Halogen bonding directed supramolecular assembly in bromo-substituted trezimides and tennimides

CrystEngComm ◽  
2014 ◽  
Vol 16 (10) ◽  
pp. 1893-1903 ◽  
Author(s):  
Pavle Mocilac ◽  
John F. Gallagher
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Crystal Structures ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Strong Hydrogen Bond ◽  
Aggregation Process ◽  
Halogen Bonds ◽  
State Aggregation ◽  
Hydrogen Bond Donors

The imide-based trezimide and tennimide macrocycle crystal structures typically aggregate as 1-D chains through C–Br⋯OC/N/π(arene) halogen bonds (withNc≤ 0.90) that dominate the solid-state aggregation process in the absence of classical strong hydrogen bond donors.

Competition between hydrogen bonds and halogen bonds: a structural study

2018 ◽  
Vol 42 (13) ◽  
pp. 10539-10547 ◽  
Author(s):  
Janaka C. Gamekkanda ◽  
Abhijeet S. Sinha ◽  
John Desper ◽  
Marijana Đaković ◽  
Christer B. Aakeröy
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Structural Study ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Hydrogen Bond Donors

O–H hydrogen-bond donors and R–CC–I halogen-bond donors are close competitors for suitable acceptor sites in solid-state assembly.

scholarly journals New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

2016 ◽  
Vol 12 ◽  
pp. 2834-2848 ◽  
Author(s):  
Pavel Nagorny ◽  
Zhankui Sun
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Recent Progress ◽  
Halogen Bonds ◽  
Hydrogen Bond Donor ◽  
New Approaches ◽  
Substrate Activation ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Hydrogen Bond Donors

Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

Harnessing uranyl oxo atoms via halogen bonding interactions in molecular uranyl materials featuring 2,5-diiodobenzoic acid and N-donor capping ligands

2017 ◽  
Vol 4 (1) ◽  
pp. 65-78 ◽  
Author(s):  
Korey P. Carter ◽  
Mark Kalaj ◽  
Christopher L. Cahill
Keyword(s):  
Solid State ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Capping Ligands

The supramolecular assembly of molecular uranyl species via halogen-oxo interactions and spectroscopic manifestations thereof are probed in the solid state.

Supramolecular assembly in metal complexes: Two structural cases

2013 ◽  
Vol 85 (2) ◽  
pp. 397-404 ◽  
Author(s):  
Mohamed Ghazzali
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Theoretical Calculations ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
One Pot ◽  
Iron Coordination ◽  
Structural Database ◽  
Molecular Components ◽  
Theoretical Analyses

With the current advances in our understanding of molecular components in the solid-state world, the relation between energy and geometry remains controversial. In this study, we deliver a concise account for supramolecular chemistry, and in order to illustrate some of its concepts we describe some structural and theoretical analyses for two unique cases of our work. We elaborate on a supramolecular model of controlled “one-pot” host–guest metal-mediated self-assembly reaction inside iron coordination polymer grid architecture, and we review halogen bonding by specifically observing M–Cl···Cl–M intermolecular interactions using Cambridge Structural Database (CSD) hit analyses with theoretical calculations.

Hydrogen and halogen bonding in the haloetherification products in chalcone

2019 ◽  
Vol 75 (3) ◽  
pp. 342-347 ◽  
Author(s):  
Aytan R. Asgarova ◽  
Ali N. Khalilov ◽  
Ivan Brito ◽  
Abel M. Maharramov ◽  
Namiq G. Shikhaliyev ◽  
...  
Keyword(s):  
Solid State ◽  
Microwave Irradiation ◽  
Noncovalent Interactions ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
Cooperative Action ◽  
Alcohol Medium

