Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds

Jennifer, Samson Jegan; Muthiah, Packianathan Thomas

doi:10.1186/1752-153x-8-20

Cited by 24 publications

(9 citation statements)

References 45 publications

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“…Nucleic acids, mainly DNA/RNA, consist pyrimidine and aminopyrimidine bases as the essential components that interact with different biological components through hydrogen bonding. − The interaction of the pyrimidine or aminopyrimidine moiety with carboxylic acid derivatives is biologically significant such as in genetic information transfer, protein–nucleic acid recognition, drug–protein interaction, etc. − In the literature, two robust synthons, viz ., heterotrimer (HT) and linear heterotetramer (LHT), are found in the cocrystals/salts of aminopyrimidine and carboxylic acids, Scheme . − The prediction of salts or cocrystals can be quickly made by the Δp K a value, as Δp K a = p K a (base) – p K a (acid). Cocrystals and salts are differentiated based on proton transfer only; however, the distinction between cocrystals and salts is important from a legal and regulatory perspective. − Both solid forms have shown their potential in enhancing pharmacological and physicochemical properties. − …”

Section: Introductionmentioning

confidence: 99%

Extensive Analyses on Expanding the Scope of Acid–Aminopyrimidine Synthons for the Design of Molecular Solids

Garg

Azim

Alam

et al. 2022

Crystal Growth & Design

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The acid−aminopyrimidine synthon is a wellknown robust synthon for cocrystal synthesis that exists both in heterotrimer (HT) and linear heterotetramer (LHT) assemblies. A rational coformer screening methodology was adopted to predict the HT and LHT for the first time. The Cambridge Structural Database (CSD) and a modified site−pair interaction energy difference (ΔE site-pair ), based on molecular electrostatic potential (MESP), were computed to propose a generalization for better predictability. Based on the generalization, four cocrystals of 4halobenzoic acid (−F, −Cl, −Br, and −I at the para position of benzoic acid) with 2-aminopyrimidine (2-AP) were predicted and obtained using a neat grinding method. Different characterization methods, viz., Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), and differential scanning calorimetry (DSC) analysis, were used to confirm the formation of cocrystals. Single-crystal XRD was used for structural confirmations. Geometrical coordinates of cocrystals and their ingredients were optimized using density functional theory (DFT) calculations at the B3LYP-D3/6-311++G(d,p) level for −F-, −Cl-, and −Brsubstituted cocrystals and the B3LYP-D3/6-311++G(d,p)/LANL2DZ level for the −I-substituted cocrystal. Extensive computational studies, viz., Frontier molecular orbitals (FMOs), MESP values, natural bond orbitals (NBO), quantum theory of atoms in molecules (QTAIM), and reduced density gradient noncovalent interaction (RDG-NCI) analyses, were done on optimized structures to gain more insights into cocrystals and the effect of halogens on the acid−aminopyrimidine synthon and strength and nature of intermolecular interactions present in the cocrystals. Moreover, the strong and weak intermolecular interactions present in the crystal structure were examined qualitatively and quantitatively using Hirshfeld surface analysis on different parameters, interaction energy calculations, and total energy frameworks.

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Section: Introductionmentioning

confidence: 99%

Extensive Analyses on Expanding the Scope of Acid–Aminopyrimidine Synthons for the Design of Molecular Solids

Garg

Azim

Alam

et al. 2022

Crystal Growth & Design

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Section: Introductionmentioning

confidence: 99%

“…Hydrogen bonds are the unique tool in molecular recognition and play a master key role in the packing of crystal structures. − Halogen bonds − have attracted significant attention from the scientific community in recent years because of their vital role in crystal packing. In the last decade, Resnati and Metrangolo et al have used halogen bonds extensively for studying the crystal packing of iodoperflurocarbon molecules with aliphatic amines. − Jennifer and Muthiah designed and synthesized the cocrystals/salts of nitrogenous bases and thiophene carboxylic acid through a combination of hydrogen and halogen bonds . Saha et al.…”

Section: Introductionmentioning

confidence: 99%

“…35−39 Jennifer and Muthiah designed and synthesized the cocrystals/salts of nitrogenous bases and thiophene carboxylic acid through a combination of hydrogen and halogen bonds. 40 Saha et al studied the halogen bond interactions in iodopyridine derivatives. 41 Priimagi et al reported the importance of halogen bonds in designing the functional materials in the fields of biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules.…”

