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

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.

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Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure

Scientific Reports ◽

10.1038/srep32852 ◽

2016 ◽

Vol 6 (1) ◽

Cited By ~ 20

Author(s):

Ryosuke Sinmyo ◽

Elena Bykova ◽

Sergey V. Ovsyannikov ◽

Catherine McCammon ◽

Ilya Kupenko ◽

...

Keyword(s):

Applied Sciences ◽

Crystal Structure ◽

Iron Oxide ◽

Iron Oxides ◽

Industrial Applications ◽

Ambient Conditions ◽

X Ray Diffraction ◽

X Ray ◽

High Pressure High Temperature ◽

Insight Into

Abstract Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth’s interior.

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Nontypical iodine–halogen bonds in the crystal structure of (3E)-8-chloro-3-iodomethylidene-2,3-dihydro-1,4-oxazino[2,3,4-ij]quinolin-4-ium triiodide

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229616003934 ◽

2016 ◽

Vol 72 (4) ◽

pp. 341-345 ◽

Cited By ~ 4

Author(s):

E. V. Bartashevich ◽

V. I. Batalov ◽

I. D. Yushina ◽

A. I. Stash ◽

Y. S. Chen

Keyword(s):

Crystal Structure ◽

Rare Case ◽

Halogen Bond ◽

Spectroscopic Properties ◽

Halogen Bonds ◽

X Ray Diffraction ◽

Weakly Bound ◽

X Ray ◽

Raman Spectroscopic

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C12H8ClINO+·I3−, described by X-ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. The influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.

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Synthesis of 1-(2-Fluorophenyl)pyrazoles by 1,3-Dipolar Cycloaddition of the Corresponding Sydnones

Molecules ◽

10.3390/molecules26123693 ◽

2021 ◽

Vol 26 (12) ◽

pp. 3693

Author(s):

Denisa Dumitrescu ◽

Sergiu Shova ◽

Constantin Draghici ◽

Marcel Mirel Popa ◽

Florea Dumitrascu

Keyword(s):

Crystal Structure ◽

Nmr Spectroscopy ◽

Cycloaddition Reaction ◽

Halogen Bonding ◽

Dipolar Cycloaddition ◽

Dimethyl Acetylenedicarboxylate ◽

Reaction Intermediates ◽

X Ray Diffraction ◽

X Ray ◽

Important Interaction

3-Arylsydnones bearing fluorine and bromine atoms on the benzene ring were synthesized from N-nitroso-2-fluorophenylglycines and characterized by NMR spectroscopy. These were employed further in synthesis of the corresponding 1-(2-fluorophenyl)pyrazoles by 1,3-dipolar cycloaddition reaction with dimethyl acetylenedicarboxylate (DMAD) as activated dipolarophile. The sydnones as reaction intermediates were characterized by single crystal X-ray diffraction analysis showing interesting features such as halogen bonding as an important interaction in modeling the crystal structure.

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Understanding the Solid-State Assembly of Pharmaceutically-Relevant N,N-Dimethyl-O-Thiocarbamates in the Absence of Labile Hydrogen Bonds

10.26434/chemrxiv.12949697 ◽

2020 ◽

Author(s):

Davin Tan ◽

Zi xuan Ng ◽

Rakesh Ganguly ◽

yongxin Li ◽

Han Sen Soo ◽

...

Keyword(s):

Crystal Structure ◽

Solid State ◽

Molecular Geometry ◽

Pharmaceutical Compounds ◽

Labile Hydrogen ◽

X Ray Diffraction ◽

Hydrogen Bond Donor ◽

X Ray ◽

Medicinal Properties ◽

Insight Into

There are many pharmaceutical compounds that do not contain N-H, O-H, and S-H hydrogen-bond donor functional groups. Some of these compounds are N,N-disubstituted O-thiocarbamates which exhibit desirable medicinal properties, yet the study of these important molecules in the solid-state has been relatively unexplored. Herein, we report the synthesis and analysis of a series of N,N-dimethyl-O-thiocarbamates, and use X-ray diffraction techniques to gain insight into how these molecules self-assemble in the solid-state and discern certain packing patterns. It was observed that the aryl-thiocarbamate C-O bonds are twisted such that the planar aryl and carbamate moieties are orthogonal. Such a non-planar molecular geometry affects the way the molecules pack and crystal structure analyses revealed four general modes in which the molecules can associate in the solid-state, with some members of the series displaying isostructural relationships. The crystal structure of a well-known yet unreported O-thiocarbamate drug, Tolnaftate, is also reported. Additionally, Hirshfeld surface analysis was also performed on these compounds as well as several related O-thiocarbamates in the literature.<br>

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Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

Materials ◽

10.3390/ma13102370 ◽

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.

