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In this study, Fe3O4 nanoparticles (FeNPs) decorated with halogenated perylene diimides (PDIs) have been used for capturing VOCs (volatile organic compounds) through noncovalent binding. Concretely, we have used tetrachlorinated/brominated PDIs as well as a nonhalogenated PDI as a reference system. On the other hand, methanol, ethanol, propanol, and butanol were used as VOCs. Experimental studies along with theoretical calculations (the BP86-D3/def2-TZVPP level of theory) pointed to two possible and likely competitive binding modes (lone pair–π through the π-acidic surface of the PDI and a halogen bond via the σ-holes at the Cl/Br atoms). More in detail, thermal desorption (TD) experiments showed an increase in the VOC retention capacity upon increasing the length of the alkyl chain, suggesting a preference for the interaction with the PDI aromatic surface. In addition, the tetrachlorinated derivative showed larger VOC retention times compared to the tetrabrominated analog. These results were complemented by several state-of-the-art computational tools, such as the electrostatic surface potential analysis, the Quantum Theory of Atoms in Molecules (QTAIM), as well as the noncovalent interaction plot (NCIplot) visual index, which were helpful to rationalize the role of each interaction in the VOC···PDI recognition phenomena. [ABSTRACT FROM AUTHOR]

The reaction between 5-acetylbarbituric acid and 4-dimethylthiosemicarbazide or 4-hexamethyleneiminyl thiosemicarbazide produces 5-acetylbarbituric-4-dimethylthiosemicarbazone (H2AcbDM) and 5-acetylbarbituric-4N-hexamethyleneiminyl thiosemicarbazone (H2Acbhexim). Eight new complexes with different copper(II) salts have been prepared and characterized using elemental analysis, molar conductance, UV–Vis, ESI-HRMS, FT-IR, magnetic moment, EPR, and cyclic voltammetry. In addition, three-dimensional molecular structures of [Cu(HAcbDM)(H2O)2](NO3)·H2O (3a), [Cu(HAcbDM)(H2O)2]ClO4 (4), and [Cu(HAcbHexim)Cl] (6) were determined by single crystal X-ray crystallography, and an analysis of their supramolecular structure was carried out. The H-bonded assemblies were further studied energetically using DFT calculations and MEP surface and QTAIM analyses. In these complexes, the thiosemicarbazone coordinates to the metal ion in an ONS-tridentate manner, in the O-enolate/S-thione form. The electrochemical behavior of the thiosemicarbazones and their copper(II) complexes has been investigated at room temperature using the cyclic voltammetry technique in DMFA. The Cu(II)/Cu(I) redox system was found to be consistent with the quasi-reversible diffusion-controlled process. [ABSTRACT FROM AUTHOR]

Two new Mn(II) and Zn(II) metal–organic compounds of 1,10-phenanthroline and methyl benzoates viz. [Mn(phen)2Cl2]2-ClBzH (1) and [Zn(4-MeBz)2(2-AmPy)2] (2) (where 4-MeBz = 4-methylbenzoate, 2-AmPy = 2-aminopyridine, phen = 1,10-phenanthroline, 2-ClBzH = 2-chlorobenzoic acid) were synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction techniques. The crystal structure analysis of the compounds revealed the presence of various non-covalent interactions, which provides stability to the crystal structures. The crystal structure analysis of compound 1 revealed the formation of a supramolecular dimer of 2-ClBzH enclathrate within the hexameric host cavity formed by the neighboring monomeric units. Compound 2 is a mononuclear compound of Zn(II) where flexible binding topologies of 4-CH3Bz are observed with the metal center. Moreover, various non-covalent interactions, such as lp(O)-π, lp(Cl)-π, C–H∙∙∙Cl, π-stacking interactions as well as N–H∙∙∙O, C–H∙∙∙O and C–H∙∙∙π hydrogen bonding interactions, are found to be involved in plateauing the molecular self-association of the compounds. The remarkable enclathration of the H-bonded 2-ClBzH dimer into a supramolecular cavity formed by two [Mn(phen)2Cl2] complexes were further studied theoretically using density functional theory (DFT) calculations, the non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. Synergistic effects were also analyzed using molecular electrostatic potential (MEP) surface analysis. [ABSTRACT FROM AUTHOR]

Two new coordination compounds comprising Mn(II) and Cu(II) viz. [Mn(bz)2(Hdmpz)2(H2O)] (1) and [Cu(crot)2(Hdmpz)2] (2) (where, bz = benzoate; crot = crotonate; Hdmpz = 3, 5-dimethyl pyrazole) were synthesized and characterized. The characterization involved a single crystal X-ray diffraction technique, FT-IR spectroscopy, electronic spectroscopy, TGA, and elemental analyses. Compounds 1 and 2 crystallize as mononuclear entities of Hdmpz with penta-coordinated Mn(II) and hexa-coordinated Cu(II), respectively. These complexes exhibit distorted trigonal bipyramidal and distorted octahedral geometries, respectively. A crystal structure analysis of compound 1 elucidates the existence of C–H⋯π and π-stacking interactions alongside O–H⋯O, N–H⋯O, and C–H⋯O H-bonding interactions contributing to the stabilization of the compound's layered assembly. Similarly, in compound 2, the crystal structure stability is attributed to the presence of hydrogen bonding in conjugation with π-stacking interactions. We conducted theoretical investigations to analyze π⋯π, H-bonding, and antiparallel CH···π non-covalent interactions observed in compounds 1 and 2. DFT calculations were performed to find out the strength of these interactions energetically. Moreover, QTAIM and non-covalent interaction (NCI) plot index theoretical tools were employed to characterize them and evaluate the contribution of the H-bonds. [ABSTRACT FROM AUTHOR]

Two new metal–organic multi-component compounds of Ni(II) and Co(II), viz. [Ni(3-CNpy)2(H2O)4]ADS·2.75H2O (1) and [Co(3-CNpy)2(H2O)4](4-ClbzSO3)2 (2) (3-CNpy = 3-cyanopyridine, ADS = anthraquinone-1,5-disulfonate, 4-ClbzSO3 = 4-chlorobenzenesulfonate), were synthesized and characterized using single crystal XRD, TGA, spectroscopic (IR, electronic) and elemental analyses. Both the compounds crystallize as multi-component compounds of Ni(II) and Co(II), with uncoordinated ADS and 4-ClbzSO3 moieties in the crystal lattice, respectively. Crystal structure analyses revealed the presence of antiparallel nitrile···nitrile and π-stacked assemblies involving alternate coordinated 3-CNpy and uncoordinated ADS and 4-ClbzSO3 moieties. Moreover, unconventional charge reverse Cl∙∙∙N halogen bonding contacts observed in compound 2 provide additional reinforcement to the crystal structure. Theoretical calculations confirm that the H-bonding interactions, along with anion–π(arene) and anion–π(CN) in 1 and π–π, antiparallel CN···CN and charge reverse Cl···N halogen bonds in 2, play crucial roles in the solid state stability of the compounds. In vitro anticancer activities observed through the trypan blue cell cytotoxicity assay reveal that the compounds induce significant concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cells, with nominal effects in normal healthy cells. Molecular docking studies reveal that the compounds can effectively bind with the active sites of anti-apoptotic proteins, which are actively involved in cancer progression. [ABSTRACT FROM AUTHOR]

