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We present 1-pentafluorophenyl-1H-pyrrole and some of its electrophilic substitution reactions: formylation and acetylations. The 2-substituted products formed in these reactions are selectively and in high yield converted into 3-substituted products by treatment with trifluoromethanesulfonic acid. A general synthesis of 3-acylpyrroles was developed by the trifluoromethanesulfonic acid-mediated rearrangement of the corresponding 2-acylpyrroles.

• Self-assembly of the dithiophosphonate tectons generating supramolecular synthons via N H···S, N H···O, C H···S, C H···O, C H···π, and lp···π interactions. • Connection between molecular and supramolecular chirality in the crystalline state (chirogenesis). • NCI index analysis supports the proposition of P-stereogenic centers. • Chiral transference of the p atom to the supramolecular helical assembly. • Spontaneous resolution process to generate the homochiral crystal. The self-assembly of the dithiophosphonate tectons synthesized in this work generated novel supramolecular synthonsvia N H···S, N H···O, C H···S, C H···O, C H···π, and lp···π interactions. The reaction of the salts with chloro dithiastibocanes X(CH 2 CH 2 S) 2 SbCl (X = O , S) led to the formation of coordination compounds in which the crystal structures showed two new supramolecular synthons stabilized by C H···π and lp···π interactions. The theoretical study of the electronic density of the crystal and their synthons in the solid-state used the robust NCI index to confirm the nature of the interactions found. This study confirmed the connection between molecular and supramolecular chirality in the crystalline state. Three significant features unequivocally support the findings: the role of intramolecular interactions, the electronic density differences among diastereomers, and the nature of trans-annular bonds. The characterization of the salts: ammonium-menthoxy (4-methoxyphenyl) dithiophosphonate (1), triethylammonium-menthoxy (4-methoxyphenyl)-dithiophosphonate (2), triethylammonium-biphenyl-4‑methoxy (4-methoxyphenyl) dithiophosphonate (3), and the coordination compounds O(CH 2 CH 2 S) 2 Sb[S 2 P(biphenyl-4‑methoxy)(4-MeOC 6 H 4)] (4) and S(CH 2 CH 2 S) 2 Sb[S 2 P(biphenyl-4‑methoxy)(4-MeOC 6 H 4)] (5) was carried out by elemental analyses, IR, NMR (1H, 13C, 31P), and single-crystal X-ray diffraction analysis. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Metal complexes with Schiff base ligands are interesting for biological and pharmacological applications. • A new manganese complex (3) has been synthesized and characterized. • Interesting hydrogen-bonding supramolecular synthons are present in (3) • Intermolecular electrostatic interactions play a crucial role in building supramolecular metal complexes. • Complementary experimental and theoretical methods are used for the study of (3) • Schiff base of (3) has an interesting biological activity. MnII-based coordination compound [MnII(L) 2 (NO 3)(H 2 O) 3 ]NO 3 (3) has been synthesized with Shiff's base N2-benzylidenyl isonicotinic acid hydrazide (2) and (Mn(NO 3) 2 ⋅4H 2 O). The compound is new and has been fully characterized by FT-IR, UV–visible, 1H and 13C NMR spectroscopic techniques and single-crystal X-ray diffraction complemented with a quantum chemical study performed with DFT method. The compound crystallized in the monoclinic centrosymmetric P 2 1 /n space group. The crystal structure of (3) exhibits a nitrate anion and a non-centrosymmetric complex cation [MnII(L) 2 (NO 3)(H 2 O) 3 ]+. In the molecular packing, the different entities are held together through intermolecular strong, weak and non-conventional O/N/C H⋯O hydrogen bonds, that found to be effective in stabilizing the three-dimensional network. Furthermore, the crystal structure of (3) contains interesting cyclic supramolecular homo and heterosynthons. Moreover, π–π stacking and N lone-pair ...C H intermolecular electrostatic interactions play a crucial role in building a supramolecular layered network. To better understand the contribution of different intermolecular interactions to the supramolecular assembly, Hirshfeld surface analysis was performed. The obtained results indicate that the main contributions are attributed to O H⋯O, N H⋯O and C H⋯O interactions which are the primary giver the stabilisation in the crystal. The theoretical achievements were found in a good relation with the experimental structural analysis. The HOMO and LUMO energies and molecular electrostatic potential surface were derived from the same basis and the natural population Mulliken charge distribution analysis showed the different electron donors which coordinate with manganese. In addition to that, the molecular docking for (2) and (3) investigation with the 2X22 enzyme involved in Mycobacterium tuberculosis H37Rv have been conducted in order to check the biological activity of the Schiff base and its complex. [ABSTRACT FROM AUTHOR]

