Interaction Of Nitriles Research Articles

Supramolecular assemblies involving unusual N(nitrile)∙∙∙π(fum) and nitrile-nitrile non-covalent contacts in fumarato and succinato bridged polymers of Co(II) and Ni(II): Experimental and theoretical studies

Two new Co(II) and Ni(II) coordination polymers viz. [Co(H2O)2(μ-fum)(3-CNpy)2]n (1) and {[Ni(H2O)2(μ-succ)(4-CNpy)2]·2H2O}n (2) (where, fum= fumarate, CNpy = cyanopyridine, succ = succinate) have been synthesized and characterized using single crystal XRD, elemental analysis, spectroscopic (IR and electronic) techniques and TGA. Compound 1 crystallizes as a fumarato bridged Co(II) polymer; whereas, compound 2 is a succinato bridged Ni(II) polymer. The presence of various non-covalent interactions in the compounds stabilizes the layered assemblies of the compounds. Antiparallel nitrile∙∙∙nitrile interactions are observed in both the crystal structures involving the nitrile moieties of coordinated CNpy which provide rigidity to the compounds. Further analysis reveals that the N-atom of –CN group of 3-CNpy in 1 is involved in unusual N(nitrile)∙∙∙π(fum) interactions with the π-electrons of the C=C bond of fum. Enclathrated (H2O)2 cores within the supramolecular host cavity of compound 2 provides additional reinforcement to the crystal structure. We have also carried out theoretical studies to analyze the π-stacking and H-bonding interactions present in the crystal structure of compound 1 using quantum theory of atoms-in-molecules (QTAIM), non-covalent interaction plot (NCI plot) and molecular electrostatic potential (MEP) surface analysis. The MEP value at the N-atom of the cyano group of 1 is negative and the value is neutral over the double bond of the fum; indicating the possibilities of formation of N(nitrile)∙∙∙π(fum) interactions. Energetic analysis suggests that antiparallel π-stacking observed between the 3-CNpy moieties in 1 is the most dominating force followed by N(nitrile)∙∙∙π(fum) interaction and finally the H-bonds.

Supramolecular assemblies involving energetically significant unconventional π(CN)-π and anion-π(nitrile) contacts in Zn(II) coordination compounds: Antiproliferative evaluation and theoretical studies

Two new coordination compounds of Zn(II) involving cyanopyridine ligands viz. [Zn(2,6-PDC)(3-CNpy)(H2O)2] (1) and [Zn(4-CNpy)2Cl2] (2) (2,6-PDC = 2,6-pyridinedicarboxylate, 3-CNpy = 3-cyanopyridine, 4-CNpy = 4-cyanopyridine) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FT-IR, electronic and 1H-NMR) techniques and single crystal XRD. Crystal structure analyses of 1 and 2 unfold the presence of unusual π(CN)-π interactions which provide stability to the layered assemblies of the compounds. Anion-π with parallel nitrile–nitrile interactions in 1 and unconventional anion-π(nitrile) with antiparallel nitrile-nitrile interactions in 2 also contribute to the stability of the crystal structures. Antiparallel CO⋯CO interactions give additional reinforcement to the crystal structure of 1. DFT calculations in combination with MEP surface and NCI plot/QTAIM analyses on different self-assembled supramolecular dimers of the compounds revealed that the unusual CN···π interactions in 1 and Chlorine-π(nitrile) in 2 are energetically significant. The studies also reveal that both H-bonding and π-stacking interactions are energetically important for the stability of the compounds. Compounds 1 and 2 mediated anticancer evaluation on Dalton's lymphoma (DL) cancer cells has been explored considering cytotoxicity and apoptosis assays. The compounds induce significant concentration dependent cytotoxicity in DL cells with negligible effects on normal PBMC cells. Molecular docking studies reveal that the compounds effectively interact with the active sites of antiapoptotic proteins which are actively involved in cancer progression. Pharmacophore features of the structures of the compounds have been finally identified to establish the structure activity relationships (SAR).