The cis- and trans-isomers of 6-(3-(3,4-dichlorophenyl)-1,2,4-oxadiazol-5-yl)cyclohex-3-ene-1-carboxylic acid (cis-A and trans-A) were obtained by the reaction of 3,4-dichloro-N′-hydroxybenzimidamide and cis-1,2,3,6-tetrahydrophthalic anhydride. Cocrystals of cis-A with appropriate solvents (cis-A‧½(1,2-DCE), cis-A‧½(1,2-DBE), and cis-A‧½C6H14) were grown from 1,2-dichloroethane (1,2-DCE), 1,2-dibromoethane (1,2-DBE), and a n-hexane/CHCl3 mixture and then characterized by X-ray crystallography. In their structures, cis-A is self-assembled to give a hybrid 2D supramolecular organic framework (SOF) formed by the cooperative action of O–H⋯O hydrogen bonding, Cl⋯O halogen bonding, and π⋯π stacking. The self-assembled cis-A divides the space between the 2D SOF layers into infinite hollow tunnels incorporating solvent molecules. The energy contribution of each noncovalent interaction to the occurrence of the 2D SOF was verified by several theoretical approaches, including MEP and combined QTAIM and NCIplot analyses. The consideration of the theoretical data proved that hydrogen bonding (approx. −15.2 kcal/mol) is the most important interaction, followed by π⋯π stacking (approx. −11.1 kcal/mol); meanwhile, the contribution of halogen bonding (approx. −3.6 kcal/mol) is the smallest among these interactions. The structure of the isomeric compound trans-A does not exhibit a 2D SOF architecture. It is assembled by the combined action of hydrogen bonding and π⋯π stacking, without the involvement of halogen bonds. A comparison of the cis-A structures with that of trans-A indicated that halogen bonding, although it has the lowest energy in cis-A-based cocrystals, plays a significant role in the crystal design of the hybrid 2D SOF. The majority of the reported porous halogen-bonded organic frameworks were assembled via iodine and bromine-based contacts, while chlorine-based systems—which, in our case, are structure-directing—were unknown before this study. [ABSTRACT FROM AUTHOR]

Zn(II) coordination polymers are being increasingly studied for their stability and properties. Similarly, there is a growing interest in imidazo[1,5-a]pyridine derivatives, which show great potential in luminescence and pharmaceutical applications. In this work, we successfully synthesized and crystallized three new coordination polymers, using Zn(II) as the metallic node, dicarboxylic acids of different length and nature as linkers, and a linear ditopic imidazo[1,5-a]pyridine derivative, to explore the role of this molecule as a propagator of the dimensionality of the structure or as an ancillary ligand. Our work demonstrates the structural capability of imidazo[1,5-a]pyridines in an unexplored domain for this family of ligands. Notably, we observed a pronounced ability of this heterocyclic scaffold to establish π···π interactions in the solid state. The supramolecular π-stacked assemblies were theoretically analyzed using DFT calculations based on model structures. [ABSTRACT FROM AUTHOR]

Arrhythmogenic cardiomyopathy (ACM) is a heart disease characterized by a fibrotic replacement of myocardial tissue and a consequent predisposition to ventricular arrhythmic events, especially in the young. Post-mortem studies and the subsequent diffusion of cardiac MRI have shown that left ventricular involvement in arrhythmogenic cardiomyopathy is common and often develops early. Regarding the arrhythmic risk stratification, the current scores underestimate the arrhythmic risk of patients with arrhythmogenic cardiomyopathy with left involvement. Indeed, the data on arrhythmic risk stratification in this group of patients are contradictory and not exhaustive, with the consequence of not correctly identifying patients at a high arrhythmic risk who deserve protection from arrhythmic death. We propose a literature review on arrhythmic risk stratification in patients with ACM and left involvement to identify the main features associated with an increased arrhythmic risk in this group of patients. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of the multicomponent crystals formed by 2,2′-thiodiacetic acid (H2tda) and 2,6-diaminopurine (Hdap) or N9-(2-hydroxyethyl)adenine (9heade) are detailed in this report. These crystals exist in a salt rather than a co-crystal form, as confirmed by single crystal X-ray diffractometry, which reflects their ionic nature. This analysis confirmed proton transfer from the 2,2′-thiodiacetic acid to the basic groups of the coformers. The new multicomponent crystals have molecular formulas [(H9heade+)(Htda−)] 1 and [(H2dap+)2(tda2−)]·2H2O 2. These were also characterized using FTIR, 1H and 13C NMR and mass spectroscopies, elemental analysis, and thermogravimetric/differential scanning calorimetry (TG/DSC) analyses. In the crystal packing the ions interact with each other via O–H⋯N, O–H⋯O, N–H⋯O, and N–H⋯N hydrogen bonds, generating cyclic hydrogen-bonded motifs with graph-set notation of R 2 2 (16), R 2 2 (10), R 3 2 (10), R 3 3 (10), R 2 2 (9), R 3 2 (8), and R 4 2 (8), to form different supramolecular homo- and hetero-synthons. In addition, in the crystal packing of 2, pairs of diaminopurinium ions display a strong anti-parallel π,π-stacking interaction, characterized by short inter-centroids and interplanar distances (3.39 and 3.24 Å, respectively) and a fairly tight angle (17.5°). These assemblies were further analyzed energetically using DFT calculations, MEP surface analysis, and QTAIM characterization. [ABSTRACT FROM AUTHOR]

Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2. [ABSTRACT FROM AUTHOR]

In this study, a series of electron donor (–NH2, –NMe2 and –tBu) and electron-withdrawing substituents (–F, –CN and –NO2) were used to tune the nucleophilicity or electrophilicity of a series of square planar Ni2+, Pd2+ and Pt2+ malonate coordination complexes towards a pentafluoroiodobenzene and a pyridine molecule. In addition, Bader's theory of atoms in molecules (AIM), noncovalent interaction plot (NCIplot), molecular electrostatic potential (MEP) surface and natural bond orbital (NBO) analyses at the PBE0-D3/def2-TZVP level of theory were carried out to characterize and discriminate the role of the metal atom in the noncovalent complexes studied herein. We hope that the results reported herein may serve to expand the current knowledge regarding these metals in the fields of crystal engineering and supramolecular chemistry. [ABSTRACT FROM AUTHOR]