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol-dipyridylethylene (PGL:DPE) and phloroglucinol-phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single-component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape. [ABSTRACT FROM AUTHOR]

A simple strategy for designing salt-based supramolecular gelators comprised of various nonsteroidal anti-inflammatory drugs (NSAIDs) and amantadine (AMN) (an antiviral drug) has been demonstrated using a supramolecular synthon approach. Single-crystal and powder X-ray diffraction established the existence of the well-studied gel-forming 1D supramolecular synthon, namely, primary ammonium monocarboxylate (PAM) synthon in all the salts. Remarkably five out of six salts were found to be capable of gelling methyl salicylate (MS)-an important ingredient in commercially available topical gels; one such selected biocompatible salt displayed an anti-inflammatory response in prostaglandin E2 (PGE2) assay, thereby indicating their plausible biomedical applications. [ABSTRACT FROM AUTHOR]

A new supramolecular synthon, a 2L: 1M complex of bidentate bispidine with transition metal, was suggested. A number of complex compounds of 1,5-dimethylbispidin-9-one with Cu, Ni, and Co salts (perchlorates, chlorides, bromides, nitrates, trifluoroacetates) were synthesized. The structure and composition of complexes obtained were estimated based on the combination of physicochemical methods of analysis (elemental analysis, X-ray diffraction analysis, NMR, IR, and Raman spectroscopy, electron absorption spectroscopy, ESI mass spectrometry, CVA). The composition of most complexes in the solid state corresponds to the formula MLX, and in a number of cases the fragment [ML] is retained in solution, which was shown by NMR spectroscopy for nickel complexes and by mass spectrometry for copper complexes. In the case of copper chloride, the composition of the acetonitrile solutions in the presence of the ligand depends on the ratio of starting compounds and their concentration: an increase in proportion of CuCl and concentration shifts the equilibrium to the side of complexes with higher nuclearity. A 2L: 1M complex of bispidine with metal was for the first time structurally characterized using copper( ii) nitrate derivative as an example. The CVA method showed existence of reversible electrochemical reduction of the metal for a number of complexes (the products of the reaction of 1,5-dimethylbispidin-9-one with nickel( ii) and cobalt( ii) chlorides, as well as with nickel( ii) bromide). According to the IR and Raman spectra, chelation of metals with 1,5-dimethylbispidin-9-one leads to the shift of the absorption band of the ligand carbonyl group from 1700 to 1721-1744 cm. Nickel( ii) and copper( ii) perchlorates and nitrates were concluded to be the most promising complexation agents for the binding of two NH,NH-bispidine ligands in a coordination polymer. [ABSTRACT FROM AUTHOR]

Highlights: [•] Two three-dimensional supramolecular salts 1 and 2 have been prepared. [•] Robust hydrogen bonds generate interesting anionic substructures. [•] Thermal analysis showed they undergo an irreversible phase transition. [•] Dielectric studies suggested a low-frequency thermal fluctuation. [Copyright &y& Elsevier]

In this paper we study the manifestations of cooperative effects in the formation of supramolecular synthons observed in some thiohydantoin derivatives crystals. Energetic and structural properties were analyzed from the fully optimized clusters employing a DFT/B3LYP level of calculations, which reproduce the main features of the stereochemistry and geometries of the synthons exhibited by reported crystalline structures. The calculations performed in this work have also evidenced that the cluster stabilization is mainly due to the existence of strong cooperative effects, which display energetic as well as geometrical manifestations. The stabilization energy and stabilization energy per monomer, that comprises all the intermolecular interactions between the individual molecules that form the clusters, were computed, showing that the supramolecular clusters of 5-sec-butyl-2-tioxoimidazolidin-4-one is less stable than the compound 5-isopropyl-2-tioxoimidazolidin-4-one by 1.16 Kcal/mol. Finally, through this work it has been also evidenced the need of employing large basis sets, including polarization and diffuse effects, in order to properly model all the interactions existing in systems bonded by weak interactions. [ABSTRACT FROM AUTHOR]

Synthetic supramolecular structures constructed through the cooperative action of numerous non-covalent forces are highly desirable as models to unravel and understand the complexity of systems created in nature via self-assembly. Taking advantage of the low cost of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) and the sequential nucleophilic substitution reactions with almost all types of nucleophiles, a series of six structurally related novel s-triazine derivatives 1-6 were synthesized and structurally characterized based on their physical, spectral and crystallographic data. The solid-state structures of all the six compounds showed intriguing and unique molecular duplexes featuring NH···N, CH···O and CH···π interactions. Careful analysis of different geometric parameters of the involved H-bonds indicates that they are linear, significant and are therefore responsible for guiding the three-dimensional structure of these compounds in the solid state. The prevalence of sextuple hydrogen bond array-driven molecular duplexes and the possibility of structural modifications on the s-triazine ring render these novel triazine derivatives 1-6 attractive as a platform to create heteroduplex constructs and their subsequent utility in the field of supramolecular chemistry and crystal engineering., (© 2022 The Authors.)

