On the Difference of the Properties between the Blue-Shifting Halogen Bond and the Blue-Shifting Hydrogen Bond

In the title compound, 2C14H8N4O6·CH2Cl2, the dichloromethane solvent molecule resides on a crystallographic twofold axis. The mean plane of the phthalisoimide ring is oriented at a dihedral angle of 32.93 (12)° with respect to the nitro-substituted benzene ring. An intramolecular N—H...O hydrogen bond occurs. The crystal packing features a short Cl...O halogen-bond interaction [3.093 (3) Å].

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Theoretical study of cooperativity between hydrogen bond‒hydrogen bond, halogen bond‒halogen bond and hydrogen bond‒halogen bond in ternary FX…diazine…XF (X = H and Cl) complexes

Molecular Physics ◽

10.1080/00268976.2016.1236992 ◽

2016 ◽

Vol 114 (23) ◽

pp. 3464-3474 ◽

Cited By ~ 5

Author(s):

Hamid Reza Masoodi ◽

Sotoodeh Bagheri ◽

Mahdiyeh Ranjbar

Keyword(s):

Hydrogen Bond ◽

Theoretical Study ◽

Halogen Bond

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Halogen Bonding Organocatalysis Enhanced through Intramolecular Hydrogen Bonds

Chemical Communications ◽

10.1039/d1cc05475a ◽

2022 ◽

Author(s):

Asia Marie S Riel ◽

Daniel Adam Decato ◽

Jiyu Sun ◽

Orion Berryman

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonds ◽

Halogen Bond ◽

Direct Interaction ◽

Halogen Bonding ◽

Intramolecular Hydrogen Bonds ◽

Intramolecular Hydrogen

Recent results indicate a halogen bond donor is strengthened through direct interaction with a hydrogen bond to the electron-rich belt of the halogen. Here, this Hydrogen Bond enhanced Halogen Bond...

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Cooperative interaction between hydrogen bond and N···Y interactions (Y = H, Li, F, Cl, and Br): a comparative study

Canadian Journal of Chemistry ◽

10.1139/cjc-2014-0514 ◽

2015 ◽

Vol 93 (6) ◽

pp. 626-631

Author(s):

Zahra Fallah Ebrahimi ◽

Mehdi D. Esrafili ◽

Esmail Vessally

Keyword(s):

Hydrogen Bond ◽

Comparative Study ◽

Ab Initio ◽

Halogen Bond ◽

Cooperative Interaction ◽

Ab Initio Study ◽

Absolute Value ◽

Lithium Bond ◽

Cooperative Energy

A comparative ab initio study is performed to investigate the cooperativity between the N···H hydrogen bond and the N···Y interactions in XCN···HCN···YCN complexes, where X = H, F, and Y = H, Li, F, Cl, and Br. To understand the properties of the systems better, the corresponding dimers are also studied. It is found that the lithium bond has a larger influence on the hydrogen bond than vice versa. The shortening of the N···H distances in the trimers is dependent on the strength of the H···Y interactions and they become larger in the order lithium bond > hydrogen bond > halogen bond. The estimated values of cooperative energy Ecoop are all negative with much larger Ecoop in absolute value for the systems including lithium.

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Excess volumes of an alcohol + 1,2-dichloroethane

Canadian Journal of Chemistry ◽

10.1139/v81-318 ◽

1981 ◽

Vol 59 (14) ◽

pp. 2210-2211 ◽

Cited By ~ 20

Author(s):

Nettem V. Choudary ◽

Puligundla R. Naidu

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonds ◽

Binary Mixtures ◽

Excess Volumes ◽

Hydrogen Bond Interaction ◽

Bond Interaction ◽

Break Up ◽

The Difference

Excess volumes for binary mixtures of 1,2-dichloroethane with n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol have been determined at 303.15 K. VE is positive over the whole range of composition in all the mixtures. However, it is noticed that the positive values of VE of mixtures of 1,2-dichloroethane with n-hexanol, n-heptanol, and n-octanol differ from those for the mixtures of 1,2-dichloroethane with corresponding alkanes. The difference has been explained in terms of the break up of hydrogen bonds, interstitial accommodation of 1,2-dichloroethane in alcohol aggregates, and possible hydrogen bond interaction of the type Cl … H—O between unlike molecules.