Reactions in water between the Cu2(µ-EGTA) chelate (EGTA = ethylene-bis(oxyethyleneimino)tetraacetate(4-) ion) and Hdap in molar ratios 1:1 and 1:2 yield only blue crystals of the ternary compound [Cu4(μ-EGTA)2(μ-H(N3)dap)2(H2O)2]·7H2O (1), which has been studied via single-crystal X-ray diffraction and various physical methods (thermal stability, spectral and magnetic properties), as well as DFT theoretical calculations. In the crystal, uncoordinated water is disordered. The tetranuclear complex molecule also has some irrelevant disorder in an EGTA-ethylene moiety. In the complex molecule, both bridging organic molecules act as binucleating ligands. There are two distorted five- and two six-coordinated Cu(II) centers. Each half of EGTA acts as a tripodal tetradentate Cu(II) chelator, with a mer-NO2 + O(ether, distal) conformation. Hdap exhibits the tautomer H(N3)dap, with the dissociable H-atom on its less basic N-heterocyclic atom. These features favor the efficient cooperation between Cu-N7 or Cu-N9 bonds with appropriate O-EGTA atoms, as N6-H···O or N3-H···O interligand interactions, respectively. The bridging role of both organics determines the tetranuclear dimensionality of the complex. In this crystal, such molecules associate in zig-zag chains built by alternating π–π interactions between the five- or six-atom rings of Hdap ligands of adjacent molecules. DFT theoretical calculations (using two different theoretical models and characterized by the quantum theory of "atoms in molecules") reveal the importance of these π–π interactions between Hdap ligands, as well as those corresponding to the referred hydrogen bonds in the contributed tetranuclear molecule. [ABSTRACT FROM AUTHOR]

Treatment of the [AuCl(tetrahydrothiophene)] complex with 4-chloro-2-iodo-1-isocyanobenzene furnished the gold(I) compound [AuCl(CNC6H3-4-Cl-2-I)] (1). In the crystal structure of 1, the linear C–Au–Cl group is subject to the solid-state head-to-tail pairing, which is determined by the aurophilic Au⋯Au and the rare π-holeCN⋯Cl interactions. These two types of structure-determining interactions are complementary to each other, and the system of Au⋯Au and CCN⋯Cl contacts accomplishes a 2D extended ladder-type architecture. In addition, the terminal I-atoms are involved in the three-center halogen bonding. Density functional theory calculations, employing a set of computational tools, verified the role of Au⋯Au and π-holeCN⋯Cl noncovalent bonds in the spectrum of noncovalent forces. [ABSTRACT FROM AUTHOR]

Considering that Cu(tda) chelate (tda: dithioacetate) is a receptor for adenine and related 6-aminopurines, this study reports on the synthesis, molecular and crystal structures, thermal stability, spectral properties and DFT calculations related to [Cu(tda)(9heade)(H2O)]·2H2O (1) [9heade: N9-(2-hydroxyethyl)adenine]. Concerning the molecular recognition of (metal chelate)-(adenine synthetic nucleoside), 1 represents an unprecedented metal binding pattern (MBP) for 9heade. However, unprecedentedly, the Cu(tda)-9heade molecular recognition in 1 is essentially featured in the Cu-N1(9heade) bond, without any N6-H⋯O(carboxyl tda) interligand interaction. Nevertheless, N1 being the most basic donor for N9-substituted adenines, this Cu-N1 bond is now assisted by an O2–water-mediated interaction (N6-H⋯O2 and O2⋯Cu weak contact). Also, in the crystal packing, the O-H(ol) of 9heade interacts with its own adenine moiety as a result of an O3–water-mediated interaction (O(ol)-H⋯O3 plus O3-H36⋯π(adenine moiety)). Both water-mediated interactions seem to be responsible for serious alterations in the physical properties of crystalline or grounded samples. Density functional theory calculations were used to evaluate the interactions energetically. Moreover, the quantum theory of atoms-in-molecules (QTAIM), in combination with the noncovalent interaction plot (NCIPlot), was used to analyze the interactions and rationalize the existence and relative importance of hydrogen bonding, chalcogen bonding and π-stacking interactions. The novelty of this work resides in the discovery of a novel binding mode for N9-(2-hydroxyethyl)adenine. Moreover, the investigation of the important role of water in the solid state of 1 is also relevant, along with the chalcogen bonding interactions demonstrated by the density functional theory (DFT) study. [ABSTRACT FROM AUTHOR]

Background: The brain and heart are strictly linked and the electrical physiologies of these organs share common pathways and genes. Epilepsy patients have a higher prevalence of electrocardiogram (ECG) abnormalities compared to healthy people. Furthermore, the relationship between epilepsy, genetic arrhythmic diseases and sudden death is well known. The association between epilepsy and myocardial channelopathies, although already proposed, has not yet been fully demonstrated. The aim of this prospective observational study is to assess the role of the ECG after a seizure. Materials and Methods: From September 2018 to August 2019, all patients admitted to the emergency department of San Raffaele Hospital with a seizure were enrolled in the study; for each patient, neurological, cardiological and ECG data were collected. The ECG was performed at the time of the admission (post-ictal ECG) and 48 h later (basal ECG) and analyzed by two blinded expert cardiologists looking for abnormalities known to indicate channelopathies or arrhythmic cardiomyopathies. In all patients with abnormal post-ictal ECG, next generation sequencing (NGS) analysis was performed. Results: One hundred and seventeen patients were enrolled (females: 45, median age: 48 ± 12 years). There were 52 abnormal post-ictal ECGs and 28 abnormal basal ECGs. All patients with an abnormal basal ECG also had an abnormal post-ictal ECG. In abnormal post-ictal ECG, a Brugada ECG pattern (BEP) was found in eight patients (of which two had BEP type I) and confirmed in two basal ECGs (of which zero had BEP type I). An abnormal QTc interval was identified in 20 patients (17%), an early repolarization pattern was found in 4 patients (3%) and right precordial abnormalities were found in 5 patients (4%). Any kind modification of post-ictal ECG was significantly more pronounced in comparison with an ECG recorded far from the seizure (p = 0.003). A 10:1 higher prevalence of a BEP of any type (particularly in post-ictal ECG, p = 0.04) was found in our population compared to general population. In three patients with post-ictal ECG alterations diagnostic for myocardial channelopathy (BrS and ERP), not confirmed at basal ECG, a pathogenic gene variant was identified (KCNJ8, PKP2 and TRMP4). Conclusion: The 12-lead ECG after an epileptic seizure may show disease-related alterations otherwise concealed in a population at a higher incidence of sudden death and channelopathies. Post-ictal BEP incidence was higher in cases of nocturnal seizure. [ABSTRACT FROM AUTHOR]

