Seven substituted dithiolene systems with acetylacetonate, 3,4-dimethylpyrazole (HPz), and 3,4-dimethoxybenzyl moieties were synthesized by nucleophilic substitution, cyclocondensation, and transchalcogenation reactions. The seven compounds were characterized by NMR and X-ray diffraction techniques. The single-crystal X-ray diffraction analysis revealed that 4,5-bis[(2,4-dioxopentan-3-yl)sulfanyl]-1,3-dithiol-2-one, C13H14O5S4 or DMIO(acac)2, and 4,5-bis[(3,5-dimethylpyrazol-4-yl)sulfanyl]-1,3-dithiole-2-thione methanol monosolvate, C13H14N4S5·CH3OH or DMIT(HPz)2, crystallized in the triclinic P-1 and monoclinic P21/n space groups, respectively, while 4,5-bis[(3,4-dimethoxybenzyl)sulfanyl]-1,3-dithiole-2-thione, C21H22O4S5 or DMIT(3,4-dimethoxybenzyl)2, and 4,5-bis[(3,4-dimethoxybenzyl)sulfanyl]-1,3-dithiol-2-one, C21H22O5S4 or DMIO(3,4-dimethoxybenzyl)2, crystallized in the monoclinic space groups P21/n and P21/c, respectively. Methyl 4-({[5-({[4-(methoxycarbonyl)phenyl]methyl}sulfanyl)-2-sulfanylidene-1,3-dithiol-4-yl]sulfanyl}methyl)benzoate, C21H18O4S5 or DMIT(4-methylbenzoate)2, and methyl 4-({[5-({[4-(methoxycarbonyl)phenyl]methyl}sulfanyl)-2-oxo-1,3-dithiol-4-yl]sulfanyl}methyl)benzoate, C21H18O5S4 or DMIO(4-methylbenzoate)2, crystallized in the orthorhombic P212121 and monoclinic P21/n space groups, respectively. Similarly, 4-{[(5-{[(4-carboxyphenyl)methyl]sulfanyl}-2-oxo-1,3-dithiol-4-yl)sulfanyl]methyl}benzoic acid, C19H14O5S4 or DMIO(4-methylbenzoic acid)2, crystallized in the monoclinic space group P21/c. The molecular packings of the seven crystalline compounds were stabilized by a variety of intermolecular O...H, H...H, C...H, S...H, S...S, S...O, and N...H interactions, depending on the substituent group. Hirshfeld surface analysis confirmed the presence of the above-mentioned interactions and the percentage contributions of the interatomic contacts were determined by 2D fingerprint plots in the total Hirshfeld surface. Studies of the antiproliferative activity against the NCI-60 cell line panel were performed for selected 2-oxo-1,3-dithiole-4,5-dithiolate (DMIO) derivatives.
Aminoalcohol-based ligands incorporating heteroaromatic moieties, such as 2-(pyridin-2-ylamino)ethanol (L1), are of particular interest in coordination chemistry due to their dual donor character and conformational adaptability. A series of L1-based transition-metal complexes, namely, diacetatobis[2-(pyridin-2-ylamino)ethanol]palladium(II), [Pd(C2H3O2)2(C7H10N2O)2] or [PdL12(OAc)2] (1), and the copper(II) analogue (4), tetra-μ-acetato-bis{[2-(pyridin-2-ylamino)ethanol]rhodium(II)}, [Rh2(C2H3O2)4(C7H10N2O)2] or [Rh2L12(OAc)4] (2), and the copper(II) analogue (3), and the nitrate salt 2-[(2-hydroxyethyl)amino]pyridinium nitrate, C7H11N2O+·NO3- or L1·NO3 (5), were structurally characterized using single-crystal X-ray diffraction (SCXRD). Crystallographic analyses revealed well-defined coordination modes and distinct supramolecular architectures influenced by the nature of the metal centre. These findings demonstrate the ability of the L1 ligand to form well-defined crystalline complexes with Cu, Pd and Rh ions, providing valuable crystallographic benchmarks for understanding the coordination preferences and crystal packing effects in pyridyl-aminoalcohol systems. The presented results provide a foundation for the further design of ionic traps involving thermolabile moieties.
