Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF3 and halogen (Cl or Br or I) substituted benzamides

2018 ◽  
Vol 74 (6) ◽  
pp. 574-591 ◽  
Author(s):  
Pradip Kumar Mondal ◽  
Rahul Shukla ◽  
Subha Biswas ◽  
Deepak Chopra
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Crystal Packing ◽  
Noncovalent Interactions ◽  
X Ray Diffraction ◽  
Substituted Benzamides ◽  
Size Type ◽  
Substituted Benzamide ◽  
Van Der Waals Radii

A total of 23 benzamides are obtained through a simple reaction between chloro-/bromo-/iodoaniline and trifluoromethylbenzoyl chloride and characterized using single-crystal X-ray diffraction. Crystal structures of three series of benzamides based on N-chlorophenyl–trifluoromethyl–benzamide (nine compounds), N-bromophenyl–trifluoromethyl–benzamide (six compounds), and N-iodophenyl–trifluoromethyl–benzamide (eight compounds) are prepared to analyse the halogen-mediated noncovalent interactions. The influences of Cl/Br/I and trifluoromethyl substituents on the respective interactions are examined in the presence of a strong N—H...O hydrogen bond. This exercise has resulted in the documentation of frequently occurring supramolecular synthons involving halogen atoms in the crystal packing of benzamide molecules in the solid state. In the present study, a detailed quantitative evaluation has been performed on the nature, energetics, electrostatic contributions, and topological properties of short and directional intermolecular interactions derived from the electron density on halogenated benzamides in the solid state. Besides these, the occurrence of three-, two- and one-dimensional isostructurality in halogen (Cl or Br or I) substituted benzamide analogues is also investigated. A `region of co-existence' involving halogen-based intermolecular interactions in the vicinity of the sum of the van der Waals radii has been identified. Thus, the nature of the halogen (effective size), type of interaction and the packing characteristics via presence of additional interactions establish the subtle, yet important, role of cooperativity in intermolecular interactions in crystal packing.

scholarly journals Molecular Structures Polymorphism the Role of F…F Interactions in Crystal Packing of Fluorinated Tosylates

Crystals ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 242 ◽  
Author(s):  
Dmitry E. Arkhipov ◽  
Alexander V. Lyubeshkin ◽  
Alexander D. Volodin ◽  
Alexander A. Korlyukov
Keyword(s):  
Intermolecular Interactions ◽  
Crystal Packing ◽  
Lattice Energy ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Total Contribution ◽  
X Ray ◽  
Weak Hydrogen Bonds ◽  
Intermolecular Bonding

The peculiarities of interatomic interactions formed by fluorine atoms were studied in four tosylate derivatives p-CH3C6H4OSO2CH2CF2CF3 and p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5, 7) using X-ray diffraction and quantum chemical calculations. Compounds p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) were crystallized in several polymorph modifications. Analysis of intermolecular bonding was carried out using QTAIM approach and energy partitioning. All compounds are characterized by crystal packing of similar type and the contribution of intermolecular interactions formed by fluorine atoms to lattice energy is raised along with the increase of their amount. The energy of intra- and intermolecular F…F interactions is varied in range 0.5–13.0 kJ/mol. Total contribution of F…F interactions to lattice energy does not exceed 40%. Crystal structures of studied compounds are stabilized mainly by C-H…O and C-H…F weak hydrogen bonds. The analysis of intermolecular interactions and lattice energies in polymorphs of p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) has shown that most stabilized are characterized by the least contribution of F…F interactions.

Structures of Bromoinated Oligothiophenes and Ethylenedioxythiophenes: A Combined Experimental and Theoretical Study

2012 ◽  
Vol 1402 ◽  
Author(s):  
Mamoun M. Bader ◽  
Phuong-Truc T. Pham
Keyword(s):  
Solid State ◽  
Bromine Atom ◽  
Structural Features ◽  
Published Data ◽  
X Ray Diffraction ◽  
Strong Electron ◽  
New Compounds ◽  
The Impact ◽  
Van Der Waals Radii