Dicarboxylic Acid-Based Co-Crystals of Pyridine Derivatives Involving Structure Guiding Unconventional Synthons: Experimental and Theoretical Studies

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.

Quantification of the Strength of π‐Noncovalent Interactions in Molecular Balances using Density Functional Methods

AbstractDifferent molecular balances were designed previously to compare noncovalent interactions. However, some balances are difficult to synthesise and there is a need for developing a computational approach. In this work, we probe noncovalent interactions of π systems using DFT methods to assess their reliability in reproducing experimentally measured conformer populations. Based on our results, the PW6B95D3 functional performed best, followed by M11L and ωB97XD. Additionally, the simulation of the rotation of the hydroxyl group revealed stabilising OH⋯Alkyne and OH⋯Nitrile interactions that are difficult to identify experimentally. These methods were then applied to compare the strengths of sulfur⋯π interactions in molecules which have not been explored experimentally. Compared to the hydroxyl counterpart, the simulation of the thiol group rotation showed that the geometry of the conformer with the two sulfur lone pairs oriented towards the aromatic ring or the double bond is stabilised, suggesting that S(LP)⋯π interactions can be attractive in nature. The ability of sulfur to rearrange its electronic surrounding to form an attractive interaction with π systems, including those with either electron‐donating or withdrawing groups, was also confirmed. Overall, the results show a promising future for both qualitative and quantitative assessments of the strengths of noncovalent interactions using selected DFT techniques.

Energetically significant nitrile⋯nitrile and unconventional C–H⋯π(nitrile) interactions in pyridine based Ni(II) and Zn(II) coordination compounds: Antiproliferative evaluation and theoretical studies

Two new coordination compounds viz. [Ni(2,6-PDC)(Hdmpz)(H2O)2]∙H2O (1) and [Zn(3-CNpy)2Cl2] (2) (2,6-PDC = 2,6-pyridinedicarboxylate, Hdmpz = 3,5-dimethylpyrazole, 3-CNpy = 3-cyanopyridine) have been synthesized and characterized using elemental analysis, thermogravimetric analysis, electronic, infrared spectroscopy and single crystal X-ray diffraction techniques. Crystal structure analyses reveal the presence of supramolecular assemblies involving interesting dimers with unconventional contacts in the compounds. DFT (Density Functional Theory) calculations on the supramolecular dimers in the crystal structure of 1 reveal that the sum of contributions of anion–π, π–π and other long range interactions due to the approximation of the bulk monomers is energetically significant. Molecular Electrostatic Potential (MEP) surface and Quantum Theory of Atoms in Molecules (QTAIM) analyses on the interesting supramolecular dimers of the crystal structures of 2 reveal the presence of unconventional anion⋯π contacts involving coordinated chlorido ligands and C–H⋯π(nitrile) interactions involving the π-system of the nitrile moiety of 3-cyanopyridine. Remarkably, Atoms in Molecules analysis also confirms the existence of energetically significant unconventional anti-parallel nitrile⋯nitrile interaction in the crystal structure of 2. Cell cytotoxicity of the compounds performed in Dalton's lymphoma (DL) malignant cancer cell line showed effective potency with negligible cytotoxicity in normal cells (~12%). It is interesting that compound 1has excellent cytotoxic potency with IC50 closer to cisplatin and can bind different biological targets with similar signalling pathways. Structure activity relationship (SAR) analyses of 1 and 2 based on pharmacophore modelling reveal that the molecular features associated with the structures of the compounds play important role in the biological activities.

One-Pot Synthesis of γ-Azidobutyronitriles and Their Intramolecular Cycloadditions

Efficient gram-scale, one-pot approaches to azidocyanobutyrates and their amidated or decarboxylated derivatives have been developed, starting from commercially available aldehydes and cyanoacetates. These techniques combine (1) Knoevenagel condensation, (2) Corey–Chaykovsky cyclopropanation and (3) nucleophilic ring opening of donor-acceptor cyclopropanes with the azide ion, as well as (4) Krapcho decarboxylation or (4′) amidation. The synthetic utility of the resulting γ-azidonitriles was demonstrated by their transformation into tetrazoles via intramolecular (3+2)-cycloaddition. A condition-dependent activation effect of the α-substituent was revealed in that case. Thermally activated azide–nitrile interaction did not differentiate the presence of an α-electron-withdrawing substituent in γ-azidonitriles, whereas the Lewis acid mediated (SnCl4 or TiCl4) reaction proceeded much easier for azidocyanobutyrates. This allowed us to develop an efficient procedure for converting azidocyanobutyrates into the corresponding tetrazoles.