A promising trend in the search for new more effective and selective drugs is the search for structural analogues of amino acids. The structures and activities of both enantiomeric diethyl (1S,2R)- and (1R,2S)-1,2-bis(tert-butoxycarbonylamino)propylphosphonates (as the monohydrates, C17H35N2O7P·H2O), 1 and 2, respectively, and racemic diethyl (RS)-2-(tert-butoxycarbonylamino)propylphosphonate, 3, have been determined. The antimicrobial activity of 1, 2 and 3 was tested against reference bacterial strains and showed weak bioactivity against Gram-positive bacteria. ADME (absorption, distribution, metabolism and excretion) analysis indicates that the compounds may have gastrointestinal absorption. The compounds satisfy Lipinski's rules.
A structural analysis is developed for five bromine-substituted ferrocenyl chalcones; the crystal structures of three of these compounds are reported for the first time. 3-(4-Bromophenyl)-1-ferrocenylprop-2-en-1-one (1), 3-(3-bromophenyl)-1-ferrocenylprop-2-en-1-one (2), 3-(2-bromophenyl)-1-ferrocenylprop-2-en-1-one (3), 1-(4-bromophenyl)-3-ferrocenylprop-2-en-1-one (4) and 1-(3-bromophenyl)-3-ferrocenylprop-2-en-1-one (5), all [Fe(C5H5)(C14H10BrO)], were synthesized via a base-catalyzed Claisen-Schmidt condensation between the corresponding ketone and aldehyde, yielding three compounds (1-3) with ferrocene attached to the carbonyl group (System 1) and two (4 and 5) with ferrocene attached to the alkene directly (System 3). Also, the position of the Br atom in the aromatic ring changes in each compound. The effect of these two parameters is evaluated considering distinct compound features, crystal packing and supramolecular features. The compounds crystallize in multiple space-group types, namely, P21/n (1), P212121 (2), P21/c (3), Pca21 (4) and P1 (5). The majority of the intermolecular interactions arise from the ferrocene units and aromatic rings; for all compounds, the role of bromine in the crystal packing is evident by the presence of H...Br/Br...H, C...Br/Br...C and Br...Br intermolecular interactions. The position of the Br atom has effects on the crystal density, as well as the exhibited bromine interactions. The enone connectivity in System 3 for para- and meta-substituted ferrocenyl chalcones enables shorter interactions and more participation of the enone in short contacts in comparison to System 1. This is confirmed by Hirshfeld surface analysis (red spots for short contacts) and via generated two-dimensional fingerprint plots (unique features and green regions). In addition, the title compounds were analyzed by 1H NMR, 13C NMR and IR spectroscopy, and melting-point analysis.
In this work, we explore the structural and photoluminescent properties of 1',3',6',8'-tetramethylspiro[fluorene-9,9'-xanthene] (TMSFX), C29H24O. TMSFX was synthesized via a one-pot method and crystallized in the monoclinic space group P21/c. Single-crystal X-ray diffraction revealed a unique 90° crossover between the fluorene and xanthene segments. Photoluminescence studies showed that TMSFX exhibits strong blue-white fluorescence on excitation at 321 nm, with emission peaks at 405 and 431 nm, and a fluorescence lifetime of 3.1 ns. In contrast, the methyl-free analog spiro[fluorene-9,9'-xanthene] (SFX) is non-luminescent, highlighting the critical role of methyl groups in enhancing fluorescence. These findings demonstrate the significance of methyl groups in tuning the photophysical properties of organic molecules for potential optoelectronic applications.
