scholarly journals Halogen bonding in a series of Br(CF2) n Br–DABCO adducts (n = 4, 6, 8)

2017 ◽  
Vol 73 (11) ◽  
pp. 874-879 ◽  
Author(s):  
Alan K. Brisdon ◽  
Abeer M. T. Muneer ◽  
Robin G. Pritchard
Keyword(s):  
Solid Phase ◽  
Halogen Bond ◽  
Van Der Waals ◽  
Halogen Bonding ◽  
Vapour Phase ◽  
X Ray Diffraction ◽  
Nitrogen Base ◽  
One Dimensional ◽  
X Ray ◽  
Van Der Waals Radii

Halogen bonding (XB) is a highly-directional class of intermolecular interactions that has been used as a powerful tool to drive the design of crystals in the solid phase. To date, the majority of XB donors have been iodine-containing compounds, with many fewer involving brominated analogues. We report the formation of adducts in the vapour phase from a series of dibromoperfluoroalkyl compounds, BrCF2(CF2) n CF2Br (n = 2, 4, 6), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Single-crystal X-ray diffraction studies of the colourless crystals identified 1,4-diazabicyclo[2.2.2]octane–1,4-dibromoperfluorobutane (1/1), C4Br2F8·C6H12N2, (I), 1,4-diazabicyclo[2.2.2]octane–1,6-dibromoperfluorohexane (1/1), C6Br2F12·C6H12N2, (II), and 1,4-diazabicyclo[2.2.2]octane–1,8-dibromoperfluorooctane (1/1), C8Br2F16·C6H12N2, (III), each of which displays a one-dimensional halogen-bonded network. All three adducts exhibit N...Br distances less than the sum of the van der Waals radii, with butane analogue (I) showing the shortest N...Br halogen-bond distances yet reported between a bromoperfluorocarbon and a nitrogen base [2.809 (3) and 2.818 (3) Å], which are 0.58 and 0.59 Å shorter than the sum of the van der Waals radii.

scholarly journals Halogen-bonded adduct of 1,2-dibromo-1,1,2,2-tetrafluoroethane and 1,4-diazabicyclo[2.2.2]octane

2015 ◽  
Vol 71 (10) ◽  
pp. 900-902 ◽  
Author(s):  
Alan K. Brisdon ◽  
Abeer M. T. Muneer ◽  
Robin G. Pritchard
Keyword(s):  
Intermolecular Interaction ◽  
Halogen Atom ◽  
Halogen Bonding ◽  
Vapour Phase ◽  
Noncovalent Interaction ◽  
Lewis Base ◽  
Halogen Bonds ◽  
One Dimensional ◽  
Bonding Systems ◽  
Van Der Waals Radii

Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen-bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour-phase diffusion of 1,4-diazabicyclo[2.2.2]octane (DABCO) with 1,2-dibromotetrafluoroethane results in crystals of the 1:1 adduct, C2Br2F4·C6H12N2, which crystallizes as an infinite one-dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii.

scholarly journals Azobenzene-based difunctional halogen-bond donor: towards the engineering of photoresponsive co-crystals

2013 ◽  
Vol 70 (1) ◽  
pp. 149-156 ◽  
Author(s):  
Marco Saccone ◽  
Giancarlo Terraneo ◽  
Tullio Pilati ◽  
Gabriella Cavallo ◽  
Arri Priimagi ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
X Ray Diffraction ◽  
Donor Molecule ◽  
X Ray ◽  
Covalent Interaction ◽  
Material Systems ◽  
Azo Group ◽  
Insight Into

Halogen bonding is emerging as a powerful non-covalent interaction in the context of supramolecular photoresponsive materials design, particularly due to its high directionality. In order to obtain further insight into the solid-state features of halogen-bonded photoactive molecules, three halogen-bonded co-crystals containing an azobenzene-based difunctional halogen-bond donor molecule, (E)-bis(4-iodo-2,3,5,6-tetrafluorophenyl)diazene, C12F8I2N2, have been synthesized and structurally characterized by single-crystal X-ray diffraction. The crystal structure of the non-iodinated homologue (E)-bis(2,3,5,6-tetrafluorophenyl)diazene, C12H2F8N2, is also reported. It is demonstrated that the studied halogen-bond donor molecule is a reliable tecton for assembling halogen-bonded co-crystals with potential photoresponsive behaviour. The azo group is not involved in any specific intermolecular interactions in any of the co-crystals studied, which is an interesting feature in the context of enhanced photoisomerization behaviour and photoactive properties of the material systems.