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Infrared spectroscopic characterization of hydrogen-bonded propylene oxide − ethanol and propylene oxide − 2-fluoroethanol complexes isolated in solid neon matrices

Canadian Journal of Chemistry ◽

10.1139/cjc-2013-0355 ◽

2013 ◽

Vol 91 (12) ◽

pp. 1292-1302 ◽

Cited By ~ 1

Author(s):

Osama Y. Ali ◽

Elyse Jewer ◽

Travis D. Fridgen

Keyword(s):

Hydrogen Bond ◽

Propylene Oxide ◽

Spectroscopic Characterization ◽

Hydrogen Bond Donor ◽

Hydrogen Bond Acceptor ◽

Reduced Frequency ◽

Enthalpy Of Proton Transfer ◽

The Difference ◽

Bonded Complexes ◽

Hydrogen Bonded

The infrared absorption spectra of hydrogen-bonded complexes of propylene oxide with either ethanol or 2-fluoroethanol have been recorded in neon matrices. Mixtures of propylene oxide and ethanol or propylene oxide and 2-fluoroethanol vapors were mixed with an excess of neon gas and deposited onto a KBr substrate at 4.2 K. The results indicate that hydrogen-bonded complexes were formed with propylene oxide as the hydrogen bond acceptor and either ethanol or 2-fluoroethanol as the hydrogen bond donors. The features assigned to the O−H stretch were red-shifted by 175 and 193 cm−1 for the ethanol- and 2-fluoroethanol-containing complexes, respectively. The difference in red shifts can be accounted for due to the greater acidity of 2-fluroethanol. Deuterium isotope experiments were conducted to help confirm the assignment of the O–H stretch for the complexes. As well, structures and infrared spectra were calculated using B3LYP/6-311++G(2d,2p) calculations and were used to compare with the experimental spectra. A “scaling equation” rather than a scaling factor was used and is shown to greatly increase the utility of the calculations when comparing with experimental spectra. An examination of the O–H stretching red shifts for many hydrogen-bound complexes reveals a relationship between the shift and the difference between the acidity of the hydrogen bond donor and the basicity of the hydrogen bond acceptor (the enthalpy of proton transfer). Both hydrogen-bonded complexes and proton-bound complexes appear to have a maximum in the reduced frequency value that corresponds to complexes where the hydrogen/proton are equally shared between the two bases.

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Functional properties ensue from cooperation of different interactions

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314093693 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C630-C630

Author(s):

Giuseppe Resnati ◽

Pierangelo Metrangolo ◽

Giancarlo Terraneo ◽

Gabriella Cavallo

Keyword(s):

Hydrogen Bond ◽

Self Assembly ◽

Halogen Atom ◽

Crystal Packing ◽

Halogen Bond ◽

Decisive Role ◽

Solid Materials ◽

Two Component ◽

Confined Environment ◽

Specific Profile

According to the definition recommended by IUPAC [1], a halogen bond (XB) occurs when there is evidence of a net attractive interaction between an electrophilic region in a halogen atom and a nucleophilic region in another atom. The halogen bond has many similarities with the hydrogen bond (HB) and here we discuss the specific profile of the two interactions. We also show how the cooperation between the two interactions afford crystalline systems possessing unique and useful properties. For instance, the diiodide, dibromide, and dichloride salts of the 1,6-bis(trimethylammonium)hexane cation (hexamethonium, HMET2+, cation) react with two equivalents of diiodine in a solid-gas reaction and the corresponding bis-trihalides (halogen bonded adducts) are formed [2]. No cavities are present in the starting dihalides and the observed behavior reveals the dynamically porous character of bis(trimethylammonium)alkane dihalides. In the obtained bis-trihalides a net of X-···H-C HBs (X=Cl, Br, I) plays a decisive role in controlling the crystal packing: Four cationic columns embrace an anionic twin column formed by stacking of trihalide dimers. When heated, these bis-trihalides lose one diiodine molecule and the virtually unknown tetrahalide dianions [I4]2-, [I2Br2] 2-, and [I2Cl2]2-are formed. These dianions are the product of the double pinning of a diiodine molecule by two halide anions via strong XBs. The last two tetrahalides were never obtained in solution. The confined environment of dynamically porous materials clearly confers useful synthetic opportunities relative to solution-state processes. Other cases are described wherein XB and HB cooperate in driving self-assembly processes which afford solid materials endowed with useful properties. For instance, we will discuss the formation of two-component supramolecular gels [3] wherein a bis-urea and a diiodoarene self-assemble via cooperative XB and HB.

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