Solid-state Supramolecular Architectures Research Articles

Supramolecular synthon polymorphism in modified amino acids. Structural, conformational and energy landscapes of N-benzoyl-2′-hydroxy-3-methylisovaline

The title compound, N-benzoyl-2′-hydroxy-3-methylisovaline, representing synthon polymorphism, can be interesting inter alia from the point of view of modern supramolecular biofunctional materials. A novel crystalline phase (1) was successfully synthesized and its solid-state supramolecular architecture was comprehensively compared with the previously reported polymorphic form (2), deposited in the Cambridge Structural Database as Private Communication by Karr & Fronczek. Molecular conformation, qualitative and quantitative analysis of supramolecular interactions, including evaluation of their energies, were investigated by modern experimental and theoretical methods. The geometries of S and R enantiomers were optimized using DFT at the B3LYP-D3/6-311++G(d, p) basis set level of theory. The conformational structure of these stereoisomers in water was studied using the solvation CPCM model. Water has a slight effect on the geometry and relative stability of isomers. Hirhsfeld surface analysis revealed general similarity of interactions in both polymorphs and closely related isovaline derivatives retrieved from the Cambridge Structural Database, dominated by H⋯H, O⋯H/H⋯O and C⋯H/H⋯C intermolecular contacts, contributing to about 95% of the total HS area. Nevertheless, in (2) π … π stacking interactions play significant role in driving the polymorphism formation. The interplay of basic supramolecular synthons and long-range synthon aufbau modules at subsequent levels of the supramolecular architecture is discussed in detail. Overall, the supramolecular assemblies are composed of large synthons in the form of a layer in (1) and pseudohexagonally packed ribbons in (2), sustained by relatively strong H-bonds (alternating catemer-dimer mix) and π … π contacts, respectively. For a thorough and precise interpretation, two methodologies: Gavezzotti implemented in the PIXELC vs. a novel way via energy frameworks construction in the CrystalExplorer were used. It enabled deeper insight into the quantitative evaluation of the molecular pair-wise interactions energetics in the supramolecular structures of both polymorphs, revealing further differences between them.

Solid-state supramolecular architectures of a series of Hg(ii) halide coordination compounds based on hydroxyl-substituted Schiff base ligands

Herein, six Hg(ii) coordination compounds containing Schiff base ligands were synthesized, characterized and studied using geometrical and Hirshfeld analyses as well as theoretical calculations.

The first insight into the supramolecular structures of popular drug repaglinide: Focus on intermolecular interactions in antidiabetic agents

This work is the first, according to our knowledge, complete structural report on the solid-state supramolecular architecture of antidiabetic drug repaglinide. Here, we present a series of four crystal structures, namely: an un-solvated form of repaglinide (1), repaglinide hydrochloride (2), repaglinide monohydrate (3) and repaglinide methanol solvate (4), successfully determined and fully characterized by the single-crystal X-ray diffraction method (SC-XRD) at 100 K. The (1) and (2) crystallize in the orthorhombic P212121 space group with Z = 1, while solvates exist in triclinic P-1 with Z = 2. The hierarchy and interplay of various intra- and intermolecular interactions in the creation of a 3-D supramolecular assembly using different finite groups (D), rings (R) and infinite chains (C) graph-set motifs are discussed in detail. A particular focus is put on unique halogen-bonded supramolecular synthons. Interestingly, in (2) structure, an intramolecular cyclic ring S(8) synthon was found as a consequence of the NH+ group. Solvent and water molecules play a significant role in the formation of supramolecular architectures in the context of large synthons, the so-called long-range synthon Aufbau modules (LSAM) at the higher level of the crystal organization. A qualitative and quantitative comparative investigation of intercontacts nature between the adjacent molecules in the crystal, govering the supramolecular assemblies, with respect to other members of the glinides family - nateglinide and also related antidiabetic benzoic acid derivatives, retrieved from the Cambridge Structural Database (version 5.39, update February 2018 release) was supported by 3-D Hirshfeld surface maps and the associated 2-D fingerprint plots analysis visualizing all intercontacts at once and contributing them to the total surface for each compound. It revealed numerous interactions mainly H⋯H, O⋯H, C⋯H (CH…π), but also Cl⋯H(O, C) C⋯C (π…π), N⋯H(O), C⋯O (π…lone pair), O⋯O (lone pair…lone pair) cooperatively participating in stabilization of the supramolecular structures of this class of APIs.