Cooperative action of hydrogen and halogen bonding in the reaction of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-phenylprop-2-en-1-one with HCl or HBr in alcohol medium under microwave irradiation (20 W, 80 °C, 10 min) allows the isolation of the haloetherification products (2S,3S)-3-(3-tert-butyl-5-chloro-4-hydroxyphenyl)-2-chloro-3-ethoxy-1-phenylpropan-1-one, C21H24Cl2O3, (2S,3S)-2-bromo-3-(3-tert-butyl-5-bromo-4-hydroxyphenyl)-3-methoxy-1-phenylpropan-1-one, C20H22Br2O3, and (2S,3S)-2-bromo-3-(3-tert-butyl-5-bromo-4-hydroxyphenyl)-3-ethoxy-1-phenylpropan-1-one, C21H24Br2O3, in good yields. Both types of noncovalent interactions, e.g. hydrogen and halogen bonds, are formed to stabilize the obtained products in the solid state.

Heterocyclic Tautomerism. The Solution and Crystal Structures of 1-(4',6'-Dimethylpyrimidin-2'-yl)-3-methylpyrazol-5-ol

1984 ◽  
Vol 37 (2) ◽  
pp. 459 ◽  
Author(s):  
PJ Steel ◽  
AR Whyte
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Crystal Structures ◽  
Intramolecular Hydrogen Bond ◽  
Title Compound ◽  
Intramolecular Hydrogen ◽  
Strong Intramolecular Hydrogen Bond

Both in the solid state and in solution, the title compound is shown to exist as the OH tautomer (3), which is stabilized by a strong intramolecular hydrogen bond. Crystals of the pyrazol-5-ol (3) are monoclinic: P 21/c, a 9.692(5), b 7.371(5), c 15.345(8) �, β 106.07(4)�, Z 4; the structure was refined to R 0.072 and Rw 0.062.

The15N NMR chemical shift in the characterization of weak halogen bonding in solution

2017 ◽  
Vol 203 ◽  
pp. 333-346 ◽  
Author(s):  
Sebastiaan B. Hakkert ◽  
Jürgen Gräfenstein ◽  
Mate Erdelyi
Keyword(s):  
Hydrogen Bond ◽  
Chemical Shift ◽  
Halogen Bond ◽  
Molar Fraction ◽  
Halogen Bonding ◽  
Relative Strength ◽  
Lewis Base ◽  
Halogen Bonds ◽  
Bonded Complexes

We have studied the applicability of15N NMR spectroscopy in the characterization of the very weak halogen bonds of nonfluorinated halogen bond donors with a nitrogenous Lewis base in solution. The ability of the technique to detect the relative strength of iodine-, bromine- and chlorine-centered halogen bonds, as well as solvent and substituent effects was evaluated. Whereas computations on the DFT level indicate that15N NMR chemical shifts reflect the diamagnetic deshielding associated with the formation of a weak halogen bond, the experimentally observed chemical shift differences were on the edge of detectability due to the low molar fraction of halogen-bonded complexes in solution. The formation of the analogous yet stronger hydrogen bond of phenols have induced approximately ten times larger chemical shift changes, and could be detected and correlated to the electronic properties of substituents of the hydrogen bond donors. Overall,15N NMR is shown to be a suitable tool for the characterization of comparably strong secondary interactions in solution, but not sufficiently accurate for the detection of the formation of thermodynamically labile, weak halogen bonded complexes.

scholarly journals C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), with segregatedversusalternated stacks

2014 ◽  
Vol 70 (1) ◽  
pp. 141-148 ◽  
Author(s):  
Julien Lieffrig ◽  
Olivier Jeannin ◽  
Antoine Vacher ◽  
Dominique Lorcy ◽  
Pascale Auban-Senzier ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Solid State ◽  
Mixed Valence ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
Partial Charge Transfer ◽  
Face To Face ◽  
State Association ◽  
A Charge ◽  
State Organization

