scholarly journals Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted Iodonium Ylides

Crystals ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1085
Author(s):  
Tomohiro Kimura ◽  
Shohei Hamada ◽  
Takumi Furuta ◽  
Yoshiji Takemoto ◽  
Yusuke Kobayashi
Keyword(s):  
Crystal Structures ◽  
Aromatic Ring ◽  
Natural Bond Orbital ◽  
Halogen Bonding ◽  
Electron Withdrawing Group ◽  
Iodonium Ylides

Iodonium ylides have recently attracted much attention on account of their synthetic applications. However, only a limited number of reports concerning the properties and reactivity of iodonium ylides exist, which is partly due to their instability. In this study, we synthesized several iodonium ylides that bear both an electron-withdrawing group and an aromatic ring with an ortho-t-BuSO2 group. Based on the crystal structures of the synthesized iodonium ylides in combination with natural-bond-orbital (NBO) calculations, we estimated the strength of the intra- and intermolecular halogen-bonding interactions. In addition, we investigated the reactivity of the iodonium ylides under photoirradiation.

scholarly journals π-Hole Tetrel Bonds—Lewis Acid Properties of Metallylenes

Crystals ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 112
Author(s):  
Sławomir J. Grabowski
Keyword(s):  
Quantum Theory ◽  
Crystal Structures ◽  
Lewis Acid ◽  
Natural Bond Orbital ◽  
Database Search ◽  
Lewis Base ◽  
Atoms In Molecules ◽  
Acid Properties ◽  
Structural Database ◽  
Tetrel Bonds

The MP2/aug-cc-pVTZ calculations were performed on the dihalometallylenes to indicate their Lewis acid and Lewis base sites. The results of the Cambridge Structural Database search show corresponding and related crystal structures where the tetrel center often possesses the configuration of a trigonal bipyramid or octahedron. The calculations were also carried out on dimers of dichlorogermylene and dibromogermylene and on complexes of these germylenes with one and two 1,4-dioxide molecules. The Ge⋯Cl, Ge⋯Br, and Ge⋯O interactions are analyzed. The Ge⋯O interactions in the above mentioned germylene complexes may be classified as the π-hole tetrel bonds. The MP2 calculations are supported by the results of the Quantum Theory of Atoms in Molecules (QTAIM) and the Natural Bond Orbital (NBO) approaches.

Halogen-bonding in a new family of tris(haloanilato)metallate(iii) magnetic molecular building blocks

2014 ◽  
Vol 43 (19) ◽  
pp. 7006-7019 ◽  
Author(s):  
Matteo Atzori ◽  
Flavia Artizzu ◽  
Elisa Sessini ◽  
Luciano Marchiò ◽  
Danilo Loche ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Dft Calculations ◽  
Crystal Structures ◽  
General Formula ◽  
Halogen Bonding ◽  
Building Blocks ◽  
New Family ◽  
Molecular Building Blocks

Here we report on new tris(haloanilato)metallate(iii) complexes with general formula [M(X2An)3]3−, their crystal structures, DFT calculations and magnetic properties.

Quantum-Chemical Investigations on the Structural Variability of Anion–π Interactions

2014 ◽  
Vol 69 (7) ◽  
pp. 339-348 ◽  
Author(s):  
Verena Moha ◽  
Michael Giese ◽  
Richard Moha ◽  
Markus Albrecht ◽  
Gerhard Raabe
Keyword(s):  
Gas Phase ◽  
Aromatic Ring ◽  
Energy Surface ◽  
Electrostatic Energy ◽  
Dispersion Energy ◽  
Substitution Pattern ◽  
Energy Of Interaction ◽  
Electron Withdrawing Group ◽  
Energy Surfaces ◽  
Structural Versatility

The structural versatility of anion-p interactions was investigated computationally. Employing quantum-chemically optimized structures of a series of C6H6-nFn/Br- complexes and the Coulomb law together with the London formula to calculate the electrostatic and the dispersion energy of the interaction between the anion and the π-system led to the result that up to the number of n = 2 due to a significantly repulsive electrostatic energy of interaction the dispersion energy is not sufficient to stabilize such structures in the gas phase where the anion is located above the plane defined by the aromatic ring. The energy surfaces resulting from the interaction of bromide anions with isolated arenes bearing varying numbers of fluorine atoms in different positions of the aromatic ring also show a pronounced dependency on the subsitution pattern of the aromatic system. Depending on the nature of the electron withdrawing group and its position, the energy surface can have a sharply defined energetically low minimum, in which the anion is ‘fixed’. Other substitution patterns result in very flat energy surfaces, and even a surface with more than two local minima within the scanned area was found. Thus, our study reveals the reason for the experimentally observed structural versatility depending on the substitution pattern in the solid state.

