Halogen Bonding Involving Isomeric Isocyanide/Nitrile Groups

International Journal of Molecular Sciences, Journal Year: 2023, Volume and Issue: 24(17), P. 13324 - 13324

Published: Aug. 28, 2023

2,3,5,6-Tetramethyl-1,4-diisocyanobenzene (1), 1,4-diisocyanobenzene (2), and 1,4-dicyanobenzene (3) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1·1,3,5-FIB, 2·2(1,3,5-FIB), 3·2(1,3,5-FIB), which studied by X-ray diffraction. A common feature of the structures is presence I···Cisocyanide or I···Nnitrile halogen bonds (HaBs), occurs between an iodine σ-hole isocyanide C-(or nitrile N-) atom. The diisocyanide dinitrile cocrystals 2·2(1,3,5-FIB) 3·2(1,3,5-FIB) are isostructural, thus providing a basis for accurate comparison two types noncovalent linkages C≡N/N≡C groups in composition structurally similar entities one crystal environment. bonding situation was set theoretical methods. Diisocyanides more nucleophilic than they exhibit stronger binding 1,3,5-FIB. In all structures, HaBs mostly determined electrostatic interactions, but dispersion induction components also provide noticeable contribution make attractive. Charge transfer has small (<5%) HaB it higher systems. At same time, typical electron-donor π-acceptor properties relation donor.

Language: Английский

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Utilizing “Latent” Carbon: Repositioning Hydrogen‐Bonded Synthons and Assemblies via Halogen Bonding to π‐Systems

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: May 23, 2024

Molecules bearing carboxylic acid, amide, and hydroxyl groups are ubiquitous in crystal engineering, where robust hydrogen-bonded synthons centred on these functionalities enable reliable structure design. We now show that halogen bonding to the carbon π-system of such molecules, traditionally ignored permits recognition directional assembly resulting structural subunits, leaving archetypal ring, ladder, chain homosynthons intact, but repositioned space. When applied heteromolecular synthons, this enables rearranging more complex motifs evolution binary cocrystals into ternary ones through "latent" carbon-based sites, demonstrating a rational approach build higher-order solid-state supramolecular assemblies.

Language: Английский

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Halogen Bonding Involving Isomeric Isocyanide/Nitrile Groups

Published: July 28, 2023

2,3,5,6-Tetramethyl-1,4-diisocyanobenzene (1), 1,4-diisocyanobenzene (2), and 1,4-dicyanobenzene (3) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1·1,3,5-FIB, 2·2(1,3,5-FIB), 3·2(1,3,5-FIB), which studied by XRD. Common feature of the structures is presence I···Cisocyanide or I···Nnitrile HaBs occurred between an iodine -hole isocyanide C- (or nitrile N-) atom. The diisocyanide dinitrile 2·2(1,3,5-FIB) are isostructural thus providing a basis for accurate comparison two types noncovalent linkages CN/NC groups in composition structurally similar entities one crystal environment. bonding situation was set theoretical methods. Diisocyanides more nucleophilic than they exhibit stronger binding 1,3,5-FIB. In all structures, mostly determined electrostatic interactions, but dispersion induction components also provide noticeable contribution make attractive. Charge transfer has small (&lt;5%) HaB it higher systems. At same time, typical electron-donor -acceptor properties relation donor.

Language: Английский

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Scientific School of Academician V.Yu. Kukushkin at St. Petersburg University (A Review)

Russian Journal of General Chemistry, Journal Year: 2024, Volume and Issue: 94(S1), P. S120 - S128

Published: Jan. 1, 2024

Language: Английский

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Utilizing “Latent” Carbon: Repositioning Hydrogen‐Bonded Synthons and Assemblies via Halogen Bonding to π‐Systems

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: May 23, 2024

Abstract Molecules bearing carboxylic acid, amide, and hydroxyl groups are ubiquitous in crystal engineering, where robust hydrogen‐bonded synthons centred on these functionalities enable reliable structure design. We now show that halogen bonding to the carbon π‐system of such molecules, traditionally ignored permits recognition directional assembly resulting structural subunits, leaving archetypal ring, ladder, chain homosynthons intact, but repositioned space. When applied heteromolecular synthons, this enables rearranging more complex motifs evolution binary cocrystals into ternary ones through “latent” carbon‐based sites, demonstrating a rational approach build higher‐order solid‐state supramolecular assemblies.

Language: Английский

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Metal-Bound Sulfur and Selenium Sites as Halogen Bond Acceptors: The Supramolecular Association of Rhodium(I) Half-Lantern Complexes with 1,4-Diiodotetrafluorobenzene

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(16), P. 6809 - 6818

Published: July 31, 2024

The half-lantern Rh2I complexes trans-(Ch,N)-[Rh(μ-Ch∧N)(COD)]2 (Ch = S, Se; HCh∧N 2-thiopyridine 1, 2-selenopyridine 2; COD 1,5-cyclooctadiene) were cocrystallized with 1,4-diiodotetrafluorobenzene (1,4-FIB) to give isostructural cocrystals 1·1,4-FIB and 2·1,4-FIB, both studied by X-ray crystallography. analysis of the structural data revealed a one-dimensional (1D) supramolecular arrangement, which is based on poorly explored I···[Ch]–M halogen bonding. Density functional theory (DFT) calculations, using set complementary computational methods, closely interrogated these interactions allowed estimate their energy (approximately −15 kcal/mol). In addition electrostatic dispersion interaction components, LP(Ch) → σ*(I–C) (LP lone pair) charge transfer also noticeably contributes bonding provides some covalent character this noncovalent interaction. observed assembly route integration metal-containing systems via ligand-involving bonding, include S or Se nucleophilic sites.