Charge-assisted hydrogen bond and nitrile⋯nitrile interaction directed supramolecular associations in Cu(ii) and Mn(ii) coordination complexes: anticancer, hematotoxicity and theoretical studies

Charge-assisted H-bonds and nitrile⋯nitrile interactions directed assemblies in Cu(ii) and Mn(ii) complexes have been analyzed by MEP surface and NCI plot index. Anticancer activities and hematotoxictiy have been investigated.

Supramolecular association involving nitrile–nitrile interactions in polymeric Mn(II) coordination complexes: A combined experimental and theoretical study

Two new Mn(II) coordination polymers viz. [Mn(p-NBz)2(4-CNpy)2]n (1) and [Mn(4-CNpy)2(H2BTC)2]n (2) [p-NBz = p-nitrobenzoate, H3BTC = 1,3,5-benzenetricarboxylic acid and 4-CNpy = 4-cyanopyridine] have been synthesized at room temperature and characterized by single crystal X-ray diffraction, FT-IR spectroscopy, electronic spectroscopy, elemental analyses and thermogravimetric analysis (TGA). The complexes are stabilized by several non-covalent interactions along with a rather uncommon nitrile(π)–nitrile(π) interactions resulting in layered structures. The supramolecular association in both the polymers results in 3D network structures involving CH⋯O interactions in the direction perpendicular to the existing layers. The anti-parallel CN⋯CN interaction observed in the polymeric chains of the complexes are studied using DFT calculations and characterized using the Bader’s theory of “atoms-in-molecules”. The interaction energy of the anti-parallel nitrile–nitrile interactions is similar to hydrogen bonds which are enhanced by the coordination of 4-CNpy to the Mn(II) metal centre.

On the interactions of nitriles and fluoro-substituted pyridines with silicon tetrafluoride: Computations and thin film IR spectroscopy

The nature of the interactions between silicon tetrafluoride and series of nitrogen bases, including nitriles (RCN, with R > CH3), pyridine, and various fluoro-substituted pyridines, has been investigated via quantum-chemical computations, low-temperature IR spectroscopy, and bulk reactivity experiments. Using (primarily) M06 with the 6-311+G(2df,2pd) basis set, we obtained equilibrium structures, binding energies, harmonic frequencies, and N–Si potentials in the gas-phase and in bulk dielectric media for an extensive series of 1:1 molecular complexes, including: C6H5CH2CN–SiF4, CH3CH2CN–SiF4, (CH3)3CCN–SiF4, C5H5N–SiF4, 4-FC5H4N–SiF4, 3,5-C5F2H3N–SiF4, 2,6-C5F2H3N–SiF4 and 3,4,5-C5F3H2N–SiF4. In addition, for the analogous 2:1 complexes of pyridine and 3,5-difluororpyridine, we obtained equilibrium structures, binding energies, and harmonic frequencies. The N–Si distances in the 1:1 nitrile complexes are fairly long, ranging from 2.84 Å to 2.88 Å, and the binding energies range from 4.0 to 4.2 kcal/mol (16.7–17.6 kJ/mol). Also, computations predict extremely anharmonic N–Si potentials, for which the inner portions of the curve are preferentially stabilized in dielectric media, which predict an enhancement of these interactions in condensed-phases. However, we see no evidence of bulk reactivity between C6H5CH2CN, CH3CH2CN, or (CH3)3CCN and SiF4, nor any significant interaction between (CH3)3CCN and SiF4 in low temperature IR spectra of solid, (CH3)3CCN/SiF4 thin films. Conversely, the interactions in four of the five 1:1, pyridine-SiF4 complexes are generally stronger; binding energies range from 5.7 to 9.6 kcal/mol (23.8–40.2 kJ/mol), and correspondingly the N–Si distances are relatively short (2.12–2.25 Å). The exception is 2,6-C5F2H3N–SiF4, for which the binding energy is only 3.6 kcal/mol (15.1 kJ/mol), and the N–Si distance is quite long (3.12 Å). In addition, both pyridine and 3,5-difluororpyridine were found to form stable reaction products with SiF4; but no analogous product was obtained with 2,6-difluororpyridine and SiF4, nor was any significant interaction indicated in low-temperature IR spectra of 2,6-difluororpyridine/SiF4 films. By contrast, low temperature spectra of pyridine/SiF4 and 3,5-difluororpyridine/SiF4 thin films are consistent with the presence of a distinct 2:1 reaction product. Moreover, the observed frequencies agree reasonably well with those predicted for the cis, octahedral coordination isomers of the 2:1 molecular complexes, in which the N–Si bonds are compressed slightly relative to those in the predicted gas-phase structures.