scholarly journals Interplay of Hydrogen and Halogen Bonding in the Crystal Structures of 2,6‐Dihalogenated Phenols

2021 ◽  
Vol 6 (33) ◽  
pp. 8736-8740
Author(s):  
Jonathan O. Bauer ◽  
Sarah Koschabek ◽  
Alexander Falk
Keyword(s):  
Crystal Structures ◽  
Halogen Bonding

Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding

2014 ◽  
Vol 16 (42) ◽  
pp. 22935-22952 ◽  
Author(s):  
Abhishek Shahi ◽  
Elangannan Arunan
Keyword(s):  
Hydrogen Bonding ◽  
Bond Order ◽  
Natural Bond Orbital ◽  
Halogen Bonding ◽  
Atoms In Molecules ◽  
Lithium Bonding ◽  
Intermolecular Bonding ◽  
Molecular Bonding

In D–X⋯A bonding (X = H/Cl/Li), there is a conservation of bond order that includes both ionicity and covalency in both D–X and X⋯A bonds. This should be applicable to any atom X involved in intermolecular bonding.

scholarly journals Likelihood of atom–atom contacts in crystal structures of halogenated organic compounds

IUCrJ ◽  
2015 ◽  
Vol 2 (3) ◽  
pp. 327-340 ◽  
Author(s):  
Christian Jelsch ◽  
Sarra Soudani ◽  
Cherif Ben Nasr
Keyword(s):  
Chemical Composition ◽  
Crystal Structures ◽  
Organic Compounds ◽  
Chemical Species ◽  
Halogen Bonding ◽  
Molecular Surface ◽  
Analysis Tool ◽  
Halogenated Organic Compounds ◽  
High Propensity ◽  
Crystal Contacts

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen...halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C...C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C—H...Cl and O—H...O are the preferred interactions in compounds containing both O and Cl.

Crystal structures of four δ-keto esters and a Cambridge Structural Database analysis of cyano–halogen interactions

2015 ◽  
Vol 71 (10) ◽  
pp. 921-928 ◽  
Author(s):  
Kulsoom Kamal ◽  
Hardesh K. Maurya ◽  
Atul Gupta ◽  
Prema G. Vasudev
Keyword(s):  
Crystal Structures ◽  
Crystal Packing ◽  
Noncovalent Interactions ◽  
Halogen Bonding ◽  
Cambridge Structural Database ◽  
Database Analysis ◽  
Molecular Conformations ◽  
Keto Esters ◽  
Organic Molecular Crystals ◽  
Structural Database

The revived interest in halogen bonding as a tool in pharmaceutical cocrystals and drug design has indicated that cyano–halogen interactions could play an important role. The crystal structures of four closely related δ-keto esters, which differ only in the substitution at a single C atom (by H, OMe, Cl and Br), are compared, namely ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate, C19H22N2O3, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C20H24N2O4, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21ClN2O3, (3), and the previously published ethyl 5-(4-bromophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21BrN2O3, (4) [Maurya, Vasudev & Gupta (2013).RSC Adv.3, 12955–12962]. The molecular conformations are very similar, while there are differences in the molecular assemblies. Intermolecular C—H...O hydrogen bonds are found to be the primary interactions in the crystal packing and are present in all four structures. The halogenated derivatives have additional aromatic–aromatic interactions and cyano–halogen interactions, further stabilizing the molecular packing. A database analysis of cyano–halogen interactions using the Cambridge Structural Database [CSD; Groom & Allen (2014).Angew. Chem. Int. Ed.53, 662–671] revealed that about 13% of the organic molecular crystals containing both cyano and halogen groups have cyano–halogen interactions in their packing. Three geometric parameters for the C—X...N[triple-bond]C interaction (X = F, Cl, Br or I),viz.the N...Xdistance and the C—X...N and C—N...Xangles, were analysed. The results indicate that all the short cyano–halogen contacts in the CSD can be classified as halogen bonds, which are directional noncovalent interactions.

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