Two Na(I) coordination polymers, namely, {Na(BA)2(μ-H2O)2}n{adp}n (1) and {[Na2(μ-BA)(μ-fum)(μ-H2O)4](BA)}n (2) (where, BA = boric acid, adp = adipic acid, fum = fumarate),were prepared and characterized using elemental analysis, TGA, FT-IR, and single-crystal X-ray diffraction techniques. Various unconventional supramolecular interactions, i.e., CH∙∙∙HC and parallel CO∙∙∙CO interactions, stabilize the layered assembly of compound 1. Interesting dual enclathration of BA molecules within the supramolecular host cavities formed by O-H∙∙∙O and C-H∙∙∙C interactions stabilizes the crystal structure of compound 2. The H-bonding interactions in 1 and 2 were further studied theoretically using the quantum theory of atoms in molecules (QTAIM) and the noncovalent interaction plot (NCI Plot) computational tools. The energy of the H-bonds was estimated using the potential energy density at the bond critical points. Theoretical calculations confirmed the presence of O-H∙∙∙O H-bonding interactions in both compounds, forming structure-guiding R 2 2 (8) synthons relevant for the stability of the compounds. [ABSTRACT FROM AUTHOR]

Two multi-component coordination compounds of Mn(II), viz. [Mn(H2O)6](2-Mepy)2(4-NO2bz)2·2H2O (1) and [Mn(H2O)6][Mn(2,3-PDCH)3]2 (2) (where, 2-Mepy = 2-methylpyridine, 4-NO2bz = 4-nitrobenzoate, 2,3-PDC = 2,3-pyridinedicarboxylate), have been synthesized and characterized using elemental, spectroscopic (FT-IR and electronic), TGA and single-crystal X-ray diffraction analyses. Complex 1 is a co-crystal hydrate of Mn(II) involving uncoordinated 2-Mepy, 4-NO2bz and water molecules; while compound 2 is a multi-component molecular complex salt of Mn(II) comprising cationic [Mn(H2O)6]2+ and anionic [Mn(2,3-PDCH)3]−complex moieties. The uncoordinated 2-Mepy and 4-NO2bz moieties of 1 are involved in lone-pair (l.p)-π and C–H⋯π interactions which stabilize the layered assembly of the compound. The crystal structure of compound 2 has been previously reported. However, we have explored the unusual enclathration of complex cationic moieties within the supramolecular host cavities formed by the molecular assembly of complex anionic moieties. The supramolecular assemblies obtained in the crystal structure have been further studied theoretically using DFT calculations, quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCI plot) computational tools. Theoretical studies reveal that the combination of π-staking interactions (l.p-π, π-π and C–H···π) have more structure-guiding roles compared to the H-bonds. The large binding energy of π-stacking interactions in 2 is due to the antiparallel orientation of aromatic rings and their coordination to the metal centers, thereby increasing the contribution of the dipole–dipole interactions. [ABSTRACT FROM AUTHOR]

In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in this type of compound is trigonal bipyramidal where the stereoactive lone pair at Te(IV) occupies one of the equatorial positions. In the solid state, Te(IV) tends to form pseudo-octahedral coordination by establishing strong noncovalent interactions opposite to the two covalent bonds of the equatorial plane. Such contacts can also be classified as chalcogen bonds following the recommendation of the International Union of Pure and Applied Chemistry (IUPAC). Such contacts have been analyzed energetically in this work using density functional theory (DFT) calculations, rationalized using molecular electrostatic potential (MEP) surface analysis and characterized using a combination of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIplot) computational tools. Finally, the observation of halogen bonds and type I halogen···halogen contacts is also emphasized and compared to the chalcogen bonds. Energy decomposition analysis has also been performed to compare the physical nature of chalcogen, halogen and type I interactions. [ABSTRACT FROM AUTHOR]

Unraveling the binding preferences involved in the formation of a supramolecular complex is key to properly understand molecular recognition and aggregation phenomena, which are of pivotal importance to biology. The halogenation of nucleic acids has been routinely carried out for decades to assist in their X-ray diffraction analysis. The incorporation of a halogen atom on a DNA/RNA base not only affected its electronic distribution, but also expanded the noncovalent interactions toolbox beyond the classical hydrogen bond (HB) by incorporating the halogen bond (HalB). In this regard, an inspection of the Protein Data Bank (PDB) revealed 187 structures involving halogenated nucleic acids (either unbound or bound to a protein) where at least 1 base pair (BP) exhibited halogenation. Herein, we were interested in disclosing the strength and binding preferences of halogenated A···U and G···C BPs, which are predominant in halogenated nucleic acids. To achieve that, computations at the RI-MP2/def2-TZVP level of theory together with state of the art theoretical modeling tools (including the computation of molecular electrostatic potential (MEP) surfaces, the quantum theory of "Atoms in Molecules" (QTAIM) and the non-covalent interactions plot (NCIplot) analyses) allowed for the characterization of the HB and HalB complexes studied herein. [ABSTRACT FROM AUTHOR]

In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties. To achieve that, several tetrafluorophenyl silane derivatives have been substituted at the meta and para positions by several electron donating and electron withdrawing groups (EDG and EWG, respectively), such as –NH2, –OCH3, –CH3, –H, –CF3 and –CN substituents. As electron donor molecules, we have used a series of hydrogen cyanide derivatives using the same EDGs and EWGs. We have obtained the Hammett's plots for different combinations of donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammet's σ parameter). In addition, we have used the electrostatic potential (ESP) surface analysis as well as the Bader's theory of atoms in molecules (AIM) and noncovalent interaction plot (NCI plot) techniques to further characterize the TtBs studied herein. Finally, a Cambridge Structural Database (CSD) inspection was carried out, retrieving several structures where halogenated aromatic silanes participate in tetrel bonding interactions, being an additional stabilization force of their supramolecular architectures. [ABSTRACT FROM AUTHOR]