ABSTRACTIn this work, we report the results of solid state structural study of a series of oligothiophenes and ethylenedioxythiophenes (EDOT) endowed with bromine atoms at different positions and in the presence/absence of the strong electron acceptor, the tricyanovinyl group (TCV). Five new compounds were synthesized, crystallized and their single crystal structures were determined by X-ray diffraction. The impact of bromine atom(s) on solid state packing as viewed through analysis of intermolecular interactions is presented. Comparative study using experimental, computed and published data of closely related structures shows intra-molecular interactions involving Br in the presence of TCV and EDOT. Distances shorter that the summation of the Van der Waals radii were observed which indicate the role of Br…NC, S…S and Br…Br interactions in addition to pi stack formation and planarity of these compounds due to the presence of strong electron acceptors. Possible implications of how these structural features may impact charge transport in oligothiophenes will be discussed.

scholarly journals Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines

Compounds ◽  
2021 ◽  
Vol 1 (2) ◽  
pp. 58-74
Author(s):  
Emmanuel Aubert ◽  
Emmanuel Wenger ◽  
Paola Peluso ◽  
Victor Mamane
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Medicinal Chemistry ◽  
Crystal Packing ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Halogen Bonds ◽  
Cross Coupling Reactions ◽  
Cyano Groups ◽  
Post Functionalization

Non-symmetrical chiral 4,4′-bipyridines have recently found interest in organocatalysis and medicinal chemistry. In this regard, the development of efficient methods for their synthesis is highly desirable. Herein, a series of non-symmetrical atropisomeric polyhalogenated 4,4′-bipyridines were prepared and further functionalized by using cross-coupling reactions. The desymmetrization step is based on the N-oxidation of one of the two pyridine rings of the 4,4′-bipyridine skeleton. The main advantage of this methodology is the possible post-functionalization of the pyridine N-oxide, allowing selective introduction of chlorine, bromine or cyano groups in 2- and 2′-postions of the chiral atropisomeric 4,4′-bipyridines. The crystal packing in the solid state of some newly prepared derivatives was analyzed and revealed the importance of halogen bonds in intermolecular interactions.

Salt formation, hydrogen-bonding patterns and supramolecular architectures of acridine with salicylic and hippuric acid molecules

2021 ◽  
Vol 77 (12) ◽  
Author(s):  
Suresh Suganya ◽  
Kandasamy Saravanan ◽  
Ramakrishnan Jaganathan ◽  
Poomani Kumaradhas
Keyword(s):  
Hydrogen Bonding ◽  
Intermolecular Interactions ◽  
Hippuric Acid ◽  
Crystal Packing ◽  
Noncovalent Interactions ◽  
Salt Formation ◽  
Aminosalicylic Acid ◽  
Dispersion Interactions ◽  
Supramolecular Architectures ◽  
Quantitative Contributions

The intermolecular interactions and salt formation of acridine with 4-aminosalicylic acid, 5-chlorosalicylic acid and hippuric acid were investigated. The salts obtained were acridin-1-ium 4-aminosalicylate (4-amino-2-hydroxybenzoate), C13H10N+·C7H6NO3 − (I), acridin-1-ium 5-chlorosalicylate (5-chloro-2-hydroxybenzoate), C13H10N+·C7H4ClO3 − (II), and acridin-1-ium hippurate (2-benzamidoacetate) monohydrate, C13H10N+·C9H8NO3 −·H2O (III). Acridine is involved in strong intermolecular interactions with the hydroxy group of the three acids, enabling it to form supramolecular assemblies. Hirshfeld surfaces, fingerprint plots and enrichment ratios were generated and investigated, and the intermolecular interactions were analyzed, revealing their quantitative contributions in the crystal packing of salts I, II and III. A quantum theory of atoms in molecules (QTAIM) analysis shows the charge–density distribution of the intermolecular interactions. The isosurfaces of the noncovalent interactions were studied, which allows visualization of where the hydrogen-bonding and dispersion interactions contribute within the crystal.