Redox reactive (RNC)CuII species stabilized in the solid state via halogen bond with I2

2018 ◽  
Vol 233 (6) ◽  
pp. 371-377 ◽  
Author(s):  
Margarita Bulatova ◽  
Anna A. Melekhova ◽  
Alexander S. Novikov ◽  
Daniil. M. Ivanov ◽  
Nadezhda A. Bokach
Keyword(s):  
Crystal Structure ◽  
Electron Density Distribution ◽  
Halogen Bond ◽  
Topological Analysis ◽  
Halogen Bonding ◽  
Molecular Iodine ◽  
X Ray Diffraction ◽  
Covalent Character ◽  
X Ray ◽  
Model Complex

AbstractThe crystal structure of [Cu2(μ-O)(μ-I)2(CNXyl)4]·I2(2·I2) was determined from single-crystal X-ray diffraction data. The adduct2·I2represents the first example of structurally characterized isocyanide-copper(II) complexes. In the structure of2·I2,2forms independent chains connected through molecular iodine via I···I–I···I halogen bonding. The DFT calculations and topological analysis of the electron density distribution within the formalism of Bader’s theory (QTAIM method) were performed for model complex2·I2and the obtained results allowed the attribution of these contacts to moderate strength (3.8–5.3 kcal/mol) non-covalent contacts exhibiting some covalent character.

Anion Templated Crystal Engineering of Halogen Bonding Tripodal Tris(halopyridinium) Compounds

2020 ◽  
Author(s):  
Emer Foyle ◽  
Nicholas White
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Structural Database ◽  
Van Der Waals Radii

<div>In this work four new tripodal tris(halopyridinium) receptors containing potentially halogen</div><div>bonding groups were prepared. The ability of the receptors to bind anions in competitive</div><div>CD<sub>3</sub>CN/d<sub>6</sub>-DMSO was studied using <sup>1</sup>H NMR titration experiments, which revealed that the</div><div>receptors bind chloride anions more strongly than more basic acetate or other halide ions.</div><div>The solid state self–assembly of the tripodal receptors with halide anions was investigated by</div><div>X-ray crystallography. The nature of the structures was dependent on the choice of halide</div><div>anion, as well as the crystallisation solvent. Halogen bond lengths as short as 80% of the sum</div><div>of the van der Waals radii were observed, which is shorter than any halogen bonds involving</div><div>halopyridinium receptors in the Cambridge Structural Database.</div>

Anion Templated Crystal Engineering of Halogen Bonding Tripodal Tris(halopyridinium) Compounds

2020 ◽  
Author(s):  
Emer Foyle ◽  
Nicholas White
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Structural Database ◽  
Van Der Waals Radii

<div>In this work four new tripodal tris(halopyridinium) receptors containing potentially halogen</div><div>bonding groups were prepared. The ability of the receptors to bind anions in competitive</div><div>CD<sub>3</sub>CN/d<sub>6</sub>-DMSO was studied using <sup>1</sup>H NMR titration experiments, which revealed that the</div><div>receptors bind chloride anions more strongly than more basic acetate or other halide ions.</div><div>The solid state self–assembly of the tripodal receptors with halide anions was investigated by</div><div>X-ray crystallography. The nature of the structures was dependent on the choice of halide</div><div>anion, as well as the crystallisation solvent. Halogen bond lengths as short as 80% of the sum</div><div>of the van der Waals radii were observed, which is shorter than any halogen bonds involving</div><div>halopyridinium receptors in the Cambridge Structural Database.</div>

scholarly journals Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

Materials ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2370
Author(s):  
Nikola Bedeković ◽  
Valentina Martinez ◽  
Edi Topić ◽  
Vladimir Stilinović ◽  
Dominik Cinčić
Keyword(s):  
Single Crystal ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Building Blocks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Organic Halogen ◽  
Metal Organic

In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four previously unreported cocrystals. Single crystal X-ray diffraction experiments showed that the majority of obtained cocrystals exhibited the formation of the targeted I···O and I···Br motives. These results illustrate the potential of cobaloximes as halogen bond acceptors and indicate that this type of halogen bond acceptors may offer a novel route to metal–organic halogen-bonded cocrystals.

scholarly journals Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

Materials ◽  
2019 ◽  
Vol 12 (20) ◽  
pp. 3305 ◽  
Author(s):  
Carolina von Essen ◽  
Kari Rissanen ◽  
Rakesh Puttreddy
Keyword(s):  
Coordination Polymers ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halide Ions ◽  
Halogen Bonds ◽  
Discrete Structure ◽  
Electronic Effects ◽  
X Ray Diffraction ◽  
X Ray ◽  
Supramolecular Networks

Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A–Cu and C5−X5···A–Cu halogen bonds. The reaction of the 2,5-dihalopyridines and Cu(I) salts allows the synthesis of eight 1-D coordination polymers and a discrete structure. The resulting Cu(I)-complexes are linked by C−X···A–Cu halogen bonds forming 3-D supramolecular networks. The C−X···A–Cu halogen bonds formed between halopyridine ligands and copper(I)-bound halide ions are stronger than C−X···X’–C interactions between two 2,5-dihalopyridine ligands. The C5−I5···I–Cu and C5−Br5···Br–Cu halogens bonds are shorter for C2-fluorine than C2-chlorine due to the greater electron-withdrawing power of fluorine. In 2,5-diiodopyridine-Cu(I)Br complex, the shorter C2−I2···Br–Cu [3.473(5) Å] distances are due to the combined polarization of C2-iodine by C2−I2···Cu interactions and para-electronic effects offered by the C5-iodine, whilst the long halogen bond contacts for C5−I5···Br–Cu [3.537(5) Å] are indicative that C2-iodine has a less para-electronic influence on the C5-iodine. In 2-fluoro-5-X-pyridine-Cu(I) complexes, the C2-fluorine is halogen bond passive, while the other C2-halogens in 2,5-dihalopyridine-Cu(I), including C2-chlorine, participate in halogen bonding interactions.

scholarly journals Halogen Bonding in New Dichloride-Cobalt(II) Complex with Iodo Substituted Chalcone Ligands

Crystals ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 354 ◽  
Author(s):  
Lukáš Masaryk ◽  
Ján Moncol ◽  
Radovan Herchel ◽  
Ivan Nemec
Keyword(s):  
Density Functional ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Noncovalent Interaction ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
The Density Functional Theory ◽  
Non Covalent Interactions ◽  
Covalent Interactions

The synthesis and properties of new chalcone ligand 4I-L ((2E)-1-[4-(1H-imidazol-1-yl)phenyl]-3-(4-iodophenyl)prop-2-en-1-one) and tetracoordinate Co(II) complex [Co(4I-L)2Cl2], (1a), are reported in this article. Upon recrystallization of 1a, the single crystals of [Co(4I-L)4Cl2]·2DMF·3Et2O (1b) were obtained and crystal structure was determined using X-ray diffraction. The non-covalent interactions in 1b were thoroughly analyzed and special attention was dedicated to interactions formed by the peripheral iodine substituents. The density functional theory (DFT), atoms in molecule (AIM) and noncovalent interaction (NCI) methods and electronic localization function (ELF) calculations were used to investigate halogen bond formed between the iodine functional groups and co-crystallized molecules of diethyl ether.

Experimental electron density study of the supramolecular aggregation between 4,4′-dipyridyl-N,N′-dioxide and 1,4-diiodotetrafluorobenzene at 90 K

2004 ◽  
Vol 60 (5) ◽  
pp. 559-568 ◽  
Author(s):  
Riccardo Bianchi ◽  
Alessandra Forni ◽  
Tullio Pilati
Keyword(s):  
Electron Density ◽  
Halogen Bond ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Experimental Electron Density ◽  
Supramolecular Aggregation ◽  
Density Study

The electron density of the halogen-bonded complex of 4,4′-dipyridyl-N,N′-dioxide (bpNO) with 1,4-diiodotetrafluorobenzene (F4dIb) at 90 K has been determined by X-ray diffraction and analysed. The nature of the I...O intermolecular bond connecting the bpNO and F4dIb molecules into one-dimensional infinite chains, as well as the other non-covalent interactions present in the crystal, such as C—H...O, C—H...F and C—H...I hydrogen bonds and C...C, C...N, C...I and F...F interactions, have been investigated. The integration of electron density over the atomic basins reveals the electrostatic nature of the I...O halogen bond, which is very similar to a previously analysed I...N halogen bond.

scholarly journals C—I...N and C—I...π halogen bonding in the structures of 1-benzyliodoimidazole derivatives

2017 ◽  
Vol 73 (1) ◽  
pp. 2-8 ◽  
Author(s):  
Chideraa I. Nwachukwu ◽  
Nathan P. Bowling ◽  
Eric Bosch
Keyword(s):  
Intermolecular Interaction ◽  
Intermolecular Interactions ◽  
Halogen Bond ◽  
Three Dimensional ◽  
Functional Materials ◽  
Halogen Bonding ◽  
Dimensional Structure ◽  
Halogen Bonds ◽  
One Dimensional ◽  
X Ray

Halogen bonding is a well-established and intensively studied intermolecular interaction that has also been used in the preparation of functional materials. While polyfluoroiodo- and polyfluorobromobenzenes have been widely used as aromatic halogen-bond donors, there have been very few studies of iodoimidazoles with regard to halogen bonding. We describe here the X-ray structures of three iodoimidazole derivatives, namely 1-benzyl-2-iodo-1H-imidazole, C10H9IN2, (1), 1-benzyl-4-iodo-1H-imidazole, C10H9IN2, (2), and 1-benzyl-2-iodo-1H-benzimidazole, C14H11IN2, (3), and the halogen bonds that dominate the intermolecular interactions in each of these three structures. The three-dimensional structure of (1) is dominated by a strong C—I...N halogen bond, with an N...I distance of 2.8765 (2) Å, that connects the molecules into one-dimensional zigzag ribbons of molecules. In contrast, the three-dimensional structures of (2) and (3) both feature C—I...π halogen-bonded dimers.

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