Section: ■ Introductionmentioning

confidence: 99%

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Solid-State Versatility of the Molecular Salts/Cocrystals of 2-Chloro-4-nitrobenzoic Acid: A Case Study on Halogen Bonds

et al. 2017

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2-Chloro-4-nitrobenzoic acid (2c4n) is an antiviral agent used for the treatment of HIV infection and to boost the immune response in immune deficiency diseases. In the present study, a series of eight molecular salts of 2c4n with pyridyl and benzoic acid derivatives have been synthesized by a crystal engineering approach and were characterized structurally by various spectroscopic, thermal, and X-ray diffraction techniques. Crystal structures of all synthesized molecular salts were determined by single-crystal X-ray diffraction techniques. In all synthesized molecular salts, the charge-assisted acid···pyridine/amine heterosynthon was found to be the primary supramolecular synthon. The synthesized salts, namely, 2c4n.g and 2c4n.h salts were found to be isostructural. Further, in the current work, the occurrence of weak halogen bonds in the presence of strong hydrogen bonds in the synthesized and in the reported molecular salts/cocrystals of 2c4n has been investigated. A detailed inspection of the crystal structures of salts/cocrystals of 2c4n was carried out to demonstrate the importance of halogen bonds in these crystal structures. It was found that 4 out of 8 synthesized molecular salts and 12 out of 24 reported molecular adducts of 2c4n were found to exhibit halogen bonds in their crystal structures. A similar kind of conformational change was observed for molecular salts exhibiting halogen bonds in their crystal structures; however, the conformations were found to be slightly different in other molecular salts. It was observed that two-point primary supramolecular synthon and stronger intramolecular Cl···O halogen bonds in the molecular adducts of 2c4n are found to be more susceptible to exhibit halogen bonds in their crystal structures. Halogen bond interactions played a vital role in the crystal stabilization of these molecular adducts.

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“…In our previous efforts to investigate the formation of Pb(II) complexes of quin and Pb(II) complexes of various N,N’-donating ligands we have already identified various intriguing structures with appealing supramolecular architectures [ 15 , 16 ]. We have also identified 5-tpc and quin as versatile multidentate ligands which can be used in the formation of metal complexes with interesting halogen bonding interactions [ 15 - 22 ]. As an extension of our previous work, in this study, we have investigated the complex formation of Pb(II) ions in the presence of mixed ligands (quin,phen/bipy) as well as 5-tpc and successfully obtained two novel complexes [Pb 4 (quin) 4 (bipy) 2 (5-tpc) 4 ] ( 1 ) and [Pb 4 (quin) 4 (phen) 2 (5-tpc) 4 ] ( 2 ) (bipy = 2,2’-Bipyridine, phen = 1,10-Phenanthroline, quin = 8-Hydroxy quinolinate and 5-tpc = 5-chloro thiophene 2-carboxylate) with similar cell parameters.…”

Section: Introductionmentioning

confidence: 99%

Syntheses and characterization of two novel tetranuclear lead(II) clusters self-assembled by hydrogen bonded interactions

Jennifer¹,

Muthiah²

2014

Chemistry Central Journal

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BackgroundThe usage of polynuclear metal clusters as secondary building units (SBU’s) in designing of metal organic frameworks (MOF’s) is a field of current interest. These metal clusters have attracted a great deal of attention not only due to their interesting structural topologies but also due to promising physical and chemical properties. In this regard various d,f block (transition and lanthanide) metal clusters have been widely investigated so far. Less attention is paid to construction of heavy p-block Pb(II) clusters.ResultsTwo mixed ligand Pb(II) clusters have been synthesized with bipy(2,2’-Bipyridine), phen(1,10-Phenanthroline), quin (8-Hydroxy quinolinate) and 5-tpc (5-chloro thiophene 2-carboxylate). They have been characterized by elemental analysis, IR, TGA and X-ray crystallography. X-ray diffraction analysis reveals that the complexes [Pb4(quin)4(bipy)2(5-tpc)4] (1) and [Pb4(quin) 4(phen) 2(5-tpc)4] (2) are tetranuclear. The complexes show a slight variation in unit cell parameters, due to the replacement of bipy and the phen ligands. Both complexes contain two types of Pb(II) ions which differ in the coordination geometry around the Pb(II) ion.ConclusionsIn both complexes the four lead ions Pb1,Pb2, Pb1i and Pb2i lie on the same plane bridged by the 5-tpc anions. Pb1 and Pb2 of both complexes contain a 5-tpc and quin coordinated in a bidentate chelating bridging fashion. In addition the Pb2 and Pb2i ions alone contain a bipy and phen in a bidentate chelating fashion in (1) and (2) respectively. An additional notable feature in both of these complexes are the bridging ability of the quin oxygen which forms a network of coordination bonds in between the four Pb(II) ions. In both complexes the individual units are self-assembled by C-H---Cl/C-H---S hydrogen bonding interactions to generate 2-D aggregates.

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Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds

Cited by 24 publications

References 45 publications

Extensive Analyses on Expanding the Scope of Acid–Aminopyrimidine Synthons for the Design of Molecular Solids

Extensive Analyses on Expanding the Scope of Acid–Aminopyrimidine Synthons for the Design of Molecular Solids

Solid-State Versatility of the Molecular Salts/Cocrystals of 2-Chloro-4-nitrobenzoic Acid: A Case Study on Halogen Bonds

Syntheses and characterization of two novel tetranuclear lead(II) clusters self-assembled by hydrogen bonded interactions

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