Novel aurone derivatives e.g. 2-(2-(3-methylbut-2-enyloxy)benzylidene)benzofuran-3(2H)-one (3a), 2-(2-(allyloxy)benzylidene)-7-methoxybenzofuran-3(2H)-one (3b), and 2-(5-bromo-2-(3-methylbut-2-enyloxy)benzylidene)-6-hydroxybenzofuran-3(2H)-one (3c) were synthesized. All these compounds were characterized by IR,1H and13C NMR, and Mass spectroscopy. Finally, the crystal structures were solved by single crystal X-ray diffraction data and the structures were analyzed in terms of supramolecular interactions. [Supplementary materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals for the following free supplemental resource(s): supplemental figures 1–12; Spectral data (IR, NMR, MS, and HRMS) of the compounds3a, 3band3care available in the supporting information in .pdf format. Crystallographic information files (.cif) of compounds3a, 3b, and3care available in the electronic format.] [ABSTRACT FROM AUTHOR]

The article discusses the synthesis of two isostructural explosive cocrystals that have different thermodynamic stabilities. Each cocrystal contained diacetone diperoxide (DADP) and paired with either 1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB) or 1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB). It was found that the DADP/TBNTB cocrystal was unstable. The authors conclude that the DADP/TBTNB cocrystal is formed only by means of kinetic growth methods.

We report the crystal structures of two novel coordination compounds with similar complex composition: [Cd(Ac)(Bzimpy)] ( I) and [Zn(Ac)(Bzimpy)]·HO ( II). Both compounds are monomeric. Compound I consists of a Cd(II) center heptacoordinated with three N atoms from a Bzimpy molecule and four O atoms from two bidentate acetato molecules. Compound II consists of a Zn(II) center pentacoordinated with three N atoms from a Bzimpy molecule and two O atoms from two monodentate acetato molecules. A non-coordinated water molecule completes the formula. In addition, we highlight some common features in the supramolecular assembly of both compounds and with similar structures deposited in the version 5.33 of the CSD. This assembly occur through H-bridges and π-π offset stacked interactions, giving rise to the formation of what we call 'directed ring' of two types: two molecular components R and three molecular components R. Structures are viewed as composed of well defined substructures in order to analyze them. Graphical Abstract: The crystal structures of the title compounds are reported, highlighting similarities in the form of the 3-D construction of the crystal in a set of coordination compounds of transition metals containing one molecule of neutral, non-substituted Bzimpy ligand and two identical molecules of an H-bridge acceptor, non-strong H-bridge donor co-ligand.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Multifunctional molecules are capable of assembling via different supramolecular synthons, or hydrogen bond motifs, between the same or different functional groups, leading to the possibility of cocrystal. Utilization of the interplay of dimensionality (1-D, 2-D and 3-D), orientation of functional groups of the building blocks, influence of rigid/flexible linking groups, and weak interactions provides an interesting route for the creation of novel supramolecular architectures in the crystal lattice. N-unsubstituted 1H-benzotriazole and carboxylic acid, being self-complementary molecules, offer a broad scope of study of binary compounds based on the complementary combination of H-bonding/donating sites. We report here the construction of three extended molecular networks in cocrystals of the carboxylic acid group of the acid and the 1H-benzotriazole triazole moiety. We have been able to identify four major supramolecualr synthons that would be helpful in the prediction of structural motifs for these kinds of studies. Interestingly, these heterosynthons are strikingly similar, to those of the homosynthons of the individual functional groups. The nature of the aza groups helps to enhance the overall volume of the crystal lattice thus leading to the formation of various supramolecular assemblies. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss. [ABSTRACT FROM AUTHOR]

