatives as Potential Chemotherapeutic Agents: Synthesis, Structural Insights, and Antimicrobial/Anti-Proliferative Profiles

“…In view of the previously reported observations and as a continuation of an interest in chemotherapeutic properties, − and structural informatics − of adamantane-based derivatives, we report herein the synthesis, characterization, solid-state structural features, electronic properties, vibrational spectroscopy, and preliminary antimicrobial and antiproliferative activities of two adamantane-linked isothiourea derivatives.…”

The Unconventional Noncovalent Interactions Control: Crystallographic and Theoretical Analyses of the Crystalline Structure of 1,1′‐(1‐Chloro‐4‐methoxyphenyl)dibenzene as a Case Study

“…In reference, [16] as instance, the importance of the CÀ H•••O hydrogen bond is also demonstrated in achieving the Rh 2 (II)-catalyzed asymmetric cycloisomerization of 1,n-enynes by synergistically activating the substrate and introducing the CÀ H… O bonds. Moreover, CÀ H…HÀ C contacts which represent a unique type of CÀ H … X hydrogen bonding, have engendered a stimulating debate among researchers, [17][18][19][20] with supporting evidence for their stabilizing contribution. [21][22][23][24] These dispersion-dominated interactions exhibit hydrogen bonding-like characteristics and have notable application in various fields, including synthetic chemistry, [25] crystal engineering, [26,27] and hydrogen storage materials [28] etc.…”

Supramolecular Self-Assembly Mediated by Multiple Hydrogen Bonds and the Importance of C–S···N Chalcogen Bonds in N′-(Adamantan-2-ylidene)hydrazide Derivatives

“…Continuing ongoing research efforts in the chemotherapeutic − and structural characterization − of adamantane-based derivatives, we describe herein the synthesis, structural characteristics, and antiproliferative activity of N ′-(adamantan-2-ylidene)-5-bromothiophene-2-carbohydrazide derivative 1 . The Cambridge Structural Database (CSD) search reveals five closely related structures for structure 1, and its closely related structures are compound 2 (csd refcode: YAJBES), compound 3 (csd refcode: ILESAV), compound 4 (csd refcode: OKOLOR), compound 5 (csd refocde: XEBTIJ), and compound 6 (csd refcode: NICCEH) shown in Figure .…”