Solid-state supramolecular architectures formed by co-crystallization of melamine and 2-, 3- and 4-fluorophenylacetic acids

A family of supramolecular complexes of melamine with fluorophenylacetic acid isomers using solvent-assisted and evaporation-based techniques has been prepared. Crystallization of melamine with 2-fluorophenylacetic acid yield hydrated ionic supramolecular complex (1), whereas crystallization of melamine with 3- and 4-fluorophenylacetic acids leads to formation of neutral supramolecular complexes (2, 3), all with base to acid ratio of 1:2. The supramolecular assembly is driven by the noncovalent interactions, most commonly by the hydrogen bonds. The components of the crystal 1 interact via NH⋯O and OH⋯N hydrogen bonds with R22(8) and R32(10) graphs forming ionic supramolecular complex, whereas the components in the crystals 2 and 3 interact with a graph of R22(8) forming neutral supramolecular complexes. The singly protonated melamin-1-ium residues in 1 interact each other via a pair of NH⋯N hydrogen bonds forming one dimensional chains along [−110] that interact via NH⋯O with deprotonated and neutral 2-fluorophenylacetic acid units and water molecules forming ribbon. In 2 and 3 co-crystals the melamine interacts with 3- and 4-fluorophenylacetic acids via a pair of NH⋯O hydrogen bonds forming pseudo one-dimensional supramolecular chains along [010] direction. Hirshfeld surface and analysis of 2D fingerprint plots have been analysed both quantitatively and qualitatively interactions that governing the supramolecular organisation. The IR and Raman vibrational characterization of the supramolecular complexes 1–3 was supported by the spectra of their deuterated analogues.

One-pot green synthesis of biologically relevant novel spiro[indolin-2-one-3,4'-pyrano[2,3-c]pyrazoles] and studies on their spectral and X-ray crystallographic behaviors.

Syntheses via green route and single-crystal X-ray structural investigations have been carried out for three spiro[indolin-2-one-3,4'-pyrano[2,3-c]pyrazole] derivatives, 6'-amino-2-oxo-3'-propyl-2'H-spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]-5'-carbonitrile dimethyl sulfoxide monosolvate (5a), 6'-amino-5-fluoro-2-oxo-3'-propyl-2'H-spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]-5'-carbonitrile dimethyl sulfoxide monosolvate (5b) and methyl 6'-amino-5-cyano-1-methyl-2-oxo-3'-propyl-2'H-spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]-3'-carboxylate 0.25 hydrate (5c), respectively. Compounds (5a) and (5b) crystallize in the triclinic space group P\bar 1, whereas compound (5c) crystallizes in the monoclinic space group C2/c. In molecules (5a) and (5b) all the rings are practically flat, while in (5c), the heterocyclic pyran ring adopts a flattened-boat conformation. In (5a) and (5b) the cyanide group is oriented in a (-ap) conformation, while the amino group is oriented in a (+ap) conformation with a pyran ring, but in (5c) both the cyanide and amino groups are oriented in a (-ap) conformation with the pyran ring. In the crystal structure of (5a) and (5b), the molecules are linked by an elaborate system of N-H...O and N-H...N hydrogen bonds to generate a zigzag-like construct. In (5c) molecules are linked by N-H...O hydrogen bonds, thereby generating extended chains. The present communication focuses on the detailed and comparative information about spectral behaviors, single-crystal X-ray crystallographic properties and solid-state supramolecular architectures of these synthesized compounds of potential biological interests.

Metal complexes of ditopic dithiophosphonate ligands built on a naphthalenediimide core