The two-component solid forms involving 4,4′-methylene-bis(benzenamine) included both salts and co-crystals, while 4,4′-methylene-bis(benzenamine) crystallized exclusively as a salt, in agreement with the differences in the p K values. Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon, and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton. A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H...N/O-H...O motif. The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons. In all adducts, recognition between the constituents is established through either N-H...O and/or O-H...O/O-H...N pairwise hydrogen bonds. In all adducts, COOH functional groups available on 1 and 2 interact with the N-donor compounds. The COOH moieties in 1 forms only single N-H...O hydrogen bonds, whereas in 2, it forms pairwise O-H...N/N-H...O hydrogen bonds. The supramolecular architectures are elegant and simple, with stacking of networks in 2, but a rather complex network with a threefold interpenetration pattern was found in 1. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss. [ABSTRACT FROM AUTHOR]

The results of crystallographic analyses on 1:1 and 1:4 well-defined co-crystals formed between glycine anhydride and each of 4-hydroxybenzoic acid and 3,5-dihydroxybenzoic acid are described. Neutral molecules are connected via heteromeric O-H...O and N-H...O contacts leading to different packing arrangements of supramolecular chains. On the basis of the molecular structures of glycine anhydride and carboxylic acid guests, the hydrogen bonds are arranged to give centrosymmetric synthons V and VII which are noteworthy for their robustness. Hydrogen-bond interactions between glycine anhydride and aromatic acid provide sufficient driving force to direct molecular recognition and crystal packing. Utilization of the orientation of functional groups of the building blocks, the acidity, and weak interactions provides a route for the creation of novel supramolecular architectures in the crystal lattice. Both two co-crystals contain the expected hydrogen-bonded motifs, and there has been no proton transfer from either of the two carboxylic acids to the aza compound moiety. This demonstrates that glycine anhydride is very capable of affecting the construction of binary co-crystals in a predictable and rationale manner. It is noted that synthons VIII and IX are fairly large, but the real challenge in crystal engineering is to find a big enough synthon that occurs often enough. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss. [ABSTRACT FROM AUTHOR]

Imidazole base was crystallized with different aromatic carboxylic acids 2,4-dihydroxybenzoic acid, 5-chlorosalicylic acid, and 1,8-naphthalic acid, affording three new binary molecular organic salts of [(CHN)·(CHO)] ( 1), [(CHN)·(CHOCl)]CHOCl ( 2), and [(CHN)(CHO)] ( 3). Proton transfer occurs from the COOH of carboxylic acid to nitrogen of imidazole in all complexes ( 1- 3), leading to the hydrogen bond N-H...O in all structures. To our knowledge, the recognition pattern between the carboxylic acid group and imidazole (acid-imidazole synthon) is less well-studied so far. The cooperation among COOH, COO and imidazolium cation functional groups for the observed hydrogen bond synthons is examined in the three structures. Generally, the strong N-H...O and O-H...O hydrogen bonds define supramolecular architecture and connectivity within chains, while weaker C-H...O hydrogen bonds play the dominant role in controlling the interactions between layers in these novel organic salts. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss. [ABSTRACT FROM AUTHOR]

Four hydroxybenzoic acid building blocks, m-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxyterephthalic acid, and 5-hydroxyisophthalic acid, have been synthesized as robust cocrystallizing agents and employed in reactions with piperazine, including [(CHN)·(CHO)] ( 1), [(CHN)·(CHO)] ( 2), [(CHN)·(CHO)] ( 3), and [(CHN)·(CHO)]·2HO ( 4). Hydrogen-bonded directed assemblies of four salts were validated by single-crystal X-ray diffraction analysis. In compounds 1-4, hydroxybenzoic acids are all deprotonated and piperazine molecules are all protonated to form piperazine dications and keep the chair conformation. Thermal stability of these compounds has been investigated. [ABSTRACT FROM AUTHOR]

Benzotriazole, N,N′-dimethylpiperazine and N-methylpiperazine were applied to crystallize with 5-sulfosalicylic acid (5-HSSA), affording three new binary molecular cocrystals [(CHN)·(CHOS)]·HO ( 1), [(CHN)·(CHOS)]·HO ( 2) and [(CHN)·(CHOS)]·3HO ( 3) under general conditions. Proton-transferring occurs from acid to nitrogen of N-donor compounds in all compounds 1, 2 and 3. Analysis of the hydrogen-bonding synthons and their effects on crystal packing were also presented in the context of crystal engineering and host-guest chemistry. In compound 1, 1-D infinite chains are extended to a 2-D layered architecture via strong O-H...O hydrogen bonds and then to a 3-D network by N-H...O interactions. Compou 2 and 3 both have the 1-D chain which is formed by O-H...O bonds and weak C-H...O hydrogen bonds. A common intramolecular S(6) [synthon I] ring is formed by the hydroxyl with the carboxyl group in all three compounds. [ABSTRACT FROM AUTHOR]