Pharmaceutical multicomponent solids have proved to efficiently modulate the physicochemical properties of active pharmaceutical ingredients. In this context, polyphenols are interesting coformers for designing pharmaceutical cocrystals due to their wide safety profile and interesting antioxidant properties. The novel 6-propyl-2-thiouracil multicomponent solids have been obtained by mechanochemical synthesis and fully characterized by powder and single-crystal X-ray diffraction methods. The analysis of supramolecular synthons has been further performed with computational methods, with both results revealing a robust supramolecular organization influenced by the different positions of the hydroxyl groups within the polyphenolic coformers. All novel 6-propyl-2-thiouracil cocrystals show an enhanced solubility profile, but unfortunately, their thermodynamic stability in aqueous media is limited to 24 h. [ABSTRACT FROM AUTHOR]

Two coordination compounds of Cu(II), namely, [Cu (phen)2Cl](NO3)·H2O (compound 1) and [Cu2(µ-Cl2)Cl2(Hdmpz)4] (compound 2), where phen = 1,10-phenanthroline and Hdmpz = 3,5-dimethylpyrazole, were synthesized at room temperature and characterized using elemental analysis, TGA, spectroscopic techniques (FT-IR and electronic) and single-crystal X-ray diffraction studies. The cooperative anion–π/π–π/anion–π assemblies involving the coordinated phen, along with the uncoordinated nitrate moieties, played pivotal roles in the stabilization of the crystal structure of compound 1. Unconventional type I Cl⋯Cl interactions involving the coordinated Cl atoms provided reinforcement to the crystal structure of compound 2. We theoretically explored the supramolecular assemblies observed in the crystal structures of compounds 1 and 2 using DFT calculations, MEP surface analysis and combined NCI plot/QTAIM computational tools. Theoretical analysis revealed that the antiparallel π-stacking interactions in compound 1 and the N–H···Cl H-bonds in compound 2 were the strong structure-guiding non-covalent synthons which stabilized the compounds. In the anion–π/π–π/anion–π assembly observed in compound 1, the anion–π interaction reinforced the π-stacking by reducing the electrostatic repulsion between the metal-coordinated electron-deficient phen rings. [ABSTRACT FROM AUTHOR]

Two Zn(II) coordination polymers, viz., [Zn2Cl2(H2O)2(µ-4-AmBz)2]n (1) and [ZnCl2(µ-3-AmPy)2]n (2) (4-AmBz = 4-aminobenzoate, 3-AmPy = 3-aminopyridine) have been prepared at room temperature and characterized using elemental analysis, FT-IR, electronic spectroscopy, TGA (thermogravimetric analysis) and single crystal XRD. Crystal structure analyses of the polymers unfold the presence of non-covalent anion–π, π-stacking and unusual NH2(amino)⋯π interactions which provide rigidity to the crystal structures. Unconventional Type I Cl⋯Cl interactions also play a pivotal role in the stability of compound 1. Molecular electrostatic potential (MEP) surface analysis reveals that the MEP values over the center of the aromatic rings of coordinated 4-AmBz and 3-AmPy moieties are positive on one side and negative on the other side which confirms the dual non-covalent donor-acceptor topologies of the aromatic rings and explains the concurrent formation of unusual non-covalent NH2···π and anion–π interactions. DFT (density functional theory) calculations, QTAIM (quantum theory of atoms in molecules) and NCI plot (non-covalent index) index analyses reveal that among various non-covalent contacts involved in the crystal packing of the compounds, H-bonds in compound 1 and π-interactions (NH2···π, π-π, anion–π) in compound 2 are energetically significant. We have explored in vitro cytotoxic potential of the compounds in Dalton's lymphoma (DL) cancer cells using trypan blue and apoptosis assays. The studies show that compounds 1 and 2 can significantly exhibit cytotoxicity in DL cells with minimum cytotoxicity in healthy PBMC cells. Molecular docking studies reveal that the compounds effectively bind with the antiapoptotic target proteins; thereby establishing a structure activity relationship of the compounds. [ABSTRACT FROM AUTHOR]

Two new Ni(II) and Co(II) coordination compounds, viz., [Ni(H2O)5(DMAP)](IPhth)·2H2O (1) and [Co(Hdmpz)4(H2O)2]Cl2 (2) (where DMAP = 4-dimethylaminopyridine, IPhth = Isophthalate, Hdmpz = 3,5-dimethylpyrazole),were synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR and electronic) and single-crystal X-ray diffraction techniques. Compound 1 crystallizes as a co-crystal hydrate of Ni(II), whereas compound 2 is a mononuclear compound of Co(II). The crystal structure analysis of compound 1 reveals the presence of various non-covalent interactions such as anion–π, π–π, C–H∙∙∙π, C–H∙∙∙C, etc., which stabilize the layered assembly of the compound. In compound 2, enclathration of counter chloride ions within the supramolecular trimeric host cavity plays a crucial role in the stabilization of the compound. The non-covalent interactions observed in the crystal structures were further studied theoretically, focusing on the cooperative π-stacking interactions between the DMAP and IPhth counter-ions in 1. To identify the non-covalent interactions of the compounds, Hirshfeld surfaces and their associated two-dimensional fingerprint regions were analyzed. Theoretical calculations confirm that H-bonding interactions combined with the π-stacking contacts are crucial synthons for the solid-state stability of compound 1. [ABSTRACT FROM AUTHOR]

Noncovalent interactions involving metals as electron acceptors are continuously under investigation. The term "matere bond" has been proposed to identify noncovalent donor–acceptor interactions where elements of group 7 of the periodic table play the role of the electrophilic site. Most of the works on matere bonds involve rhenium atoms usually in +7 oxidation state. This work emphasizes for the first time their importance in technetium derivatives in several oxidation states (+7, +6, +5, and +3). The Cambridge Structural Database (CSD) in combination with density functional theory (DFT) calculations are used to demonstrate the structure directing role of matere bonds in X-ray structures, even involving anion⋯anion interactions. Further characterization of the matere bonds is provided using Molecular Electrostatic Potential (MEP) surface calculations, the "Quantum Theory of Atoms in Molecules" (QTAIM), and Natural Bond Orbital (NBO) analyses. It should be emphasized that some types of matere bonds reported herein have not been previously described in literature. [ABSTRACT FROM AUTHOR]

