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.

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.

Submolecular partitioning of morphine hydrate based on its experimental charge density at 25 K

2005 ◽  
Vol 61 (4) ◽  
pp. 443-448 ◽  
Author(s):  
S. Scheins ◽  
M. Messerschmidt ◽  
P. Luger
Keyword(s):  
Electron Density ◽  
Electron Density Distribution ◽  
Theoretical Calculations ◽  
Topological Analysis ◽  
Theoretical Studies ◽  
X Ray Diffraction ◽  
X Ray ◽  
Resolution Single ◽  
Experimental Electron Density ◽  
Experimental Charge Density

The electron density distribution of morphine hydrate has been determined from high-resolution single-crystal X-ray diffraction measurements at 25 K. A topological analysis was applied and, in order to analyze the submolecular transferability based on an experimental electron density, a partitioning of the molecule into atomic regions was carried out, making use of Bader's zero-flux surfaces to yield atomic volumes and charges. The properties obtained were compared with the theoretical calculations of smaller fragment molecules, from which the complete morphine molecule can be reconstructed, and with theoretical studies of another opiate, Oripavine PEO, reported in the literature.

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

2016 ◽  
Vol 72 (4) ◽  
pp. 341-345 ◽  
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.

The whole range of hydrogen bonds in one crystal structure: neutron diffraction and charge-density studies of N,N-dimethylbiguanidinium bis(hydrogensquarate)

2011 ◽  
Vol 67 (6) ◽  
pp. 552-559 ◽  
Author(s):  
Mihaela-Diana Şerb ◽  
Ruimin Wang ◽  
Martin Meven ◽  
Ulli Englert
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
High Resolution ◽  
Hydrogen Bonds ◽  
Neutron Diffraction ◽  
Electron Density ◽  
Organic Salt ◽  
X Ray Diffraction ◽  
Covalent Character ◽  
X Ray

N,N-Dimethylbiguanidinium bis(hydrogensquarate) features an impressive range of hydrogen bonds within the same crystal structure: neighbouring anions aggregate to a dianionic pair through two strong O—H...O interactions; one of these can be classified among the shortest hydrogen bonds ever studied. Cations and anions in this organic salt further interact via conventional N—H...O and nonclassical C—H...O contacts to an extended structure. As all these interactions occur in the same sample, the title compound is particularly suitable to monitor even subtle trends in hydrogen bonds. Neutron and high-resolution X-ray diffraction experiments have enabled us to determine the electron density precisely and to address its properties with an emphasis on the nature of the X—H...O interactions. Sensitive criteria such as the Laplacian of the electron density and energy densities in the bond-critical points reveal the incipient covalent character of the shortest O—H...O bond. These findings are in agreement with the precise geometry from neutron diffraction: the shortest hydrogen bond is also significantly more symmetric than the longer interactions.

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

Molecules ◽  
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.

Synthesis, crystal structure and topological analysis of a three-dimensional polymeric network based on zinc(II), potassium and 5-sulfobenzene-1,3-dicarboxylate (SIP)

2018 ◽  
Vol 74 (8) ◽  
pp. 981-985
Author(s):  
Flávia H. Silva ◽  
Chris H. J. Franco ◽  
Charlane C. Corrêa ◽  
Renata Diniz
Keyword(s):  
Crystal Structure ◽  
Topological Analysis ◽  
Three Dimensional ◽  
Strong Interactions ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structural Rigidity ◽  
Dimensional Network ◽  
Point Symbol

Aromatic polycarboxylate linkers provide structural rigidity and strong interactions among the metal centre and the carboxylate O atoms. A new three-dimensional coordination polymer namely, catena-poly[potassium [tetraaqua(μ-5-sulfobenzene-1,3-dicarboxylato)zinc(II)]], {K[Zn(C8H3O7S)(H2O)4]} n or {K[Zn(SIP)(H2O)4]} n , where SIP is 5-sulfobenzene-1,3-dicarboxylate or 5-sulfoisophthalate, was obtained and characterized by elemental analysis and IR vibrational spectroscopy, and the single-crystal structure was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/n with Z = 4. Topological analysis revealed that K—O interactions form a two-dimensional network, which is uninodal 4-connected and can be described with a point symbol (44.62), and this plane network is classified as sql/Shubnikov. The layers are connected by Zn2+ ions coordinated to the SIP linker, forming a three-dimensional network. This net is a trinodal (3,5,6)-connected system with point symbol (3.44.52.62.73.83).(3.44.52.62.7).(3.72).

Attractive halogen···halogen interactions in crystal structure of trans-dibromogold(III) complex

2020 ◽  
Vol 235 (10) ◽  
pp. 477-480 ◽  
Author(s):  
Alexander G. Tskhovrebov ◽  
Alexander S. Novikov ◽  
Andreii S. Kritchenkov ◽  
Victor N. Khrustalev ◽  
Matti Haukka
Keyword(s):  
Self Assembly ◽  
Electron Density Distribution ◽  
Topological Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Elemental Analyses ◽  
Nmr Techniques ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
C Nmr

AbstractA synthesis of the trans-dibromogold(III) t-Bu-Xantphos complex and its self-assembly into infinite 1-dimensional chain in the solid state is reported. The new complex characterized using elemental analyses (C, H, N), ESI-MS, 1H and 13C NMR techniques and X-ray diffraction analysis. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of QTAIM method at the ωB97XD/DZP-DKH level of theory reveal that strength of attractive intermolecular non-covalent interactions Br···Br in the crystal is 1.2–1.6 kcal/mol.

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.

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