The synthesis and crystallographic analysis of a new tris-THF compound, obtained by chemical degradation of a penta-THF precursor, is reported. The molecular structure of the tris-THF compound allows to definitively assess the stereoconfiguration of the parent penta-THF compound, that was known only partially. The tris-THF compound crystallizes in the monoclinic C2/ c space group with unit cell parameters a = 21.621(8), b = 7.481(4), c = 30.801(9) Å, β = 94.08(3)°, Z = 8. The final refinement converged to R = 0.0804 for 1,706 independent observed reflections having I > 2σ(I). The tris-THF compound adopts in the solid state a flexuous and wavy conformation due to the cis- trans- trans configuration of the three THF rings and to intramolecular H bonding. Molecules in the crystals form H-bonded chains that are wrapped around the crystallographic binary screw axes. The chains are also bonded to each other by H-bonding through $$ R_{4}^{4} (8) $$ and $$ R_{2}^{2} (14) $$ring motifs. Graphical Abstract: The tris-THF compound adopts in the solid state a flexuous and wavy conformation due to the cis- trans- trans configuration of the three THF rings and to intramolecular H bonding. Molecules in the crystals form H-bonded chains that are wrapped around the crystallographic binary screw axes. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

A V-shape diquinoline was synthesized so that it used nitro groups as alternative sensor groups to the halogens employed previously. The solid-state structure of its inclusion compound with formic acid was carefully investigated in term of crystal engineering and supramolecular chemistry. A ternary inclusion complex was obtained and its supramolecular interactions were carefully investigated and presented. The suitable X-ray crystals were obtained by crystallization of the host diquinoline from formic acid. The structure adopted acid⋯pyridine hydrogen-bonded cocrystal in addition to other non-covalent interactions. No proton-transfer process was detected; no salt formation. Graphical Abstract: A V-shape diquinoline was synthesized so that it used nitro groups as alternative sensor groups to the halogens employed previously. The solid-state structure of its inclusion compound with formic acid was carefully investigated in term of crystal engineering and supramolecular chemistry. A ternary inclusion complex was obtained and its supramolecular interactions were carefully investigated and presented. The suitable X-ray crystals were obtained by crystallization of the host diquinoline from formic acid (Figure 1).[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of Ni(dtc)2 [dtc=diethyldithiocarbamate] has been achieved by the interaction of NiL(ClO4)2 with sodium diethyldithiocarbamate. Although single crystal structure of this complex was already reported (R =10.6%), we were able to refine crystal structure up to R =2.99%. We also observed rare C–H⋯Ni anagostic interactions generally exhibited by d8 complexes which were overlooked previously. To investigate the structure of Ni(dtc)2 in solution, variable temperature NMR spectra in solution have also been recorded between 25 and −50°C. Ni(dtc)2 was also tested for antibacterial and antifungal activities. It showed higher activity against the bacteria and fungi than the known antibiotics. [ABSTRACT FROM AUTHOR]

The cocrystals of a pharmaceutical model rac-ibuprofen with two pyridine-containing cocrystal formers were synthesized and their solid-state structures were carefully investigated in terms of crystal engineering and supramolecular chemistry. The target cocrystals were obtained by solvent-free grinding of rac-ibuprofen with the given cocrystal former and then suitable X-ray crystals were grown in acetonitrile solution and characterized by X-ray crystallography. Both structures adopted homo and hetero supramolecular synthons as well as other noncovalent interactions. [ABSTRACT FROM AUTHOR]

This article investigates the recent research on a series of anilic acid molecules. The crystallisation of molecules in high symmetry space groups is discussed and rationalised by the arrangement of charge-transfer complexes, which leads to the occurrence of repeated embrace motifs. Since 1997, cyananilic acid (2,5-dicyano-3,6-dihydroxy-1,4-benzoquinone) has been explored due to its valuable physico-chemical features. It is an organic acid that has Mott-insulator properties and organic ferroelectricity. Understanding these properties is an active area of supramolecular chemistry. [ABSTRACT FROM AUTHOR]