Ditopic ligands consisting of two dithiophosphonate donor groups attached to a 1,4,5,8-naphthalenediimide core through ether spacers of different length have been synthesized and characterized. The NDI[(CH2CH2O)n(An)PS2NH4]2 ligands (n=1: 1a-[NH4]2; n=2: 1b-[NH4]2; NDI=naphthalenediimide; An=anisole) react with Ph3SnCl and (Ph3P)2CuNO3 in a 1:2 ratio to yield bimetallic complexes (1a-[SnPh3]2 and 1a-[Cu(PPh3)2]2 for n=1, and 1b-[SnPh3]2 and 1b-[Cu(PPh3)2]2 for n=2), and with Ph2SnCl2 in a 1:1 ratio to form bimetallic ({1a-[SnPh2]}2) and monometallic (1b-[SnPh2]) macrocycles. Structural characterization of these compounds revealed monodentate and anisobidentate coordination modes of the dithiophosphonate group, as well as the presence of metal-sulfur secondary bonds. While the ditopic nature of the ligand does not have an influence over the coordination behavior of the individual –PS2 groups, the length of the naphthalenediimide-dithiophosphonate linker lead to different solid-state supramolecular architectures. Cooperative π–π stacking and C–H⋯π interactions organize the supramolecular structures of these complexes, generating two-dimensional sheets (in the case of “short-arm” ligand: 1a-[SnPh3]2 and 1a-[Cu(PPh3)2]2) and mono-dimensional chains (in the case of “long-arm” ligand: 1b-[SnPh3]2). In the case of {1a-[SnPh2]}2 and 1b-[SnPh2] metallacycles, π–π stacking interactions between NDI central moieties produce infinite π–π stacked chains and discrete dimers, respectively.

Medium-ring aminocyclitols: a concise synthesis of nine-membered aminocarbasugar analogs and the solid-state supramolecular architectures of two key precursors

A stereocontrolled synthesis of nine-membered aminocarbasugar analogs (amino-cyclononanoses) from a rigid bicyclo[4.3.1]deca-2,4-dien-10-one platform, harboring a latent functionalized cyclononane ring, is described.

Solid-state supramolecular architectures by p-sulfonatocalix[5]arene with bispyridinium derivatives: factors of spacers and terminal groups

Three solid-state supramolecular structures were obtained by inclusion complexation of p-sulfonatocalix[5]arene with 1,2-bis(4,4′-methylpyridinium)ethane, 1,2-bis(4,4′-aminopyridinium)ethane and 1,4-bis(pyridinium)butane. All three complexes have been thoroughly examined from the aspects of binding mode, stoichiometry and extended structure. Effects of guest molecules, especially spacers and terminal groups, on host conformation, binding and extended structures were carefully compared and summarized.

A self-assembled supramolecular solid for catalytic application

Abstract A 1,8-naphthalenecarboxylic anhydride-4,5-dicarboxylate (L) bridged copper(II) dimeric molecular module [Cu2L2(DMF)2(H2O)2] (1) can self-organize into a solid-state supramolecular architecture. The combination of the multitopic contact sites of hydrogen bonds coupled with two bulky aromatic cores promoted the molecule to self-link into a solid-state supramolecular architecture, which was almost insoluble in water and common organic solvents. Solid 1 can heterogeneously catalyze the cross-coupling of arylboronic acids with imidazole in the absence of a base or additive to generate the corresponding coupling products in excellent yields in methanol at 50 °C, which can be recovered and recycled by a simple filtration and was used for six consecutive cycles with consistent activity.

Supramolecular architectures of simple aminoanthraquinones: Revised structure of 1-aminoanthraquinone

The solid-state supramolecular architectures of 1-aminoanthraquinone and 1,5-diaminoanthraquinone were determined by single-crystal X-ray structural analysis. In this paper, revised model − in space group P2 1/ c − is given for the crystal structure of 1-aminanthraquinone. 1-Aminoantaquinone molecules are joined together in infinite chains by N H⋯O hydrogen bonds and stacked by face-to-face π−π and C H⋯π interactions thus creating layers and the characteristic herring-bone motif. In the structure of 1,5-diaminoanthraquinone the molecules are connected via N H⋯O hydrogen bonds in the 2D networks of (4,4) topology. These molecular networks are further stacked by face-to-face π−π and carbonyl−carbonyl interactions. The supramolecular organizations of these two compounds are compared with other simple aminoanthraquinones (with at least one non-substituted amino group) thus providing more insights into the basic principles of the solid-state assembling for this class of molecules.

'Metalloaromaticity' of metal chelate ring. π–π stacking interactions in solid-state supramolecular architecture of copper(II) complexes with aromatic ligands

'Metalloaromaticity' of metal chelate ring. π–π stacking interactions in solid-state supramolecular architecture of copper(II) complexes with aromatic ligands

Control of Supramolecular Architecture in LB Films: Tiling the Plane With Macrorings and Interlocking the Modules

Abstract A strategy to control a solid state supramolecular architecture is reported and illustrated by the elaboration of a two dimensional polymer of molecular thickness.