Three rare-earth selenates, namely, poly[diaquadi-μ-selenato-μ-selenito-diytterbium], [Yb2(SeO3)(SeO4)2(H2O)2]n, poly[μ-(hydrogen selenito)-μ-selenato-ytterbium], [Yb(HSeO3)(SeO4)]n, and poly[[tetraaquatri-μ-selenato-dithulium] monohydrate], {[Tm2(SeO4)3(H2O)4]·H2O}n, were synthesized by hydrothermal methods. Single-crystal X-ray diffraction (SCXRD) analysis shows that all three compounds form three-dimensional framework structures constructed from interconnected LnOx polyhedra (Ln = Yb, Tm; x = 7-8) and selenate (SeO42-) and/or selenite (SeO32-) groups. Their compositions were further supported by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and their oxidation states were assessed by bond-valence-sum (BVS) calculations.
Salcaprozate sodium (SNAC) is a clinically approved oral permeation enhancer, notably used in the formulation of oral semaglutide. Despite its pharmaceutical importance, the crystallographic information of SNAC or its free acid form, salcaprozoic acid {systematic name: 8-[(2-hydroxyphenyl)formamido]octanoic acid, C15H21NO4, denoted HNAC}, has not been reported previously. Here, we present the first crystallographic and physicochemical characterization of HNAC using single-crystal X-ray diffraction and complementary analytical techniques. The structure reveals the molecular conformation, hydrogen-bonding network and packing features of HNAC, supported by a complementary solid-state dataset. These findings provide fundamental insights into the structural and physicochemical properties of this physiologically relevant form of SNAC.
The molecular structures of two novel cobalt aminodiphosphine (PNP) complexes (1 and 2) are reported, namely, bis[bis(diphenylphosphanyl)(pentyl)amine-κ2P,P']chloridocobalt(III) di-μ-chlorido-bis[dichloridocobalt(II)], [CoCl(C29H31NP2)2][Co2Cl6], and bis[bis(diphenylphosphanyl)(propan-2-yl)amine-κ2P,P']chloridocobalt(III) di-μ-chlorido-bis[dichloridocobalt(II)], [CoCl(C27H27NP2)2][Co2Cl6], featuring variation in the N-atom substituent, i.e. n-pentyl in complex 1 and isopropyl in complex 2. The asymmetric unit of complex 1 contains a five-coordinated cationic [CoCl{κ2-P,P-(N)-C5H11}2]2+ species and a [Co2(μ2-Cl)2Cl4]2- anion, while complex 2 includes a five-coordinated cation [CoCl{κ2-P,P-(N)-C3H7}2], half a [Co2(μ2-Cl)2Cl4]2- anion, and disordered diethyl ether and dichloromethane solvent molecules. The impact of ligand-induced strain, particularly due to the small bite angles of the PNP aminodiphosphine ligands, was examined in the context of geometric constraints and their influence on stability and reactivity. A Cambridge Structural Database (CSD) survey, along with a noncovalent interaction (NCI) analysis of the analogous [TMCln(PNP)2] (where TM = transition metal and n = 1 or 2) core, revealed an inverse correlation between P-TM-P bite angles and N...TM contact distances. This correlation is attributed to the influence of the van der Waals radius of the metal: smaller metals allow wider bite angles and stronger N...TM contacts, whereas larger metals favour narrower bite angles and longer N...TM distances. NCI analysis indicated significant steric repulsion at the TM...N contacts, reflecting strain imposed by ligand geometry. A comparison of sign(λ2)ρ eigenvalues suggests that Mo-P bonds exhibit weaker attractive interactions relative to Co-P and Ru-P bonds, with Cr-P bonds being the weakest. These findings provide pointers to structural and electronic factors governing coordination in PNP-ligated transition-metal complexes, offering rational design and catalytic and material applications.