Comparing Crystallizations in Three Dimensions and Two Dimensions: Behavior of Isomers of [2,2′-Bipyridine]dicarbonitrile and [1,10-Phenanthroline]dicarbonitrile

Various symmetric isomers of [2,2′-bipyridine]dicarbonitrile and [1,10-phenanthroline]dicarbonitrile were crystallized from solution and also deposited as monolayers adsorbed on graphite. The resulting three- and two-dimensional (3D and 2D) structures were studied by single-crystal X-ray diffraction and scanning tunneling microscopy, respectively. Previous comparisons of 3D and 2D structures have provided new understanding of molecular organization and have revealed that crystals and adlayers can have closely analogous structures despite the effects of the underlying surface, especially when organization is dominated by strong intermolecular interactions within a single plane. The present study extends previous work by showing that analogous 3D and 2D structures can be formed even when association is directed by weaker intermolecular forces, as exemplified by C–H···N interactions of nitriles.

Unusually Stable Triazine‐based Organic Superstructures

AbstractSolid‐state reactions have been rapidly gaining popularity in organic chemistry owing to their simplicity, efficiency, and selectivity compared to liquid‐phase reactions. Herein, we describe the formation of superstructures through the solid‐state reaction of an organic single‐crystal. The superstructure of 5,5′,5′′‐(1,3,5‐triazine‐2,4,6‐triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5‐tricyanobenzene (TCB) single crystals. The TIPN superstructure was confirmed by single crystal X‐ray diffraction and visualized by transmission electron microscopy. The superstructure has hexagonally packed 1‐dimensional (1D) channels along the crystal axis. Furthermore, the superstructure arises from interdigitated nitrile interactions in the crystal lattice, and thus has electron‐beam tolerance and very high thermal stability.

Unusually Stable Triazine-based Organic Superstructures.

Solid-state reactions have been rapidly gaining popularity in organic chemistry owing to their simplicity, efficiency, and selectivity compared to liquid-phase reactions. Herein, we describe the formation of superstructures through the solid-state reaction of an organic single-crystal. The superstructure of 5,5',5''-(1,3,5-triazine-2,4,6-triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5-tricyanobenzene (TCB) single crystals. The TIPN superstructure was confirmed by single crystal X-ray diffraction and visualized by transmission electron microscopy. The superstructure has hexagonally packed 1-dimensional (1D) channels along the crystal axis. Furthermore, the superstructure arises from interdigitated nitrile interactions in the crystal lattice, and thus has electron-beam tolerance and very high thermal stability.