It has been proposed that late transition metals with low coordination numbers (square planar or linear) can act as nucleophiles and participate in σ-hole interactions as electron donors. This is due to the existence, in this type of metal complexes, of a pair of electrons located at high energy d-orbitals (dz2 or dx2-y2), which are adequate for interacting with antibonding σ-orbitals [σ*(X–Y)] where Y is usually an electron withdrawing element and X an element of the p-block. This type of d[M]→σ*(X–Y) interaction has been reported for metals of groups 9–11 in oxidation states +1 and +2 (d8 and d10) as electron donors and σ-holes located in halogen and chalcogen atoms as electron acceptors. To our knowledge, it has not been described for σ-holes located in pnictogen atoms. In this manuscript, evidence for the existence of pnictogen bonding involving the square planar Pt(II) metal as the electron donor and Sb as the electron acceptor is provided by using an X-ray structure retrieved from the Cambridge Structural Database (CSD) and theoretical calculations. In particular, the quantum theory of atoms in molecules (QTAIM), the noncovalent interaction plot (NCIPlot) and molecular electrostatic potential (MEP) methods were used. Moreover, to further confirm the nature of the Sb···Pt(II) contact, a recently developed method was used where the electron density (ED) and electrostatic potential (ESP) distribution were compared along the Sb···Pt(II) bond path. [ABSTRACT FROM AUTHOR]

Metal ion interactions with nuclei acids and their constituents represent a multi-faceted and growing research field. This contribution deals with molecular recognition between synthetic purine 17 nucleosides and first-row transition metal complexes, with O- and/or N-amino chelators which are able to 18 engage in intra-molecular N-H···(N or O) and O-H···(N or O) interligand interactions. Crystals of these complexes can also display inter-molecular aromatic π-stacking and/or other non-conventional interactions. In this manuscript, we used 2-(2-aminoethoxy)ethanol (2aee) as a potential N,O(e),O(ol)-chelator for nickel(II). However, unexpectedly, the reaction between NiCl2, acyclovir (acv), and 2aee in methanol afforded parallelepiped apple-green crystals of [Ni(acv-H)(MeO)(H2O)]4·8H2O, (1) a tetranuclear molecule with an equimolar Ni(II):µ3-methanolate(1-):µ2-N7,O6-acyclovirate(1-) (acv-H) ratio. The µ2-N7,O6-(acv-H) metal-binding pattern (MBP) is unprecedented in terms of both its anionic and bridging roles. The single-crystal X-ray diffraction structure as well as thermogravimetric analysis and the (FT-IR +Vis-UV) spectra of 1 are reported. Theoretical density functional theory (DFT) calculations are used to analyse the antiparallel π-stacking interactions that govern the formation of self-assembled dimers in the solid state. [ABSTRACT FROM AUTHOR]

The series of substituted 1,2,4-selenodiazolium tetraphenylborate complexes were synthesized via cyclization between 2-pyridylselenylchloride, followed by the anion metathesis, and fully characterized. The utilization of tetraphenylborate anion, a strong π-electron donor via its phenyl rings, promoted the formation of assemblies exhibiting selenium–π interactions. The chalcogen bonding (ChB) interactions involving the π-systems of the tetraphenylborate anion were studied using density functional theory (DFT) calculations, where "mutated" anions were used to estimate the strength of the Se···π chalcogen bonds. Moreover, molecular electrostatic potential (MEP) surfaces were used to investigate the electron-rich and poor regions of the ion pairs. The quantum theory of atoms-in-molecules (QTAIM) and the noncovalent interaction (NCI) plot methods based on the topology of the electron density were used and combined to characterize the ChBs. The investigation reported herein disclosed that the formation of symmetrical dimers can be broken by the introduction of a stronger π-acceptor and, consequently, forming stronger Se···π contacts with selenodiazolium cations. [ABSTRACT FROM AUTHOR]

The chalcogen bond has been recently defined by the IUPAC as the attractive noncovalent interaction between any element of group 16 acting as an electrophile and any atom (or group of atoms) acting as a nucleophile. Commonly used chalcogen bond donor molecules are divalent selenium and tellurium derivatives that exhibit two σ-holes. In fact, the presence of two σ-hole confers to the chalcogen bonding additional possibilities with respect to the halogen bond, the most abundant σ-hole interaction. In this manuscript, we demonstrate that selenoxides are good candidates to be used as σ-hole donor molecules. Such molecules have not been analyzed before as chalcogen bond donors, as far as our knowledge extends. The σ-hole opposite to the Se=O bond is adequate for establishing strong and directional ChBs, as demonstrated herein using the Cambridge structural database (CSD) and density functional theory (DFT) calculations. Moreover, the effect of the metal coordination of the selenoxide to transition metals on the strength of the ChB interaction has been analyzed theoretically. The existence of the ChBs has been further supported by the quantum theory of atoms in molecules (QTAIM) and the noncovalent interaction plot (NCIPlot). [ABSTRACT FROM AUTHOR]

The series of benzylic-substituted 1,2,4-selenodiazolium salts were prepared via cyclization reaction between 2-pyridylselenyl chlorides and nitriles and fully characterized. Substitution of the Cl anion by weakly binding anions promoted the formation supramolecular dimers featuring four center Se2N2 chalcogen bonding and two antiparallel selenium⋯π interactions. Chalcogen bonding interactions were studied using density functional theory calculations, molecular electrostatic potential (MEP) surfaces, the quantum theory of atoms-in-molecules (QTAIM), and the noncovalent interaction (NCI) plot. The investigations revealed fundamental role of the selenium⋯π contacts that are stronger than the Se⋯N interactions in supramolecular dimers. Importantly, described herein, the benzylic substitution approach can be utilized for reliable supramolecular dimerization of selenodiazolium cations in the solid state, which can be employed in supramolecular engineering. [ABSTRACT FROM AUTHOR]

The term matere bond has been recently used to refer to an attractive noncovalent interaction between any element of group 7 acting as an electrophile and any atom (or group of atoms) acting as a nucleophile. The utilization of metals such as σ-hole donors is starting to attract the attention of the scientific community. In this manuscript, a comparison between matere bonds and well-known σ-hole interactions (halogen and chalcogen bonds) is carried out using three X-ray structures, retrieved from the Cambridge structural database (CSD), and density functional theory calculations (DFT). The novelty of this work resides in the utilization of a neutral Re(VII) system as the matere bond donor and multivalent chalcogen and halogen donors. In fact, as far as our knowledge extends, the description of σ-hole interactions in Se(VI) is unprecedented in the literature. The σ-hole interactions in Re(VII), Se(VI) and Cl(VII) electron acceptors are analyzed and compared using several computational tools. [ABSTRACT FROM AUTHOR]