Dissymmetric ligands have garnered interest due to their ability to simultaneously coordinate to multiple different acceptors. Herein, we report the synthesis of a dissymmetric thioether N,N'-bidentate ligand, namely, 2-[(6-chloropyrimidin-4-yl)sulfanyl]pyrimidine-4,6-diamine (C8H7ClN6S, L1), along with its hydrated form (C8H7ClN6S·H2O). In addition, we describe the structure of a nitrate salt of the protonated ligand {4,6-diamino-2-[(6-chloropyrimidin-4-yl)sulfanyl]pyrimidin-1-ium nitrate, C8H8ClN6S+·NO3-} and a cobalt(II) complex of L1 (dichlorido{2-[(6-chloropyrimidin-4-yl-κN3)sulfanyl]pyrimidine-4,6-diamine-κN3}cobalt(II), [CoCl2(C8H7ClN6S)]). The structures of all four compounds were determined by single-crystal X-ray diffraction and Hirshfeld surface analyses were performed. These analyses reveal unengaged hydrogen-bond donors and acceptors in both the neutral ligand and its water solvate, while protonation or metal coordination induces a conformational change that enables full engagement of hydrogen-bond donors. These structural insights have implications for the molecular design of ligands in ion-sensing applications.
The crystallization of a trimetallic cobalt-molybdenum-sodium metal-organic <!?tlsb=-0.05pt>framework, poly[μ-benzene-1,3,5-tricarboxylato-tetra-μ-oxido-cobaltmolybdenumtrisodium], UOW-10 or [Na3Co(MoO4)(BTC)]n, is achieved by solvothermal synthesis using benzene-1,3,5-tricarboxylic acid (H3BTC, C9H6O6) as a ligand precursor, Na2MoO4·2H2O and Co(NO3)2·2H2O as metal sources, and N,N-dimethylformamide (DMF) as the solvent. 3D electron diffraction (3D ED) reveals that the structure crystallizes in the monoclinic space group P21/c, with lattice parameters of a = 9.718 (2), b = 18.250 (3), c = 6.892 (9) Å, α = γ = 90, β = 96.156 (15)°, V = 1214.7 (4) Å3 and Z = 4. The phase purity of the bulk sample was confirmed using synchrotron powder X-ray diffraction. The organic ligands form a 2D layer, where cobalt and molybdenum are found, with sodium cations located between the layers. There are four crystallographically distinct sodium sites: three exhibit a distorted octahedral coordination geometry, while the remaining site is seven-coordinate. The cobalt has trigonal bipyramidal coordination geometry and molybdenum exhibits a tetrahedral coordination geometry. Half the sodium cations in the structure forms 1D column-like motifs via shared oxygen edges along the crystallographic c axis, which are cross-linked in b by the cobalt and molybdenum sites via bridging O atoms, while the other half of the sodium cations form 2D ribbons in the ac plane, propagating along c, linked by sharing oxygen edges and faces. The optical properties of UOW-10 were investigated through the use of UV-Vis spectroscopy, showing a bandgap of 1.8 eV. Deconvolution of the features in the visible-light region reveals that four peaks are present, which can all be ascribed to the d-d transitions from the trigonal bipyramidal cobalt. By means of thermogravimetric analysis (TGA) and variable-temperature powder X-ray diffraction (VT-PXRD), it is demonstrated that the material has thermal stability to 410 °C, after which structure collapse occurs, leading to a mixture of Na2MoO4, CoO and Co3Mo above 900 °C.
Nicotinamide (Nico) and derivatives of pyridine are important materials in both the pharmaceutical and agrochemical industries. In the 21st century, pyridine-based agrochemical products achieved commercial success because of their structural diversity and different modes of action that can be explored to improve the effectiveness of the compounds. In this article, we explore the cocrystallization of nicotinamide/isonicotinamide and substituted pyridines and their synthons to understand their ease of formation. A cocrystal of Nico and 2-chloro-3-hydroxypyridine (2Cl3OHPY) was synthesized using solution and mechanochemical methods, and characterized by X-ray diffraction. The structural stability and intermolecular interaction of the (Nico)·(2Cl3OHPY) cocrystal were investigated using differential scanning calorimetry (DSC) and density functional theory (DFT). The cocrystal has strong chain (N-H...N), dimer (N-H...O) and discrete (N-H...O) hydrogen bonds with energy strengths of -31.21, -66.99 and -36.82 kJ mol-1, respectively, and a short C-H...π bond that builds a twisted three-dimensional structure (viewed along the c axis) and stabilizes the crystal packing. The results show that the compound is chemically stable, and the two dominating interactions are electrostatic and dispersion energies. An analysis of the aromatic amide and pyridine synthon in the CSD reveals the presence of close supporting interactions that strengthen the N-H...N hydrogen bond. The understanding of the structural properties and intermolecular interactions in the (Nico)·(2Cl3OHPY) cocrystal and NH2...Npy synthon provided in this study could be used to design materials for different applications, including pigments, explosives, drugs, agrochemicals and food additives.
