scholarly journals Functional properties ensue from cooperation of different interactions

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.

scholarly journals (Z)-3-[2-(2,4-Dinitrophenyl)hydrazin-1-ylidene]isobenzofuran-1(3H)-one dichloromethane hemisolvate

2014 ◽  
Vol 70 (4) ◽  
pp. o418-o418
Author(s):  
Palak Agarwal ◽  
Pragati Mishra ◽  
Nikita Gupta ◽  
Neelam ◽  
Priyaranjan Sahoo ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Benzene Ring ◽  
Dihedral Angle ◽  
Title Compound ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Solvent Molecule ◽  
Twofold Axis ◽  
Bond Interaction ◽  
The Mean

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].

Cyclic networks of halogen-bonding interactions in molecular self-assemblies: a theoretical N—X...NversusC—X...N investigation

2017 ◽  
Vol 73 (2) ◽  
pp. 179-187
Author(s):  
Ruben D. Parra ◽  
Álvaro Castillo
Keyword(s):  
Electron Density ◽  
Self Assembly ◽  
Metal Ion ◽  
Halogen Atom ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Nbo Analysis ◽  
Binding Energies ◽  
Cyclic Network ◽  
Ability To Drive

The geometries and energetics of molecular self-assembly structures that contain a sequential network of cyclic halogen-bonding interactions are investigated theoretically. The strength of the halogen-bonding interactions is assessed by examining binding energies, electron charge transfer (NBO analysis) and electron density at halogen-bond critical points (AIM theory). Specifically, structural motifs having intramolecular N—X...N (X= Cl, Br, or I) interactions and the ability to drive molecular self-assemblyviathe same type of interactions are used to construct larger self-assemblies of up to three unit motifs. N—X...N halogen-bond cooperativity as a function of the self-assembly size, and the nature of the halogen atom is also examined. The cyclic network of the halogen-bonding interactions provides a suitable cavity rich in electron density (from the halogen atom lone pairs not involved in the halogen bonds) that can potentially bind an electron-deficient species such as a metal ion. This possibility is explored by examining the ability of the N—X...N network to bind Na+. Likewise, molecular self-assembly structures driven by the weaker C—X...N halogen-bonding interactions are investigated and the results compared with those of their N—X...N counterparts.

Quantum Chemical Dissection of the Shortest P=O⋅⋅⋅I Halogen Bond: The Decisive Role of Crystal Packing Effects

2017 ◽  
Vol 23 (24) ◽  
pp. 5687-5691 ◽  
Author(s):  
Tobias A. Schaub ◽  
Rebecca Sure ◽  
Frank Hampel ◽  
Stefan Grimme ◽  
Milan Kivala
Keyword(s):  
Quantum Chemical ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Decisive Role ◽  
Crystal Packing Effects ◽  
Packing Effects

scholarly journals Halogen-Bonding-Driven Self-Assembly of Solvates of Tetrabromoterephthalic Acid

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 198
Author(s):  
Nucharee Chongboriboon ◽  
Kodchakorn Samakun ◽  
Winya Dungkaew ◽  
Filip Kielar ◽  
Mongkol Sukwattanasinitt ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Phase Transitions ◽  
Self Assembly ◽  
Solid Phase ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Cooperative Effect ◽  
Hydrogen Bonding Interactions ◽  
Solvent Molecules

Halogen bonding is one of the most interesting noncovalent attractions capable of self-assembly and recognition processes in both solution and solid phase. In this contribution, we report on the formation of two solvates of tetrabromoterephthalic acid (H2Br4tp) with acetonitrile (MeCN) and methanol (MeOH) viz. H2Br4tp·2MeCN (1MeCN) and H2Br4tp·2MeOH (2MeOH). The host structures of both 1MeCN and 2MeOH are assembled via the occurrence of simultaneous Br···Br, Br···O, and Br···π halogen bonding interactions, existing between the H2Br4tp molecular tectons. Among them, the cooperative effect of the dominant halogen bond in combination with hydrogen bonding interactions gave rise to different supramolecular assemblies, whereas the strength of the halogen bond depends on the type of hydrogen bond between the molecules of H2Br4tp and the solvents. These materials show a reversible release/resorption of solvent molecules accompanied by evident crystallographic phase transitions.