Four co-crystals involving dicarboxylic acids and pyridine derivatives, viz. (ox)0.5(2-CNpy) (1), (adp)(4-CNpy)2 (2), (tp)(4-CNpy)2 (3) and (adp)(3-CNpy)2 (4) (ox = oxalic acid, tp = terephthalic acid, adp = adipic acid, CNpy = cyanopyridine), have been synthesized at room temperature in water medium. Crystal-structure analysis of co-crystal 1 reveals the presence of unconventional O···π(oxalic acid)-hole interaction with the C-C bond of ox moiety, along with parallel nitrile–nitrile interactions. The structural topologies of co-crystals 2–4 unfold the presence of antiparallel nitrile–nitrile interactions involving the CNpy moieties. The molecular associations involving the H-bonds and other unconventional contacts among the co-formers of the multicomponent co-crystals are analyzed using density functional theory (DFT) calculations combined with molecular electrostatic potential (MEP) surface, quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction (NCI) plot computational tools. The computational studies revealed the presence of unconventional O···π-hole interaction in 1 and the H-bonded synthons with π-stacked nitrile contacts involving CNpy moieties in co-crystals 2–4. The energetic features of the noncovalent contacts reveal the crucial roles of the H-bonding synthons and π-stacking interactions in the multicomponent compounds. [ABSTRACT FROM AUTHOR]

We report high-level ab initio calculations (CCSD(T)(full)/CBS//SCS-RI-MP2(full)/aug-cc-pwCVTZ) that demonstrate the importance of cooperativity effects when Anion–π and CH/π interactions are simultaneously established with benzene as the π-system. In fact, most of the complexes exhibit high cooperativity energies that range from 17% to 25.3% of the total interaction energy, which is indicative of the strong influence of the CH/π on the Anion–π interaction and vice versa. Moreover, the symmetry-adapted perturbation theory (SAPT) partition scheme was used to study the different energy contributions to the interaction energies and to investigate the physical nature of the interplay between both interactions. Furthermore, the Atoms in Molecules (AIM) theory and the Non-Covalent Interaction (NCI) approach were used to analyze the two interactions further. Finally, a few examples from the Protein Data Bank (PDB) are shown. All results stress that the concurrent formation of both interactions may play an important role in biological systems due to the ubiquity of CH bonds, phenyl rings, and anions in biomolecules. [ABSTRACT FROM AUTHOR]

Osme bonds have been recently defined as the attractive interaction between an element of group 8 acting as an electrophile and any atom or group of atoms acting as a nucleophile. To date, the known examples of osme bonds in X-ray structures involve mostly the highly reactive OsO4 and amines and amine oxides. In this work, evidence supporting the existence of osme bonds in osmium(VI) derivatives is reported. In particular, nitrido-osmium(VI) complexes that present square-pyramidal geometries are well disposed to participate in osme bonds opposite to the Os≡N bond. By using a combination of experimental and theoretical results, the existence and importance of this new class of σ-hole interactions is demonstrated in the solid state of several nitrido-osmium(VI) derivatives. [ABSTRACT FROM AUTHOR]

Background: Limited data is available about the outcome of TLE in patients with vs. without high energy leads in the last decade. Methods: This is an analysis of consecutive patients undergoing TLE at a high-volume TLE centre from 2001 to 2021 using the stepwise approach. Baseline characteristics, procedural details and outcome of patients with high energy lead (ICD group) vs. without high energy lead (non-ICD group) were compared. Results: Out of 667 extractions, 991 leads were extracted in 405 procedures (60.7%) in the ICD group and 439 leads in 262 procedures (39.3%) in the non-ICD group. ICD patients were significantly younger (median 67 vs. 74 years) and were significantly less often female (18.1% vs. 27.7%, p < 0.005 for both). Advanced extraction tools were used significantly more often in the ICD group (73.2% vs. 37.5%, p < 0.001), but there were no significant differences in the successful removal (98.8% vs. 99.2%) or complications (4.7% vs. 3.1%) between the groups (p > 0.2 for both). Discussion: Using the stepwise approach, overall procedural success was high and complication rate was low in a high-volume centre. In patients with a high energy lead, the TLE procedure was more complex, but outcome was similar to comparator patients. [ABSTRACT FROM AUTHOR]

The crystal structure of a new zonisamide cocrystal, an anticonvulsant drug used to treat the symptoms of epilepsy and Parkinson's disease, with ϵ-caprolactam is reported herein. The structure has been solved by direct space methodologies from powder X-ray diffraction data. The refinement of the structure was conducted by the Rietveld method assisted by the dispersion-corrected density-functional theory (D-DFT) calculations and periodic boundary conditions. Further analysis of the structure reveals several H-bonded synthons and self–assembled dimers that have been further analyzed by DFT calculations and other computational tools such as molecular electrostatic potential (MEP) surfaces and the quantum theory of "atom-in-molecules" (QTAIM). [ABSTRACT FROM AUTHOR]

The synthesis and structural characterization of a series of supramolecular complexes of bicyclic cationic pyridine-fused 1,2,4-selenodiazoles with various anions is reported. The binding of trifluoroacetate, tetrachloroaurate, tetraphenylborate, perrhenate, and pertechnetate anions in the solid state is regarded. All the anions interact with selenodiazolium cations exclusively via a pair of "chelating" Se⋯O and H⋯O non-covalent interactions, which make them an attractive, novel, non-classical supramolecular recognition unit or a synthon. Trifluoroacetate salts were conveniently generated via novel oxidation reaction of 2,2′-dipyridyl diselenide with bis(trifluoroacetoxy)iodo)benzene in the presence of corresponding nitriles. Isolation and structural characterization of transient 2-pyridylselenyl trifluoroacetate was achieved. X-ray analysis has demonstrated that the latter forms dimers in the solid state featuring very short and strong Se⋯O and Se⋯N ChB contacts. 1,2,4-Selenodiazolium trifluoroacetates or halides show good solubility in water. In contrast, (AuCl4)−, (ReO4)−, or (TcO4)− derivatives immediately precipitate from aqueous solutions. Structural features of these supramolecular complexes in the solid state are discussed. The nature and energies of the non-covalent interactions in novel assembles were studied by the theoretical methods. To the best of our knowledge, this is the first study that regards perrhenate and pertechnetate as acceptors in ChB interactions. The results presented here will be useful for further developments in anion recognition and precipitation involving cationic 1,2,4-selenodiazoles. [ABSTRACT FROM AUTHOR]

In this work the crystal structure of the previously described orthorhombic polymorph of the coupling reagent Oxyma has been revised, corrected now as centrosymmetric and analyzed by means of DFT calculations. In the solid state the structure forms a network of H-bonds and self–assembled dimers that are held together by the formation of N···C π–hole interactions involving the C-atom of the imino group. The H-bonding and π–hole interactions observed in the solid state were rationalized using molecular electrostatic potential (MEP) surfaces, focusing on the H-bond donor-acceptor groups and the π-hole observed above and below the molecular plane. The interactions and their interplay have been characterized by using two methodologies based on the topology of the electron density, which are the quantum theory of "atom-in-molecules" (QTAIM) and the noncovalent interaction plot (NCIplot). [ABSTRACT FROM AUTHOR]