Among various glycolates, potassium glycolate glycolic acid (PGGA), ammonium glycolate glycolic acid (AGGA) and rubidium glycolate glycolic acid (RGGA) are isostructural, with the general formula A(C2H3O3)(C2H4O3) (A = K, NH4 and Rb). However, whether Na+ can occupy the A site and its effects on structure and properties remained unknown. This study synthesized sodium glycolate glycolic acid (SGGA), analyzed its composition, structure, vibrational spectra and thermal behaviour, and compared the results with PGGA. SGGA has the formula Na+·C2H3O3-·C2H4O3 or Na(C2H3O3)(C2H4O3), with orthorhombic crystallinity. Although the salt lacks chiral C atoms, it crystallizes in the unique chiral space group P212121. Among various glycolates, only PGGA and RGGA display relatively similar powder X-ray diffraction (PXRD) patterns, while those of other glycolates are distinctly different, providing a key basis for distinguishing A(C2H3O3)(C2H4O3) glycolates. Although SGGA and PGGA show closely related vibrational spectra and thermal behaviour due to structural similarities, differences are observed in certain spectral peaks. Moreover, PGGA decomposes into carbonates at a marginally higher temperature than SGGA. This work provides insight into glycolic acid bonding and the structural role of Na+ in glycolates, guiding new mineral discovery.
Mercaptopyridines, heteroaromatic compounds containing thiol groups, are widely studied for their applications in coordination chemistry, supramolecular design and materials science due to their selective binding properties and photoresponsiveness. In this work, we investigated the crystallization of 4-mercaptopyridine with cyanuric acid under strictly controlled conditions. A solution of both components in aqueous ethanol was subjected to UV irradiation and then allowed to crystallize slowly at 4 °C, followed by ambient conditions. Three crystalline products were isolated and were structurally characterized, namely, a cocrystal of cyanuric acid with 1,2-di(pyridin-4-yl)disulfane, C10H8N2S2·C3H3N3O3, (I), a cocrystal of cyanuric acid with di(pyridin-4-yl)sulfane, C10H8N2S·C3H3N3O3, (II), and a new 3:2 cocrystal of cyanuric acid with di(pyridin-4-yl)sulfane, 2C10H8N2S·3C3H3N3O3, (III). No crystalline material was obtained under dark conditions, and cocrystal (III) was observed only after UV irradiation, which also yielded larger and better-quality single crystals than visible light. The results are consistent with oxidative coupling of 4-mercaptopyridine in solution under the applied conditions, giving disulfane and sulfane species that subsequently cocrystallize with cyanuric acid. Two of the cocrystals correspond to previously reported forms [CSD refcodes KIRGIF and KIRGOL; Gogoi et al. (2023). J. Mol. Struct. 1289, 135806], whereas cocrystal (III) is reported here for the first time.