Intermolecular N-H...O Hydrogen Bonding Assisted by Resonance. II. Self Assembly of Hydrogen-Bonded Secondary Enaminones in Supramolecular Catemers

1998 ◽  
Vol 54 (1) ◽  
pp. 50-65 ◽  
Author(s):  
V. Bertolasi ◽  
P. Gilli ◽  
V. Ferretti ◽  
G. Gilli
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Self Assembly ◽  
Crystal Packing ◽  
Average Distance ◽  
Conjugated Systems ◽  
Structural Database ◽  
Bond Strengths ◽  
Chemical Groups

The crystal structures of 15 compounds containing the 2-en-3-amino-1-one heterodienic system and forming intermolecular N—H...O hydrogen bonds assisted by resonance (RAHB) are reported: (1) 3-phenylamino-2-cyclohexen-1-one; (2) 3-(4-methoxyphenylamino)-2-cyclohexen-1-one; (3) 3-(4-chlorophenylamino)-2-cyclohexen-1-one; (4) 3-(4-methoxyphenylamino)-2-methyl-2-cyclohexen-1-one; (5) 3-(4-methoxyphenylamino)-5-methyl-2-cyclohexen-1-one; (6) 3-isopropylamino-5,5-dimethyl-2-cyclohexen-1-one; (7) 3-phenylamino-5,5-dimethyl-2-cyclohexen-1-one; (8) 3-(3-methoxyphenylamino)-5,5-dimethyl-2-cyclohexen-1-one; (9) N,N-3-aza-pentane-1,5-bis[1-(3-oxo-5,5-dimethyl-1-cyclohexenyl)]; (10) 3-phenylamino-6,6-dimethyl-2-cyclohexen-1-one; (11) 3-(2-methoxyphenylamino)-6,6-dimethyl-2-cyclohexen-1-one; (12) 3-(3-chlorophenylamino)-6,6-dimethyl-2-cyclohexen-1-one; (13) 3-(4-chlorophenylamino)-6,6-dimethyl-2-cyclohexen-1-one; (14) 1-(4-chlorophenyl)-4-(4-chlorophenylamino)-6-methyl-2-pyridone; (15) 3-(4-chlorophenylamino)-5-phenyl-2-cyclopenten-1,4-dione. All compounds form intermolecular N—H...O=C hydrogen bonds assisted by resonance connecting the heteroconjugated enaminonic groups in infinite chains. Chain morphologies are analyzed to find out crystal engineering rules able to predict and interpret the crystal packing. Simple secondary enaminones [i.e. (1)–(13) together with a number of structures retrieved from the Cambridge Structural Database] are found to form hydrogen bonds having π-delocalizations, as characterized by a C=O bond-length average of 1.239 ± 0.004 Å, and hydrogen-bond strengths, represented by the N...O average distance of 2.86 ± 0.05 Å, very similar to those previously found for amides. Enaminones, however, can be easily substituted by chemical groups able to influence both π-conjugations and N...O hydrogen-bond distances. Some substituted enaminones, retrieved from the literature, display, in fact, N...O hydrogen-bond distances as short as 2.627 Å and large π-delocalizations with C=O double-bond distances as long as 1.285 Å. These effects appear to be associated with (a) the presence of further π-conjugated systems involving the C=O and NH groups of the enaminone moiety or (b) the transformation of the enaminone carbonyl group in an amidic function.

Competition between hydrogen and halogen bonding in the structures of 5,10-dihydroxy-5,10-dihydroboranthrenes

2014 ◽  
Vol 70 (1) ◽  
pp. 157-171 ◽  
Author(s):  
Krzysztof Durka ◽  
Sergiusz Luliński ◽  
Katarzyna N. Jarzembska ◽  
Jaromir Smętek ◽  
Janusz Serwatowski ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Structural Diversity ◽  
Interesting Case ◽  
Molecular Arrangement ◽  
Supramolecular Arrangements