In this study the ability of metal coordinated Chalcogen (Ch) atoms to undergo Chalcogen bonding (ChB) interactions has been evaluated at the PBE0-D3/def2-TZVP level of theory. An initial CSD (Cambridge Structural Database) inspection revealed the presence of square planar Pd/Pt coordination complexes where divalent Ch atoms (Se/Te) were used as ligands. Interestingly, the coordination to the metal center enhanced the σ-hole donor ability of the Ch atom, which participates in ChBs with neighboring units present in the X-ray crystal structure, therefore dictating the solid state architecture. The X-ray analyses were complemented with a computational study (PBE0-D3/def2-TZVP level of theory), which shed light into the strength and directionality of the ChBs studied herein. Owing to the new possibilities that metal coordination offers to enhance or modulate the σ-hole donor ability of Chs, we believe that the findings presented herein are of remarkable importance for supramolecular chemists as well as for those scientists working in the field of solid state chemistry. [ABSTRACT FROM AUTHOR]

Three novel bis-urea fluorescent low-molecular-weight gelators (LMWGs) based on the tetraethyl diphenylmethane spacer—namely, L1, L2, and L3, bearing indole, dansyl, and quinoline units as fluorogenic fragments, respectively, are able to form gel in different solvents. L2 and L3 gel in apolar solvents such as chlorobenzene and nitrobenzene. Gelator L1 is able to gel in the polar solvent mixture DMSO/H2O (H2O 15% v/v). This allowed the study of gel formation in the presence of anions as a third component. An interesting anion-dependent gel formation was observed with fluoride and benzoate inhibiting the gelation process and H2PO4−, thus causing a delay of 24 h in the gel formation. The interaction of L1 with the anions in solution was clarified by 1H-NMR titrations and the differences in the cooperativity of the two types of NH H-bond donor groups (one indole NH and two urea NHs) on L1 when binding BzO− or H2PO4− were taken into account to explain the inhibition of the gelation in the presence of BzO−. DFT calculations corroborate this hypothesis and, more importantly, demonstrate considering a trimeric model of the L1 gel that BzO− favours its disruption into monomers inhibiting the gel formation. [ABSTRACT FROM AUTHOR]

Six new multicomponent solids of 9-ethyladenine and oxalic acid have been detected and characterized. The salt screening has been performed by mechanochemical and solvent crystallization processes. Single crystals of the anhydrous salts in 1:1 and 2:1 nucleobase:coformer molar ratio were obtained by solution crystallization and elucidated by single-crystal X-ray analysis. The supramolecular interactions observed in these solids have been studied using density functional theory (DFT) calculations and characterized by the quantum theory of "atoms in molecules" (QTAIM) and the noncovalent interaction plot (NCIPlot) index methods. The energies of the H-bonding networks observed in the solid state of the anhydrous salts in 1:1 and 2:1 nucleobase:coformer are reported, disclosing the strong nature of the charge assisted NH···O hydrogen bonds and also the relative importance of ancillary C–H··O H-bonds. [ABSTRACT FROM AUTHOR]

Any time the pharmaceutical industry develops a new drug, potential polymorphic events must be thoroughly described, because in a crystalline pharmaceutical solid, different arrangements of the same active pharmaceutical ingredient can yield to very different physicochemical properties that might be crucial for its efficacy, such as dissolution, solubility, or stability. Polymorphism in cocrystal formulation cannot be neglected, either. In this work, two different cocrystal polymorphs of the non-steroidal anti-inflammatory drug niflumic acid and caffeine are reported. They have been synthesized by mechanochemical methods and thoroughly characterized in solid-state by powder and single crystal X-ray diffraction respectively, as well as other techniques such as thermal analyses, infrared spectroscopy and computational methods. Both theoretical and experimental results are in agreement, confirming a conformational polymorphism. The polymorph NIF–CAF Form I exhibits improved solubility and dissolution rate compared to NIF–CAF Form II, although Form II is significantly more stable than Form I. The conditions needed to obtain these polymorphs and their transition have been carefully characterized, revealing an intricate system. [ABSTRACT FROM AUTHOR]

In this review, several examples of the application of pnictogen (Pn) (group 15) and chalcogen (Ch) bonding (group 16) interactions in organocatalytic processes are gathered, backed up with Molecular Electrostatic Potential surfaces of model systems. Despite the fact that the use of catalysts based on pnictogen and chalcogen bonding interactions is taking its first steps, it should be considered and used by the scientific community as a novel, promising tool in the field of organocatalysis. [ABSTRACT FROM AUTHOR]

This manuscript reports the synthesis and X-ray characterization of two octahydro-1H-4,6-epoxycyclopenta[c]pyridin-1-one derivatives that contain the four most abundant halogen atoms (Ha) in the structure with the aim of studying the formation of Ha···Ha halogen bonding interactions. The anisotropy of electron density at the heavier halogen atoms provokes the formation of multiple Ha···Ha contacts in the solid state. That is, the heavier Ha-atoms exhibit a region of positive electrostatic potential (σ-hole) along the C–Ha bond and a belt of negative electrostatic potential (σ-lumps) around the atoms. The halogen bonding assemblies in both compounds were analyzed using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, the quantum theory of "atom-in-molecules" (QTAIM), the noncovalent interaction plot (NCIplot), and the electron localization function (ELF). [ABSTRACT FROM AUTHOR]

Elements from groups 14–18 and periods 3–6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4−, PF6−, ClO4−, etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ–hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bondings for group 18. In general, σ–hole interactions exhibit different features when moving along the same group (offering larger and more positive σ–holes) or the same row (presenting a different number of available σ–holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ–hole interactions, complemented with molecular electrostatic potential surfaces of model systems. [ABSTRACT FROM AUTHOR]

Among non-covalent interactions, halogen bonding is emerging as a new powerful tool for supramolecular self-assembly. Here, along with a green and effective method, we report three new halogen-bonded cocrystals containing uracil derivatives and 1,2,4,5-tetrafluoro-3,6-diiodobenzene as X-bond donor coformer. These multicomponent solids were prepared both by solvent-drop grinding and solution methods and further characterized by powder and single-crystal X-ray diffraction, Fourier-transformed infrared spectroscopy, and thermal methods (TGA-DSC). In order to study the relative importance of hydrogen versus halogen bonds in the crystal packing, computational methods were applied. [ABSTRACT FROM AUTHOR]