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

Materials ◽

10.3390/ma12203305 ◽

2019 ◽

Vol 12 (20) ◽

pp. 3305 ◽

Cited By ~ 5

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.

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Crystal structures of bis(phenoxy)silicon phthalocyanines: increasing π–π interactions, solubility and disorder and no halogen bonding observed

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s205698901600935x ◽

2016 ◽

Vol 72 (7) ◽

pp. 988-994 ◽

Cited By ~ 4

Author(s):

Benoît H. Lessard ◽

Alan J. Lough ◽

Timothy P. Bender

Keyword(s):

Crystal Structure ◽

Single Crystal ◽

Crystal Structures ◽

Halogen Bonding ◽

X Ray Diffraction ◽

X Ray ◽

Π Interactions ◽

Silicon Phthalocyanines ◽

Solution Processable

We report the syntheses and characterization of three solution-processable phenoxy silicon phthalocyanines (SiPcs), namely bis(3-methylphenoxy)(phthalocyanine)silicon [(3MP)2-SiPc], C46H30N8O2Si, bis(2-sec-butylphenoxy)(phthalocyanine)silicon [(2secBP)2-SiPc], C44H24I2N8O2Si, and bis(3-iodophenoxy)(phthalocyanine)silicon [(3IP)2-SiPc], C52H42N8O2Si. Crystals grown of these compounds were characterized by single-crystal X-ray diffraction and the π–π interactions between the aromatic SiPc cores were studied. It was determined that (3MP)2-SiPc has similar interactions to previously reported bis(3,4,5-trifluorophenoxy)silicon phthalocyanines [(345 F)2-SiPc] with significant π–π interactions between the SiPc groups. (3IP)2-SiPc and (2secBP)2-SiPc both experienced a parallel stacking of two of the peripheral aromatic groups. In all three cases, the solubility of these molecules was increased by the addition of phenoxy groups while maintaining π–π interactions between the aromatic SiPc groups. The solubility of (2secBP)2-SiPc was significantly higher than other bis-phenoxy-SiPcs and this was exemplified by the higher observed disorder within the crystal structure.

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

Crystals ◽

10.3390/cryst10050354 ◽

2020 ◽

Vol 10 (5) ◽

pp. 354 ◽

Cited By ~ 1

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.

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Understanding the Solid-State Assembly of Pharmaceutically-Relevant N,N-Dimethyl-O-Thiocarbamates in the Absence of Labile Hydrogen Bonds

10.26434/chemrxiv.12949697.v1 ◽

2020 ◽

Author(s):

Davin Tan ◽

Zi xuan Ng ◽

Rakesh Ganguly ◽

yongxin Li ◽

Han Sen Soo ◽

...

Keyword(s):

Crystal Structure ◽

Solid State ◽

Molecular Geometry ◽

Pharmaceutical Compounds ◽

Labile Hydrogen ◽

X Ray Diffraction ◽

Hydrogen Bond Donor ◽

X Ray ◽

Medicinal Properties ◽

Insight Into

There are many pharmaceutical compounds that do not contain N-H, O-H, and S-H hydrogen-bond donor functional groups. Some of these compounds are N,N-disubstituted O-thiocarbamates which exhibit desirable medicinal properties, yet the study of these important molecules in the solid-state has been relatively unexplored. Herein, we report the synthesis and analysis of a series of N,N-dimethyl-O-thiocarbamates, and use X-ray diffraction techniques to gain insight into how these molecules self-assemble in the solid-state and discern certain packing patterns. It was observed that the aryl-thiocarbamate C-O bonds are twisted such that the planar aryl and carbamate moieties are orthogonal. Such a non-planar molecular geometry affects the way the molecules pack and crystal structure analyses revealed four general modes in which the molecules can associate in the solid-state, with some members of the series displaying isostructural relationships. The crystal structure of a well-known yet unreported O-thiocarbamate drug, Tolnaftate, is also reported. Additionally, Hirshfeld surface analysis was also performed on these compounds as well as several related O-thiocarbamates in the literature.<br>

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