Orientational Effects and Random Mixing in 1-Alkanol + Nitrile Mixtures

1-Alkanol + alkanenitrile or + benzonitrile systems have been investigated by means of the molar excess functions—enthalpies (HmE), isobaric heat capacities (Cp,mE), volumes (VmE), and entropies—and using the Flory model and the concentration–concentration structure factor (SCC(0)) formalism. From the analysis of the experimental data available in the literature, it is concluded that interactions are mainly of dipolar type. In addition, large HmE values contrast with rather low VmE values, indicating the existence of strong structural effects. HmE measurements have been used to evaluate the enthalpy of the hydroxyl–nitrile interactions (ΔHOH–CN). They are stronger in methanol systems and become weaker when the alcohol size increases. In solutions with a given short chain 1-alkanol (up to 1-butanol), the replacement of ethanenitrile by butanenitrile weakens the mentioned interactions. Application of the Flory model shows that orientational effects exist in methanol or 1-nonanol, or 1-decanol + ethanenitrile mixtures. In the former solution, this is due to the existence of interactions between unlike molecules. For mixtures including 1-nonanol or 1-decanol, the systems at 298.15 K are close to their UCST (upper critical solution temperature), and interactions between like molecules are dominant. Orientational effects also are encountered in methanol or ethanol + butanenitrile mixtures because self-association of the alcohol plays a more important role. Aromaticity effect seems to enhance orientational effects. For the remainder of the systems under consideration, the random mixing hypothesis is attained to a rather large extent. Results from the application of the SCC(0) formalism show that homocoordination is the dominant trend in the investigated solutions, and are consistent with those obtained from the Flory model.

Theoretical investigations on the hydrogen bonding of nitrile isomers with H2O, HF, NH3 and H2S

The hydrogen bonds formed by the interaction of nitriles with water, hydrogen fluoride, ammonia and hydrogen sulphide have been studied using B3LYP and second-order Møller–Plesset perturbation (MP2) methods and 6-311+ + G(d,p) basis set. The energies and structures of 80 hydrogen-bonded complexes between nitriles and small molecules were examined systematically using B3LYP and MP2 procedure. Categorisation of the hydrogen bonds involved in the various complexes led to an ordering of hydrogen bond donor and acceptor abilities for some functional groups. The interaction energies have been corrected for the basis set superposition error using Boy's counterpoise correction method. The Morokuma energy decomposition analysis reveals that the strong interactions are due to the attractive contributions from the electrostatic (ES), polarisation (PL) and charge transfer (CT) components. The topological parameters, electron density and Laplacian of electron density show excellent correlation with the hydrogen bond length. Natural bond orbital (NBO) analysis has also been performed to study the CT from proton acceptor to the antibonding orbital of the H–Y bond in the proton donor part of complexes. The frequency analysis of C–H…Y bond in the complexes indicates the blue-shifting nature largely in case of sp2 hybridised carbon atom.

Enzyme–Substrate Binding Landscapes in the Process of Nitrile Biodegradation Mediated by Nitrile Hydratase and Amidase

The continuing discharge of nitriles in various industrial processes has caused serious environmental consequences of nitrile pollution. Microorganisms possess several nitrile-degrading pathways by direct interactions of nitriles with nitrile-degrading enzymes. However, these interactions are largely unknown and difficult to experimentally determine but important for interpretation of nitrile metabolisms and design of nitrile-degrading enzymes with better nitrile-converting activity. Here, we undertook a molecular modeling study of enzyme-substrate binding modes in the bi-enzyme pathway for degradation of nitrile to acid. Docking results showed that the top substrates having favorable interactions with nitrile hydratase from Rhodococcus erythropolis AJ270 (ReNHase), nitrile hydratase from Pseudonocardia thermophila JCM 3095 (PtNHase), and amidase from Rhodococcus sp. N-771 (RhAmidase) were benzonitrile, 3-cyanopyridine, and L-methioninamide, respectively. We further analyzed the interactional profiles of these top poses with corresponding enzymes, showing that specific residues within the enzyme's binding pockets formed diverse contacts with substrates. This information on binding landscapes and interactional profiles is of great importance for the design of nitrile-degrading enzyme mutants with better oxidation activity toward nitriles or amides in the process of pollutant treatments.