The reactions of racemic four-coordinated macrocyclic nickel(II) complexes [Ni(rac-L)](ClO4)2 (L is 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) with (S)- and (R)-phenyllactic acid in acetonitrile/water gave the two six-coordinated enantiomers [(R,R)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane][(S)-phenyllactato]nickel(II) perchlorate, [Ni(C9H9O3)(C16H36N4)]ClO4 or [Ni(S-Pla)(RR-L)]ClO4 (Λ-1), and [(S,S)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane][(R)-phenyllactato]nickel(II) perchlorate, [Ni(R-Pla)(SS-L)]ClO4 (Δ-1), respectively (Pla is phenyllactate). The reaction of [Ni(rac-L)](ClO4)2 with rac-Pla- produced a conglomerate, in which the RR and SS enantiomers preferentially coordinated to S-Pla- and R-Pla-, respectively, to give racemic Λ-1 and Δ-1. Chiral resolution during the reaction yielded enantiopure crystals. Single-crystal X-ray diffraction analyses showed that the NiII ions coordinated with the four N atoms of the macrocyclic ligand in a folded configuration and with two O atoms from the carboxylate and hydroxyl groups in complexes Λ-1 and Δ-1, to display octahedral coordination geometry. Compounds Λ-1 and Δ-1 are enantiomers that display hydrogen bonding of the [Ni(S-Pla)(RR-L)]+ and [Ni(R-Pla)(SS-L)]+ monomers to form one-dimensional zigzag chains. The homochiral natures of Λ-1 and Δ-1 were confirmed by circular dichroism spectral measurements.
The [3+2] cycloaddition of a chiral acridine-derived alkene with 2,4,6-trimethylbenzonitrile N-oxide yields two regioisomeric isoxazoline cycloadducts, each formed as a pair of diastereomers. Single-crystal X-ray diffraction analysis of (1S,2R,5S)-5-methyl-2-(propan-2-yl)cyclohexyl (4S,5S)-5-(acridin-4-yl)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1,2-oxazole-4-carboxylate (6b) and (1S,2R,5S)-5-methyl-2-(propan-2-yl)cyclohexyl (4R,5R)-4-(acridin-4-yl)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1,2-oxazole-5-carboxylate (7a) cycloadducts, both C36H40N2O3, unambiguously establishes the regiochemistry of the cycloaddition and the relative configuration at the newly formed stereogenic centres. The molecular structures reveal a rigid acridine framework linked to a slightly puckered isoxazoline ring, with the ester substituent adopting distinct orientations depending on the regiochemical outcome. In the solid state, the molecules are stabilized by weak C-H...O contacts involving the isoxazoline and ester functionalities, and by weak C-H...π interactions. These crystallographic results provide reliable structural benchmarks for acridine-based isoxazoline derivatives obtained via 1,3-dipolar cycloaddition reactions.
This article contributes to the development of Paper-Based Analytical Devices (PADs), a low-cost field-friendly platform for screening low-quality medicines. Our investigation focuses on famotidine, the active pharmaceutical ingredient (API) in Pepcid AC [an over-the-counter medicine used to treat gastroesophageal reflux disease (GERD)]. We report the successful isolation and characterization of several new crystalline forms of famotidine, focusing on the API itself rather than its PAD-activated colored complex. These forms include a famotidine hydrochloride polymorph, C6H14N7O2S+·Cl- (I), a famotidine hydrochloride hemihydrate salt, C6H14N7O2S+·Cl-·0.5H2O (II), and a famotidine nitrate salt, C6H14N7O2S+·NO3- (III). Unexpectedly, we also characterized a hydrolyzed famotidine complex, N-(diaminomethylene)-4-({[3-oxo-3-(sulfamoylamino)propyl]sulfanyl}methyl)thiazol-2-aminium chloride sesquihydrate, C8H15N6O3S3+·Cl-·1.5H2O (IV). The crystal structures reveal significant solid-state diversity: hemihydrate salt II exhibits two symmetry-independent famotidine hydrochloride molecules per asymmetric unit, while sesquihydrate salt IV shows four crystallographically-independent hydrochloride molecules and six symmetry-independent water molecules per standard unit. All four complexes display extensive hydrogen-bonded networks in the solid state. The detailed structural characterization of these crystalline complexes generates fundamental solid-state chemistry data; this knowledge is essential for predicting and controlling the drug performance and formulation stability of famotidine and crucially informs our development of PADs.