X-ray crystallographic and computational studies are reported for a series of boranthrenes, substituted with halogen atoms. The role of competitive hydrogen (O—H...O, O—H...F, C—H...O) and halogen (Cl...Cl, O...Br, F...F) bonding interactions on the molecular arrangement in the crystal structures is discussed. The structural analysis and calculations reveal that the O—H...O hydrogen bond in the unsubstituted derivative 5,10-dihydroxy-5,10-dihydroboranthrene, C12H10B2O2, is of moderate strength (ca−20 kJ mol−1), but weaker than that in the related thiophene derivative 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b]dithiophene, C8H6B2O2S2(ca−40 kJ mol−1). This is due to shielding of the OH group by the H atoms in the β-position of the boranthrene unit. Structural diversity derived from the flexibility of the O—H...O hydrogen bond facilitates the occurrence of other competitive interactions. For instance, in the 1,6-difluoro derivative, C12H8B2F2O2, the crystal packing results from O—H...F and F...F interactions. In turn, the 1,6-dibromo derivative, C12H8B2Br2O2, is dominated by Br...O halogen-bond interactions. In the most interesting case, the 1,6-dichloro derivative, C12H8B2Cl2O2, molecular disorder leads to the formation of two different supramolecular arrangements co-existing in the crystal lattice, one based on the Cl...Cl and C—H...O bonds, and the other stabilized by O—H...O hydrogen bonds. Calculations performed with density-functional theory (DFT;CRYSTAL09) andPIXELmethodologies show that both lattices are characterized by similar energy values (ca−100 kJ mol−1). A mixed arrangement with random or short-range-ordered molecular orientations can also be expected.

Halogen Substituent Effects on Concentration-Controlled Self-Assembly of Fluorenone Derivatives: Halogen Bond versus Hydrogen Bond

2019 ◽  
Vol 123 (7) ◽  
pp. 4349-4359 ◽  
Author(s):  
Meiqiu Dong ◽  
Kai Miao ◽  
Juntian Wu ◽  
Xinrui Miao ◽  
Jinxing Li ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Self Assembly ◽  
Halogen Bond ◽  
Substituent Effects

scholarly journals Influence of Halogen Substituent on the Self-Assembly and Crystal Packing of Multicomponent Crystals Formed from Ethacridine and Meta-Halobenzoic Acids

Crystals ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 79 ◽  
Author(s):  
Artur Mirocki ◽  
Artur Sikorski
Keyword(s):  
Self Assembly ◽  
Halogen Atom ◽  
Crystal Packing ◽  
The Self ◽  
Water Molecules ◽  
Stacking Interactions ◽  
Ethoxy Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Relationship

In order to determine the influence of halogen substituent on the self-assembly of the 6,9-diamino-2-ethoxyacridinium cations and 3-halobenzoate anions in the crystals formed from ethacridine and halobenzoic acids, the series of ethacridinium meta-halobenzoates dihydrates: ethacridinium 3-chlorobenzoate dihydrate (1), ethacridinium 3-bromobenzoate dihydrate (2), and ethacridinium 3-iodobenzoate dihydrate (3), were synthesized and structurally characterized. Single-crystal X-ray diffraction measurements showed that the title compounds crystallized in the monoclinic P21/c space group and are isostructural. In the crystals of title compounds, the ions and water molecules interact via N–H⋯O, O–H⋯O and C–H⋯O hydrogen bonds and π–π stacking interactions to produce blocks. The relationship between the distance X⋯O between the halogen atom (X=Cl, Br, I) of meta-halobenzoate anion and the O-atom from the ethoxy group of cation from neighbouring blocks and crystal packing is observed in the crystals of the title compounds.

scholarly journals Chalcogen Bond versus Weak Hydrogen Bond: Changing Contributions in Determining the Crystal Packing of [1,2,5]-Chalcogenadiazole-Fused Tetracyanonaphthoquinodimethanes

2021 ◽  
Vol 03 (02) ◽  
pp. 090-096
Author(s):  
Yusuke Ishigaki ◽  
Kota Asai ◽  
Takuya Shimajiri ◽  
Tomoyuki Akutagawa ◽  
Takanori Fukushima ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Molecular Design ◽  
Crystal Packing ◽  
Cyano Group ◽  
Density Functional Theory Calculations ◽  
Weak Hydrogen Bond ◽  
Functional Theory ◽  
Chalcogen Bond ◽  
Thiadiazole Ring

The crystal structures of a series of tetracyanonaphthoquinodimethanes fused with a selenadiazole or thiadiazole ring revealed that their molecular packing is determined mainly by two intermolecular interactions: chalcogen bond (ChB) and weak hydrogen bond (WHB). ChB between Se and a cyano group dictates the packing of selenadiazole derivatives, whereas the S-based ChB is much weaker and competes with WHB in thiadiazole analogues. This difference can be explained by different electrostatic potentials as revealed by density functional theory calculations. A proper molecular design that weakens WHB can change the contribution of ChB in determining the crystal packing of thiadiazole derivatives.

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