Abstract: In the study of supramolecular synthons formed by the imide group, four polycyclic imides (2–5) with unsubstituted NH group have been synthesized. The parent compound (1), obtained previously, and its derivatives 2–5 have been characterized by an elemental analysis, FTIR, 1H NMR, 13C NMR and X-ray crystallography methods. The differences in supramolecular structure were discussed on the basis of the X-ray analysis and the solid-state IR spectra. Selected theoretical calculations of vibrational spectra and binding energies confirm the observations that follow from experiment. In particular, the observed splittings of bands corresponding to Cing vibrations in the solid-state IR spectra of 1, 2 and 5 are well predicted by quantum chemical calculations. The molecules 1–5, having chiral centers, crystallize in centrosymmetric space groups as racemic compounds. In the solid state the association motifs of the imide fragments seem to be related to the structure (molecular shape and substituents) of the interacting molecules. The strongest interactions are the Nimide–H…Oimide/epoxy hydrogen bonds. They stabilize cyclic dimers (1,2), infinite chains (3,5) and other patterns (4) in crystal architecture. Additionally, in the crystals electrostatic interactions involving Care observed; they form parallel (1) and anti-parallel (3,4) motifs. [Copyright &y& Elsevier]

Abstract: 1,2,3,4,5-Pentafluorodiphenyl disulfide (1) was synthesized from C6F5SCl and C6H5SSiMe3 in quantitative yield. The homo-crystals of disulfide 1 and co-crystals of 1,1′,2,2′,3,3′,4,4′,5,5′-decafluorodiphenyl disulfide (2) with naphthalene (stoichiometry 1:2, complex 4) and diphenyl disulfide (3) with octafluoronaphthalene (stoichiometry 2:1, complex 5) were prepared followed by XRD characterization. In the crystal lattice of 1, face-to-face and face-to-edge PhH/PhF orientations of neighboring rings were observed together with face-to-edge PhF/PhF orientations. For the face-to-face PhH/PhF orientation, the large offset of PhH and PhF groups excludes their π-stacking interaction which is very non-typical of the field. The crystal lattice of 4 reveals standard π-stacking interactions of the arene–polyfluoroarene type. While in the lattice of 4 each PhF ring interacts alternating with naphthalenes, in 5 two disulfides 3 are bridged by one octafluoronaphthalene with only one of the PhH rings of each disulfide interacting with the polyfluoroarene π-system. The large offset of neighboring molecules excludes however their π-stacking interactions in complex 5. An attempt to prepare 2/3 co-crystals failed. [Copyright &y& Elsevier]

Abstract: A set of six N-benzyl-3-spiro-succinimides with evaluated anticonvulsant activity has been crystallographically studied. In all crystals, in the absence of strong H-bond donors, only weak H-bonds of C–H…Oen found as intermolecular interactions. For six crystals, two main packing motifs of the strongest interactions of C(sp3)–H…Ormed two alternative supramolecular synthons. Additionally in all crystals, interactions with aromatic donors have been identified. The analogy in the chemical formulas of the studied species has been complemented by the similarity in the H-bonding patterns in the crystals. However, no relationship between molecular conformation and packing motif variations has been found. [Copyright &y& Elsevier]

Abstract: From X-ray diffraction data, the crystal lattice of 1,2,3,4-tetrafluoronaphthalene 1 is composed of infinite π-stacks revealing π–π interactions of the arene-arene, arene-polyfluoroarene and polyfluoroarene-polyfluoroarene types. On replacement of the C2-F fragment of 1 by a N atom (i.e. in going from 1 to 1,3,4-trifluoroisoquinoline 2) the enlarged offset of neighboring molecules within the stacks excludes their π–π interactions, and only the Fπ interaction of fluorine atom of the C1-F bond of one molecule with hydrocarbon ring of another is observed. Networks of shortened Ch xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si6.gif" overflow="scroll"> ⋯ Hld>1 and 2) and NHld>2) contacts also contribute to supramolecular tectonics of the crystals. Quantum chemical calculations at the PBE/cc-pVTZ level of theory on dimers of 1 and 2 result in geometries somewhat different from those observed in the solid state. [Copyright &y& Elsevier]

The asymmetric dithiadiazene BrC 6 F 4 NSNSC 6 H 4 NO 2 crystallizes in the space group P -1 and exhibits a 1D polar chain structure linked via structure-directing Br···O 2 N synthons. [ABSTRACT FROM AUTHOR]

After making a comparison between inorganic pigments and quinacridone, several experimental results ensuing from 30 years of research are presented. Following this, the bridging hydrogen bond and crystal engineering are treated with some definitions, the pigment finishing is touched upon and the π…σ correlation is introduced. This is regarded as mesomerism between two non-covalent bond types, namely charge transfer and H bonds. It is compared with the lattice of the carbon blacks and thus used to explain the excellent stability of the quinacridones. In conclusion, Desiraju''s supramolecular synthons serve in the interpretation of the somewhat abstract π…σ correlation. Quinacridone crystals are made up solely of π…π charge transfer bonds and bridging hydrogen bonds i.e. they contain both of these non-covalent bonding types in compact form. This means that each and every quinacridone molecule is in itself a source of supramolecular mesomerism which encompasses the entire crystal lattice. [Copyright &y& Elsevier]