Lithium–Sulfur Battery Cathode Enabled by Lithium–Nitrile Interaction

Lithium sulfide is a promising cathode material for high-energy lithium ion batteries because, unlike elemental sulfur, it obviates the need for metallic lithium anodes. Like elemental sulfur, however, a successful lithium sulfide cathode requires an inherent mechanism for preventing lithium polysulfide dissolution and shuttling during electrochemical cycling. A new scheme is proposed to create composites based on lithium sulfide uniformly dispersed in a carbon host, which serve to sequester polysulfides. The synthesis methodology makes use of interactions between lithium ions in solution and nitrile groups uniformly distributed along the chain backbone of a polymer precursor (e.g., polyacrylonitrile), to control the distribution of lithium sulfide in the host material. The Li(2)S-carbon composites obtained by carbonizing the precursor are evaluated as cathode materials in a half-cell lithium battery, and are shown to yield high galvanic charge/discharge capacities and excellent Coulombic efficiency, demonstrating the effectiveness of the architecture in homogeneously distributing Li(2)S and in sequestering lithium polysulfides.

Physicochemical studies of molecular interactions in binary mixtures of toluene with some aliphatic nitriles at different temperatures

Densities ρ, ultrasonic speeds u and viscosities η of binary mixtures of toluene with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN), including those of pure liquids are measured over the entire composition range at 298.15, 303.15 and 308.15 K and at atmospheric pressure. From these experimental data, isentropic compressibility k s, molar isentropic compressibility K s, excess molar volume V m E, partial molar volumes V̅ m,1 ° and V̅ m,2 °, excess partial molar volumes V̅ m,1 °E and V̅ m,2 °E of the components at infinite dilution are calculated. The variation of these properties with composition and temperature of the binary mixtures is discussed in terms of molecular interactions between unlike molecules of the mixtures. The values of V m E are found negative for all the mixtures at each temperature studied, indicating the presence of specific interactions between toluene and AN/PN/BN molecules. The variations of V m E values with composition indicate that the interactions in these mixtures follow the order: AN > PN > BN, i.e., the toluene–nitrile interaction decreases with increase in alkyl chain length in these nitrile molecules.

Molecular interaction studies and theoretical estimation of ultrasonic speeds using scaled particle theory in binary mixtures of toluene with homologous nitriles at different temperatures

Densities, ρ, ultrasonic speeds, u, and viscosities, η of binary mixtures of toluene with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN), including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K, respectively. From these experimental data, excess intermolecular free length, L f E , the deviations in ultrasonic speed, Δ u, excess acoustic impedance, Z E and excess free energy of activation Δ G* E are calculated. The variation of these excess parameters indicates the presence of specific interactions between toluene and AN/PN/BN molecules, and the interactions follow the order: AN > PN > BN, i.e., the toluene–nitrile interaction decreases with increase in alkyl chain length. Moreover, the theoretical ultrasonic speeds are computed based on the scaled particle theory and compared with the experimentally measured values.

Bridge Orientation as a Selector of Intermolecular Interactions in a Series of Crystalline Isomeric Benzylideneanilines

Comparison of the crystal structures of compounds we have designated “bridge-flipped isomers,” which on the molecular level differ only in the orientation of a bridge of atoms connecting two larger parts of the molecule, offers a useful context for the examination and evaluation of intermolecular interactions and their robustness as supramolecular synthons. Intermolecular interactions in the crystal structures of five pairs of bridge-flipped isomeric benzylideneanilines are examined here, including interactions between nitrile groups and ring hydrogen atoms, between halogen atoms, and between nitrile groups and halogen atoms. Of these, only the halogen−nitrile interaction in which the halogen is iodine is present in both bridge-flipped isomers of the pair, although its influence on the molecular packing arrangement is insufficient to compel the two isomers to assume identical packing arrangements. Pairwise analysis of crystal structures of bridge-flipped isomers thus provides a perspective beyond that pro...

A guest-templated (6,3)-sheet constructed using asymmetric hydrogen-bonding anions

A hydrogen-bonded (6,3)-sheet similar to that of trimesic acid, containing asymmetric anions as the three-connecting nodes joined by NH⋯nitrile interactions, is templated by a cationic Cu(II) guest species.