Butane-1,4-diyl bis(trifluoromethane-1-sulfonate), C6H8F6O6S2 or Bu(OTf)2, crystallizes in the monoclinic space group P21/c, with the crystal packing mainly stabilized by chalcogen and fluorine-fluorine interactions. Temperature-dependent X-ray diffraction measurements reveal smooth, continuous and anisotropic thermal expansion without any indication of phase instability or structural phase transition. The anisotropic contraction along the a and b axes leads to progressive shortening of the intermolecular distances and a concomitant reorganization of the short intermolecular contacts, consistent with SAPT2/jun-cc-pVDZ interaction energies calculated for dimers extracted from the crystal structures. Notably, theoretical conformational searches failed to reproduce the solid-state geometry. Biological assays indicate that Bu(OTf)2 does not exhibit cytotoxic properties toward either leukemia cells or healthy cells. Gravimetric measurements further indicate that Bu(OTf)2 is poorly soluble in water.
A novel asymmetrical bis-Schiff base, 3-({(E)-[bis(pyridin-2-yl)methylidene]hydrazinylidene}methyl)-1H-indole, C20H15N5 (3-D), incorporating both pyridine and indole units, was synthesized and structurally characterized alongside its cadmium(II) complex bis[3-({(E)-[bis(pyridin-2-yl)methylidene]hydrazinylidene}methyl)-1H-indole]dichloridocadmium(II) trihydrate, [CdCl2(C20H15N5)2]·3H2O (3-D-Cd). Single-crystal X-ray diffraction revealed that both compounds adopt discrete molecular architectures, with the complex exhibiting pronounced π-π stacking interactions, as confirmed by density functional theory (DFT) calculations. Comprehensive spectroscopic characterization (elemental analysis, HRMS, NMR, UV-Vis and fluorescence) was performed. Cytotoxicity assays against A375, A549 and HeLa cancer cell lines, as well as normal HFF-1 cells, demonstrated that, while 3-D is minimally toxic, 3-D-Cd selectively inhibits tumour cell proliferation with significantly reduced toxicity toward normal cells compared to CdCl2. These findings suggest the potential of 3-D as a detoxifying ligand and of 3-D-Cd as a candidate for use as a low-toxicity metal-based anticancer agent.
Crystals of formamidinium antimony, halides, FA3Sb2X9 {FA = [CH(NH2)2]+; X = Br- and I-} {or triformamidinium nonahalidodiantimony, (CH5N2)3[Sb2X9]}, have been synthesized using a counter diffusion crystal growth (CDCG) method in silica gel and their structures determined from single-crystal X-ray diffraction data. FA3Sb2Br9 belongs to the trigonal space group P3m1, which is known as the Cs3Bi2Br9 structure type, and FA3Sb2I9 belongs to the hexagonal space group P63/mmc, called the Cs3Cr2Cl9 structure type. The change of the anion type from bromide to iodide results in the change of the structure type and the connectivity of the Sb-X octahedra. These structures are described and compared to the crystal types known for vacancy-ordered triple-perovskites.
2-{[4-(4-Bromophenyl)-1H-1,2,3-triazol-1-yl]methyl}phthalimide, C17H11BrN4O, was synthesized by click chemistry employing a copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition. The molecule adopts an angular structure and was found to crystallize in the monoclinic system (space group P21/n, Z = 4). Reaction with morpholine in the presence of a base afforded 4-{[4-(4-bromophenyl)-2H-1,2,3-triazol-2-yl]methyl}morpholine, C13H15BrN4O, as the major product, involving a nucleophilic substitution of morpholine for the phthalimide group and migration of the substituent from N1 to N2 on the 1,2,3-triazole ring. The morpholine-substituted compound likewise crystallizes in the monoclinic system (space group P21/c, Z = 4) with the molecule exhibiting an angular shape. Both crystal structures appear to be governed by close packing, with weak C-H...O and C-H...N hydrogen bonds as the prevailing intermolecular interactions.