The nature of hydrogen bonding in R22(8) crystal motifs – a computational exploration

R²₂(8), a commonly occurring motif in organic crystals, has been examined here through ab initio and density functional theory (DFT) methods. The 11 R²₂(8) motifs reported by Allen et al. have been classified into five types; their structural features, hydrogen-bonding patterns and the kind of interactions stabilising these motifs have been studied. Results reveal that the electronegativity of donor atoms plays a major role in directing the hydrogen bonds, whereas their positions in the motif have been found to be less important. Quantum theory of atoms in molecules (QTAIM) and reduced density gradient-based non-covalent-interaction analyses have been used to understand the weak interactions between monomers. Homonuclear interactions within the motifs have been found to be stronger with higher covalent character at the bond critical points than heteronuclear interactions. In addition, a localised molecular orbital energy decomposition analysis (LMOEDA) has been accomplished to provide useful insight into various long- and short-range interactions that contribute to the total stabilisation energies. The stabilising n → σ* interactions have been explained using natural bond orbital (NBO) analysis. Overall, this study provides the essential criteria for an organic crystal to be in an R²₂(8) motif and further discusses the different combinations of hydrogen-bonding features within the R²₂(8) motifs.     

Total ordering for intuitionistic fuzzy numbers

Intuitionistic fuzzy set plays a vital role in decision making, data analysis, and artificial intelligence. Many decision‐making problems consist of different types of datum, where fuzzy set theoretical approaches may fail to obtain the optimal decision. Numerous approaches for intuitionistic fuzzy decision‐making problem have been introduced in the literature to overcome these short comings. But there is no single approach that can be used to solve all kinds of problems because of the partial ordering defined on the collection of intuitionistic fuzzy numbers (IFNs). Even though ranking of fuzzy numbers have been studied from early seventies in the last century, a total order on the entire class of fuzzy numbers has been introduced by Wang and Wang (Fuzzy Sets Syst 2014, 243, 131–141) only on 2014. A total order on the collection of all IFN is an open problem till today. In this article, a total order on the entire class of IFN using upper lower dense sequence in the interval [0, 1] is proposed and compared with existing techniques using illustrative examples, further an algorithm (which is problem independent) for solving any intuitionistic fuzzy multicriteria decision‐making problem (Intuitionistic fuzzy MCDM) is introduced. This new total ordering on IFNs generalizes the total ordering defined in Wang and Wang ( 22 ) for fuzzy numbers. © 2016 Wiley Periodicals, Inc. Complexity 21: 54–66, 2016     

Asymptotic analysis of quasi-steady n-heptane droplet combustion supported by cool-flame chemistry

A skeletal chemical-kinetic mechanism for n-heptane cool flames is simplified to the maximum extent possible by introduction of steady-state approximations for intermediaries, following procedures employed previously in addressing two-stage ignition. A pair of ordinary differential equations in mixture-fraction space is thereby obtained, describing the quasi-steady structures of the temperature and heptylketohydroperoxide fields. Application of activation-energy asymptotics for the partial-burning regime to this pair of equations is shown to provide convenient expressions for flame structures and the extinction condition associated with maximally reduced chemistry. With the mixture-fraction co-ordinate related to radius, these results are used to address droplet-combustion experiments that have been performed in the International Space Station. Droplet diameters at extinction are predicted as functions of the oxygen concentration in the atmosphere and are compared with experiment. While the results are encouraging concerning qualitative predictions of dependences of extinction diameters on atmospheric conditions, there are noticeable quantitative differences that point to deficiencies in the analysis, likely resulting from a number of oversimplifications. Further investigation is therefore recommended.     

Tuning nonlinear optical and optoelectronic properties of vinyl coupled triazene chromophores: a density functional theory and time-dependent density functional theory investigation

Triazenes are a unique class of polyazo compounds containing three consecutive nitrogen atoms in an acyclic arrangement and are promising NLO candidates. In the present work, a series of 15 donor-π-acceptor type vinyl coupled triazene derivatives (VCTDs) with different acceptors (-NO(2), -CN, and -COOH) have been designed, and their structure, nonlinear response, and optoelectronic properties have been studied using density functional theory and time-dependent density functional theory methods. B3LYP/6-311g(d,p) optimized geometries of the designed candidates show delocalization from the acceptor to donor through a π-bridge. Molecular orbital composition analysis reveals that HOMO is stabilized by the π-bridge, whereas acceptors play a major role in the stabilization of LUMO. Among the three acceptors, nitro derivatives are found to be efficient NLO candidates, and tri- and di-substituted cyano and carboxylic acid derivatives also show reasonably good NLO response. The effect of solvation on these properties has been studied using PCM calculations. From TDDFT calculations, the computed absorption spectra of these candidates lie in the range of 350-480 nm in the gas phase and have positive solvatochromism. The ground-state stabilization interactions are accounted from NBO calculations. In an effort to substantiate the thermal stability of the designed candidates, computations have been done to identify the weak interactions in the systems through NCI and AIM analysis. In summary, 10 out of 15 designed candidates are found to have excellent NLO and optoelectronic properties.     

Water-Mediated Strecker Reaction: An Efficient and Environmentally Friendly Approach for the Synthesis of α-Aminonitriles via a Three-Component Condensation

The synthesis of α-aminonitriles by a direct three component Strecker reaction has been achieved in water, which is found to be an inexpensive, non-toxic and eco-friendly reaction medium for the nucleophilic addition. This protocol is effective to a wide variety of substrates with different functional groups and does not require the use any other catalyst.     

4‐Aminopyridinium 4‐aminobenzoate dihydrate and 4‐aminopyridinium nicotinate

In the title compounds, 4‐aminopyridinium 4‐aminobenzoate dihydrate, C₇H₆NO₂⁻·C₅H₇N₂⁺·2H₂O, (I), and 4‐aminopyridinium nicotinate, C₅H₇N₂⁺·C₆H₄NO₂⁻, (II), the aromatic N atoms of the 4‐aminopyridinium cations are protonated. In (I), the asymmetric unit is composed of two 4‐aminopyridinium cations, two 4‐aminobenzoate anions and four water molecules, and the compound crystallizes in a noncentrosymmetric space group. The two sets of independent molecules of (I) are related by a centre of symmetry which is not part of the space group. In (I), the protonated pyridinium ring H atoms are involved in bifurcated hydrogen bonding with carboxylate O atoms to form an R₁²(4) ring motif. The water molecules link the ions to form a two‐dimensional network along the (10) plane. In (II), an intramolecular bifurcated hydrogen bond generates an R₁²(4) ring motif and inter‐ion hydrogen bonding generates an R₄²(16) ring motif. The packing of adduct (II) is consolidated via N—H...O and N—H...N hydrogen bonds to form a two‐dimensional network along the (10) plane.     

Iodine-catalyzed one-pot synthesis of amides from nitriles via Ritter reaction

Ritter reactions of alcohols and tert-butyl acetate with various nitriles were performed using iodine as a mild and effective catalyst under heating conditions to afford the corresponding amides in good to excellent yields.