Cocrystallization of the dithiadiazolyl (DTDA) radicals p-XC 6 F 4 CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p-XC 6 F 4 CNSSN] 2 [TEMPO] (1-5) whose structures all reflect a common S 4 ⋅⋅⋅O supramolecular motif. The nature of this interaction was probed by DFT calculations (M06/aug-cc-pVDZ) on 1 which revealed that the enthalpy of formation of the [C 6 F 5 CNSSN] 2 [TEMPO] supramolecular motif from [C 6 F 5 CNSSN] 2 and TEMPO is substantial (-54.0 kJ mol -1 ). Electronic structure calculations revealed a TEMPO-based doublet S= 1 / 2 configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is +78.9 kJ mol -1 higher in energy. An atoms-in-molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2-5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN⋅⋅⋅S-S synthon is sacrificed in order to form the new S 4 ⋅⋅⋅O interaction., (© 2022 Wiley-VCH GmbH.)

Two polymorphic forms of a conformationally flexible molecule, 5-[(Diphenylphosphoryl)methyl]-4-(prop-2-en-1-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione, were obtained by crystallization and characterized by X-ray diffraction analysis and differential scanning calorimetry. The relative stability of polymorphic forms was estimated with DFT calculations of crystal structures and isolated molecules. It turns out, that in the first more dense polymorph with higher cohesion energy and crystal lattice energy, the molecule adopts an energetically unfavorable conformation, and forms dimers with lower H-bond strength, as compared to the second polymorph. On the other hand, in the second polymorph, the molecule adopts almost the lowest-energy conformation and forms infinite chains via strong H-bonds. The first form that seems to be more thermodynamically stable at room temperature transforms into the second form via two endothermic phase transitions; the apparent irreversibility of the transition is due to high energy difference between the molecular conformations in crystals. [ABSTRACT FROM AUTHOR]

• A salt hydrate (4CA5SSA) was synthesized based on crystal engineering approach. • The crystal structure is stabilized by N H...O, O H...O and C H...O hydrogen bonding interactions. • The title crystal is thermally stable up to 239 °C. • The synthesized compound was evaluated for its antimicrobial activities. • Title crystal shows significant antioxidant activities comparison to the standard ascorbic acid. An organic molecular salt hydrate crystal, 4-chloroanilinium-5-sulfosalicylate monohydrate (4CA5SSA) was obtained in 2:2:1 ratio. A proton of SO 3 H group in 5-sulfosalicylic acid was transferred to nitrogen atom of 4-chloroaniline leading to form primary N H...O hydrogen bonding in its crystal structure. R 2 2(8) motif is also observed due to homo dimmer synthon of carboxylic acid. Further, the strong N H...O and O H...O hydrogen bonding interactions construct the supramolecular architecture whereas weak C H...O hydrogen bonds play the dominant role in controlling the interactions between layers in 4CA5SSA salt hydrate. The thermal stability of title crystal was determined by TG/DTA thermogravimetric analysis. The in vitro antimicrobial activity of 4CA5SSA crystal was investigated against bacterial and fungal pathogens. The title compound was also evaluated for its in vitro antioxidant susceptibilities through DPPH radical scavenging methods. [Display omitted] [ABSTRACT FROM AUTHOR]

• Adeninium derivatives are interesting for pharmaceutical and optical applications. • Two new adeninium-based hybrid materials have been synthesized and characterized. • Complementary experimental and theoretical approaches are used in this work. • DFT calculations confirm the inorganic organic charge transfer. • The 3D packings are controlled by hydrogen bonds and electrostatic interactions. In this paper, we report preparation and structure determination of two new adeninium-based hybrid compounds formed with selenious acid: adeninium hydrogen diselenite (I) and adeninium hydrogen selenite (II). Single crystals of (I) and (II) were obtained by slow evaporation and their X-ray structures are reported coupled with a quantum chemical density functional theory (DFT) studies. In the atomic arrangement, the different entities are held together through N/O—H ··· O, N—H ··· N and C—H ··· N/O hydrogen bonds on the Watson−Crick, Hoogsteen and sugar sites. Their overall three-dimensional architectures are mostly controlled by electrostatic interactions between the inorganic anion and organic cation frameworks and by hydrogen bonding. Furthermore, the crystal structures of (I) and (II) contain supramolecular homo and heterosynthons which are present in most similar structures. The similarities and subtle differences of the intermolecular interactions in the two crystal structures have been investigated and discussed using Hirshfeld surface analysis, fingerprint plots, and contact enrichment. The theoretical results are in good relation with the experimental structural analysis and confirm that the charge transfer occurs from inorganic anions to organic cations. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Multiple supramolecular functionalities of cyclic α-alkoxy tellurium-trihalides (including Te---O, Te---X (X = Br, I) and Te---π(C=C) supramolecular synthons) afford rich crystal packing possibilities, which consequently results in polymorphism or Z' > 1 crystal structures. Example of three crystal forms of cyclohexyl-ethoxy-tellurium-trihalides, one of which combines the packing of two others, affords a unique model to observe the supramolecular synthon evolution at the early stages of crystallization, when crystals on the way find themself at a carrefour between the evolutionally close routes, but fail to choose between two energetically close packing patterns, so taking the "middle path", which incorporates both of them (and results in two crystallographically independent molecules). In general, this allows a better understanding of the existing structures, and an instrument to search for the new polymorphic forms. [ABSTRACT FROM AUTHOR]