Oxidation of diiodoethylenedithiotetrathiafulvalene (EDT-TTF-I2), C8H4I2S6, with the strong oxidizer tetrafluorotetracyanoquinodimethane (TCNQF4), C12F4N4, affords, depending on the crystallization solvent, two polymorphs of the 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), represented asD2A. In both salts, the TCNQF4is reduced to the radical anion state, and is associated through short C—I...NC halogen bonds to two EDT-TTF-I2molecules. The two polymorphs differ in the solid-state association of these trimericD–A–Dmotifs. In polymorph (I) the trimeric motif is located on an inversion centre, and hence both EDT-TTF-I2molecules have +0.5 charge. Together with segregation of the TTF and TCNQ derivatives into stacks, this leads to a charge-transfer salt with high conductivity. In polymorph (II) two crystallographically independent EDT-TTF-I2molecules bear different charges, close to 0 and +1, as deduced from an established correlation between intramolecular bond lengths and charge. Overlap interactions between the halogen-bondedD0–A^{{-}{\bullet}}–D^{{+}{\bullet}} motifs give rise, in a perpendicular direction, to diamagneticA22−andD0–D22+–D0entities, where the radical species are paired into the bonding combination of respectively the acceptor LUMOs and donor HOMOs. The strikingly different solid-state organization of the halogen-bondedD–A–Dmotifs provides an illustrative example of two modes of face-to-face interaction between π-type radicals, into either delocalized, uniform chains with partial charge transfer and conducting behaviour, or localized association of radicals into face-to-faceA22−andD22+dyads.

scholarly journals Affirmative polymorph generation of annulenes by using CH/O interactions

2014 ◽  
Vol 70 (a1) ◽  
pp. C543-C543
Author(s):  
Ichiro Hisaki ◽  
Norimitsu Tohnai ◽  
Mikiji Miyata
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Methyl Ester ◽  
Ester Group ◽  
Strong Hydrogen Bond ◽  
Weak Hydrogen Bond ◽  
Conjugated Molecules ◽  
Pi Conjugated ◽  
Polymorphic Crystals ◽  
Benzene Rings

CH/O interaction is recognized as a weak hydrogen bond with less directionality, compared with a strong hydrogen bond such as that between carboxylic acids. Therefore, the interaction does not seem to be suitable for precise design of crystal structures. In connection with this, however, we emphasized that the CH/O interaction, particularly that provided by methyl ester group, can utilize for affirmative generation of polymorphs of cyclic pi conjugated molecules. Since functionality of solid state materials based on pi conjugated molecules is crucially affected by their molecular arrangements, polymorphs are exactly appropriate systems to reveal the superstructure-dependent properties of such the materials, and therefore, affirmative preparation of polymorphs of pi conjugated molecules is challenging. Herein, we describe formation, crystallographic characterization, and superstructure-dependent properties of polymorphs of methyl ester functionalized dehydrobenzoannulenes (DBAs), a family of cyclic conjugated molecules consisted of benzene rings and acetylene units. We synthesized five DBA derivatives 1-5 with two types of annulene cores (octadehydrodibenzo[12]annulene and octadehydrotribenzo[14]annulene cores) and different number and position of methyl ester groups (Scheme1). These derivatives exhibit two to five polymorphic crystals with physical properties strongly depending with their supramolecular structures.[1-3] We believe that the present polymorph generation is exactly provided by rotationally flexible conformations of the ester groups and versatile ways of directionally tolerant CH/O interactions of the ester groups.

scholarly journals Crystal structure of 2-tert-butyl-1,3-thiazolo[4,5-b]pyridine

2014 ◽  
Vol 70 (9) ◽  
pp. o932-o932 ◽  
Author(s):  
Gamal A. El-Hiti ◽  
Keith Smith ◽  
Amany S. Hegazy ◽  
Ali M. Masmali ◽  
Benson M. Kariuki
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Title Compound ◽  
Strong Hydrogen Bond ◽  
Linear Interaction ◽  
Tert Butyl ◽  
Compound C ◽  
Butyl Group ◽  
Librational Motion ◽  
Hydrogen Bond Donors

The title compound, C10H12N2S, does not contain any strong hydrogen-bond donors but two long C—H...N contacts are observed in the crystal structure, with the most linear interaction linking molecules along [010]. The ellipsoids of thetert-butyl group indicate large librational motion.

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