Complementary, Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals

Speetzen, Erin D.; Nwachukwu, Chideraa I.; Bowling, Nathan P.; Bosch, Eric

doi:10.3390/molecules27051527

Cited by 6 publications

(6 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…anion-π, cation-π, π-stacking, C-H/π, σ/π-hole, lone-pair/π, etc., play decisive roles in the stability of the compounds owing to their combined strength, directionality and ability to act synergistically [13][14][15]. The cooperative interplay of π-stacking interactions also attracts researchers from the crystal engineering viewpoint [16,17]. The inclusion of self-assembled guests within the host cavities in supramolecular architectures usually depends on the molecular association and the size of the molecules [18].…”

Section: Introductionmentioning

confidence: 99%

Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies

et al. 2023

View full text Add to dashboard Cite

Two multi-component coordination compounds of Mn(II), viz. [Mn(H2O)6](2-Mepy)2(4-NO2bz)2·2H2O (1) and [Mn(H2O)6][Mn(2,3-PDCH)3]2 (2) (where, 2-Mepy = 2-methylpyridine, 4-NO2bz = 4-nitrobenzoate, 2,3-PDC = 2,3-pyridinedicarboxylate), have been synthesized and characterized using elemental, spectroscopic (FT-IR and electronic), TGA and single-crystal X-ray diffraction analyses. Complex 1 is a co-crystal hydrate of Mn(II) involving uncoordinated 2-Mepy, 4-NO2bz and water molecules; while compound 2 is a multi-component molecular complex salt of Mn(II) comprising cationic [Mn(H2O)6]2+ and anionic [Mn(2,3-PDCH)3]−complex moieties. The uncoordinated 2-Mepy and 4-NO2bz moieties of 1 are involved in lone-pair (l.p)-π and C–H⋯π interactions which stabilize the layered assembly of the compound. The crystal structure of compound 2 has been previously reported. However, we have explored the unusual enclathration of complex cationic moieties within the supramolecular host cavities formed by the molecular assembly of complex anionic moieties. The supramolecular assemblies obtained in the crystal structure have been further studied theoretically using DFT calculations, quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCI plot) computational tools. Theoretical studies reveal that the combination of π-staking interactions (l.p-π, π-π and C–H···π) have more structure-guiding roles compared to the H-bonds. The large binding energy of π-stacking interactions in 2 is due to the antiparallel orientation of aromatic rings and their coordination to the metal centers, thereby increasing the contribution of the dipole–dipole interactions.

show abstract

Section: Introductionmentioning

confidence: 99%

Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies

et al. 2023

View full text Add to dashboard Cite

show abstract

“…Hirshfeld surface mapped over d norm for T1. generated using TONTO B3LYP/6-311G(d,p) (Mackenzie et al, 2017) for T2 and B3LYP/DGDZVP (Torubaev & Samigullina, 2022;Speetzen et al, 2022;Mackenzie et al, 2017) for the other three iodine species (Fig. 9).…”

Section: Figurementioning

confidence: 99%

Competition between chalcogen and halogen bonding assessed through isostructural species

Silva¹,

Maguères²,

Аверкиев³

et al. 2022

Acta Crystallogr C

View full text Add to dashboard Cite

The amino group of 2-amino-5-(4-halophenyl)-1,3,4-chalcogenadiazole has been replaced with bromo/iodo substituents to obtain a library of four compositionally related compounds. These are 2-iodo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4I2N2S, 2-bromo-5-(4-bromophenyl)-1,3,4-selenadiazole, C8H4Br2N2Se, 2-bromo-5-(4-iodophenyl)-1,3,4-selenadiazole, C8H4BrIN2Se, and 2-bromo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4BrIN2S. All were isostructural and contained bifurcated Ch...N (Ch is chalcogen) and X...X (X is halogen) interactions forming a zigzag packing motif. The noncovalent Ch...N interaction between the chalcogen-bond donor and the best-acceptor N atom appeared preferentially instead of a possible halogen bond to the same N atom. Hirshfeld surface analysis and energy framework calculations showed that, collectively, a bifurcated chalcogen bond was stronger than halogen bonding and this is more structurally influential in this system.

show abstract

“…Earlier studies had demonstrated that the electron-poor m-dinitrobenzene formed colored �-stacked cocrystals with electronrich aminobenzenes (Bryce et al, 1988;McNeil et al, 2013). Recently, we extended this to include ditopic halogen bonding to related 4-{[(dimethylamino)phenyl]ethynyl}pyrimidines (Speetzen et al, 2022).…”

Section: Introductionmentioning

confidence: 98%

π-Complexation and C—H hydrogen bonding in the formation of colored cocrystals

2023

View full text Add to dashboard Cite

The present study evaluates the potential combination of charge-transfer electron-donor–acceptor π–π complexation and C—H hydrogen bonding to form colored cocrystals. The crystal structures of the red 1:1 cocrystals formed from the isomeric pyridines 4- and 3-{2-[4-(dimethylamino)phenyl]ethynyl}pyridine with 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene, both C14H4F4N2O4·C15H14N2, are reported. Intermolecular interaction energy calculations confirm that π-stacking interactions dominate the intermolecular interactions within each crystal structure. The close contacts revealed by Hirshfeld surface calculations are predominantly C—H interactions with N, O, and F atoms.

show abstract

Complementary, Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals

Cited by 6 publications

References 38 publications

Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies

Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies

Competition between chalcogen and halogen bonding assessed through isostructural species

π-Complexation and C—H hydrogen bonding in the formation of colored cocrystals

Contact Info

Product

Resources

About