The synthesis, structural characterization and influence of solvents on the crystal packing of solvated complexes of ethacridine with phthalic acid: 6,9-diamino-2-ethoxyacridinium phthalate methanol solvate (1), 6,9-diamino-2-ethoxyacridinium phthalate ethanol solvate (2), 6,9-diamino-2-ethoxyacridinium phthalate isobutanol solvate (3), and 6,9-diamino-2-ethoxyacridinium phthalate tert-butanol solvate monohydrate (4) are described in this article. Single-crystal XRD measurements revealed that the compounds 1–4 crystallized in the triclinic P-1 space group, and the 6,9-diamino-2-ethoxyacridinium cations, phthalic acid anions and solvent molecules interact via strong N–H···O, O–H···O, C–H···O hydrogen bonds, and C–H···π and π–π interactions to form different types of basic structural motifs, such as: heterotetramer bis[···cation···anion···] in compound 1 and 2, heterohexamer bis[···cation···alcohol···anion···] in compound 3, and heterohexamer bis[···cation···water···anion···] in compound 4. Presence of solvents molecule(s) in the crystals causes different supramolecular synthons to be obtained and thus has an influence on the crystal packing of the compounds analyzed. [ABSTRACT FROM AUTHOR]

The synthesis, analytical characterisation and four X-ray structures of aromatic sulfonester trimers featuring a meta -substitution are reported. The title compounds feature either resorcinol or a 1,3-benzenedisulfonyl moiety as a central unit; one of the trimers exists in two polymorphic forms. Depending on the C aryl -SO 2 -O-C aryl torsion angles two main conformations have been detected: U- and W-shape. Only little influenced by the molecular conformation the prevailing non-covalent interaction in the packing of all four title structures are C–H⋯O contacts. Thereby, aromatic H atoms in ortho position to oxysulfonyl groups serve as hydrogen bonding donor and S O units as hydrogen bonding acceptors. In all cases the structures contain cyclic supramolecular synthons featurin R 2 2 (10) g either graph- R 2 2 (12) set descriptor for the resorcinol trimers and for benzenedisulfonic acid derivatives respectively. One of the two supramolecular synthons is also present in most published sulfontriester X-ray structures uninfluenced from the aromatic substitution pattern. Image 1 • Aromatic sulfonester trimers exist in two main conformations: U- and W-shape. • Prevailing non-covalent interactions are C–H⋯O contacts. • Aromatic H atoms ortho to OSO 2 groups serve as H donor and S O units as H acceptors. • Cyclic supramolecular synthons of the type R 2 2 (X) (X = 10–12) are commons motifs. [ABSTRACT FROM AUTHOR]

The nature of bifurcated hydrogen bonds prompted us to analyze the energy of supramolecular motifs on the example of new structures of carboxylic acids salts with amines, which guarantee a multitude of such interactions. Experimental and theoretical studies of four dicarboxylic salts with primary amine: ethylammonium succinate hydrate (1), tartrate hydrate (2) phthalate hydrate (3) and terephthalate (4) has been investigated along with study of the strength of interactions between the anions and cations. The complete topological analysis of the charge density for all new structures allowed designation of the estimated Cumulative Dissociation Energy (eCDE). Image 1 • A traditional structure refinement based on a spherical atom model, was improved by the use of transferred multipolar charge density parameters. • Interactions in the solid-state have also been characterized and classified by means of their estimated cumulative dissociation energy. • The analysis carried out on new structures prove the usefulness of self-organization mechanisms description. [ABSTRACT FROM AUTHOR]