Synthesis, growth, structure and characterization of molybdenum zinc thiourea complex crystals

2015 ◽  
Vol 71 (3) ◽  
pp. 285-292 ◽  
Author(s):  
M. Rajasekar ◽  
K. Muthu ◽  
A. Aditya Prasad ◽  
R. Agilandeshwari ◽  
SP Meenakshisundaram
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Intermolecular Interactions ◽  
Crystal Packing ◽  
Second Harmonic ◽  
Morphological Changes ◽  
Strong Interactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cell Parameters

Single crystals of molybdenum-incorporated tris(thiourea)zinc(II) sulfate (MoZTS) are grown by the slow evaporation solution growth technique. Crystal composition as determined by single-crystal X-ray diffraction analysis reveals that it belongs to the orthorhombic system with space groupPca21and cell parametersa= 11.153 (2),b= 7.7691 (14),c= 15.408 (3) Å,V= 1335.14 (4) Å3andZ= 4. The surface morphological changes are studied by scanning electron microscopy. The vibrational patterns in FT–IR are used to identify the functional group and TGA/DTA (thermogravimetric analysis/differential thermal analysis) indicates the stability of the material. The structure and the crystallinity of the material were confirmed by powder X-ray diffraction analysis and the simulated X-ray diffraction (XRD) closely matches the experimental one with varied intensity patterns. The band gap energy is estimated using diffuse reflectance data by the application of the Kubelka–Munk algorithm. The relative second harmonic generation (SHG) efficiency measurements reveal that MoZTS has an efficiency comparable to that of tris(thiourea)zinc(II) sulfate (ZTS). Hirshfeld surfaces were derived using single-crystal X-ray diffraction data. Investigation of the intermolecular interactions and crystal packingviaHirshfeld surface analysis reveal that the close contacts are associated with strong interactions. Intermolecular interactions as revealed by the fingerprint plot and close packing could be the possible reasons for facile charge transfer leading to SHG activity.

Halogen bonding between entirely negative fluorine atoms? Evidence from the crystal packing of some gold(i) and gold(iii) complexes with extensively fluorinated m-terphenyl ligands and triphenylphosphane

CrystEngComm ◽  
2020 ◽  
Vol 22 (48) ◽  
pp. 8285-8289
Author(s):  
Alexandru Sava ◽  
Krisztina T. Kegyes ◽  
Bianca T. Popuş ◽  
Bernadette C. Dan ◽  
Cristian Silvestru ◽  
...  
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Crystal Packing ◽  
Halogen Bonding ◽  
Terphenyl Ligands

Intermolecular interactions between fluorine atoms, analogous to halogen bonding, are able to drive the solid-state arrangement of molecules.

scholarly journals NMR crystallography, diffraction and modeling of small organic molecules

2014 ◽  
Vol 70 (a1) ◽  
pp. C1088-C1088
Author(s):  
Luís Miguel Monteiro Mafra
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Crystal Packing ◽  
Computational Study ◽  
Chemical Shifts ◽  
Hybrid Approach ◽  
X Ray Diffraction ◽  
Structure Solution ◽  
Nmr Crystallography

Solid-state NMR (SSNMR) is a powerful atomic-level characterization technique able to study the local chemical environment of a nucleus in crystalline/amorphous solids. Toward a better understanding of how small molecules self-assemble in the solid-state and reorganizes to produce its hydrate/anhydrous forms, an experimental SSNMR, X-ray diffraction (XRD), and computational study of the supramolecular assemblies of selected small pharmaceuticals is presented. The effect of crystal packing on the 1H and 13C chemical shifts including nonconventional hydrogen bonds, pi···pi and CH···pi contacts, is studied through computer simulations. It will be shown that NMR chemical shifts are sensitive detectors of hydration/dehydration states in highly insoluble antibiotics.[1] Recently, SSNMR became an important gadget in the process of crystal structure solution in powders. This is a non-trivial task and using powder XRD methods alone may often lead to the wrong structure solution. In this talk, a new hybrid approach for structure determination of crystalline solids, will be presented, based on the combination of SSNMR, XRD and an ensemble of computational-assisted structure solution tools including a genetic algorithm based on evolution-inspired operators repeatedly applied to populations of possible crystal structure solutions that evolve to eventually produce the best new offspring candidates. Such methodologies are successfully applied to challenging cases involving multiple component crystals composed by flexible molecules such as a trihydrate β-lactamic antibiotic [2] and an azole-based co-crystal featuring an hydrogen bond network of α-helixes involving NH···N/CH···π intermolecular interactions. ACKNOLEDGEMENTS: Supported by Fundação para a Ciência e a Tecnologia (FCT), Portuguese National NMR Network (RNRMN), CICECO (PEst-C/CTM/LA0011/2013), FEDER, COMPETE, and University of Aveiro. FCT is greatly acknowledge for the consolidation grant IF/01401/2013.

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