Language: Английский

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Chalcogen Bonding between Tellurium(II) and the Isocyanide Carbon

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 24, 2024

A novel type of chalcogen bond between tellurium(II) and the carbon atom isocyanide groups has been discovered in five cocrystals: 1·TePyF2 (two polymorphs), 2·TePyF2, 3·2TeTolF2, 3·TePyF2. These were obtained by cocrystallization monoisocyanide compounds CN-Np (Np-1 is 1-naphthyl; 1) CNC6H4CCPh (2) bis-isocyanide 1,4-(CN)2C6Me4 (3) with chalcolanes TePyF2 TeTolF2 (PyF = 4-NC5F4, TolF 4-CF3C6F4). The structures studied X-ray diffraction, revealing Te···C distances 2.9–3.2 Å (77–85% Bondi vdW sum) also characterized ATR FTIR spectroscopy. Computational analysis, including density functional theory (DFT) calculations, energy decomposition analysis (EDA), molecular electrostatic potential (MEP), quantum atoms molecules (QTAIM), noncovalent interaction (NCI) plot, natural orbital (NBO) showed that these bonds are primarily but relatively significant contributions. Monofunctional acceptors (1 2) form di- oligomers, while bifunctional acceptor creates extended supramolecular structures. Interaction strengths range from −6.4 to −9.6 kcal/mol for Te···CN contacts.

Language: Английский

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1,2,4-Oxadiazole Ring as the Halogen-Bond Acceptor: The Case Study of Dibenzoiodolium 1,2,4-Oxadiazolates

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

Three dibenzoiodolium 3-aryl-1,2,4-oxadiazolates (4a–c) were synthesized and characterized by 1H 13C{H} NMR as well HRMS in both positive negative modes. The solid-state structures of these compounds determined X-ray diffraction. Two them obtained isostructural monohydrates (4a·H2O 4b·H2O), whereas the third structure (4c) represents a monocomponent system. In case 4c, I···N halogen bonding (HaB) involving N4 atom heterocyclic anion was identified, which is first report on 1,2,4-oxadiazole ring acting HaB acceptor. Moreover, all structures, strong I···O HaBs between iodine(III) center exocyclic oxygen 1,2,4-oxadiazolate revealed, including rare example bifurcate I···(O,O) with two different anions (4c). DFT calculations using periodic boundary conditions confirmed existence nature interactions.

Language: Английский

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Synthesis and Structure Characterization of Three Pharmaceutical Compounds Based on Tinidazole

Crystals, Journal Year: 2023, Volume and Issue: 13(6), P. 947 - 947

Published: June 12, 2023

Tinidazole (TNZ), a 5-nitroimidazole derivative, has received increasing attention due to its pharmacological activities in treatment for amebic and parasitic infections. In this paper, we synthesized three novel drug supramolecular compounds successfully based on TNZ. The discussed were formed by TNZ 2,6-dihydroxybenzoic acid (2,6-DHBA), 4-methylsalicylic (4-MAC), 5-chloro-2-hydroxybenzoic (5-C-2-HBA). N-H···O O-H···O hydrogen bonds weak C-H···O are the primary intermolecular forces construction of compounds. Crystal structure analysis revealed that all exhibit three-dimensional frameworks consisting non-covalent interactions. Furthermore, six synthons, Ⅰ R22 (8), Ⅱ R21(6), Ⅲ R22(12), Ⅳ R33(9), Ⅴ Ⅵ through various found Moreover, resulting pharmaceutical show improved stability. Single-crystal X-ray diffraction analysis, infrared spectroscopy (IR), element thermogravimetric (TGA) reported.

Language: Английский

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Structure and Reactivity of Halogenated GC PNA Base Pairs – A DFT Approach

Journal of Experimental Biology and Agricultural Sciences, Journal Year: 2023, Volume and Issue: 11(5), P. 800 - 808

Published: Nov. 30, 2023

The present study explored the structural and reactivity relationship of halogenated G-C PNA base pairs using density functional theory (DFT) calculations. halogens such as F, Cl, Br are substituted by replacing H atoms involved in H-bonds pairs. All structures were optimized B3LYP/6-311++G** level, positive frequencies confirmed their equilibrium states. To understand variations considered systems, bond distances R─X, R─H, X/H•••Y angles R─X•••Y analyzed. obtained parameters interaction energies comparable with previous theoretical reports. In addition, (Eint) quantum molecular descriptors (QMD) also calculated to difference between systems non-halogenated counterparts. this study, enhancement properties has been demonstrated, which indicates improved responsive characteristics various chemical reactions. Based on available results, carefully considering substitutional position, facilitate better accommodation for triplex formation dsDNA/dsRNA. Therefore, it is concluded that would make them potential candidates biological applications.

Language: Английский

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