Catalyzed syntheses of novel series of spiro thiazolidinone derivatives with nano Fe2O3: spectroscopic, X-ray, Hirshfeld surface, DFT, biological and docking evaluations.

Twelve spiro thiazolidinone compounds (A-L) were synthesized via either conventional thermal or ultrasonication techniques using Fe2O3 nanoparticles. The modification of the traditional procedure by using Fe2O3 nanoparticles led to enhancement of the yield of the desired candidates to 78-93% in approximately half reaction time compared with 58-79% without catalyst. The products were fully characterized using different analytical and spectroscopic techniques. The structure of the two derivatives 4-phenyl-1-thia-4-azaspirodecan-3-one (A) and 4-(p-tolyl)-1-thia-4-azaspirodecan-3-one (B) were also determined using single crystal X-ray diffraction and Hirshfeld surface analysis. The two compounds (A and B) were crystallized in the orthorhombic system with Pbca and P212121 space groups, respectively. In addition, the crystal packing of compounds revealed the formation of supramolecular array with a net of intermolecular hydrogen bonding interactions. The energy optimized geometries of some selected derivatives were performed by density functional theory (DFT/B3LYP). The reactivity descriptors were also calculated and correlated with their biological properties. All the reported compounds were screened for antimicrobial inhibitions. The two derivatives, F and J, exhibited the highest levels of bacterial inhibition with an inhibition zone of 10-17 mm. Also, the two derivatives, F and J, displayed the most potent fungal inhibition with an inhibition zone of 15-23 mm. Molecular docking investigations of some selected derivatives were performed using a B-DNA (PDB: 1BNA) as a macromolecular target. Structure and activity relationship of the reported compounds were correlated with the data of antimicrobial activities and the computed reactivity parameters.

Crystal structure determination and Hirshfeld surface analysis of N-acetyl-N-3-meth-oxy-phenyl and N-(2,5-di-meth-oxy-phen-yl)-N-phenyl-sulfonyl derivatives of N-[1-(phenyl-sulfon-yl)-1H-indol-2-yl]methanamine.

Two new [1-(phenyl-sulfon-yl)-1H-indol-2-yl]methanamine derivatives, namely, N-(3-meth-oxy-phen-yl)-N-{[1-(phenyl-sulfon-yl)-1H-indol-2-yl]meth-yl}acetamide, C24H22N2O4S, (I), and N-(2,5-di-meth-oxy-phen-yl)-N-{[1-(phenyl-sulfon-yl)-1H-indol-2-yl]meth-yl}benzene-sulfonamide, C29H26N2O6S2, (II), reveal a nearly orthogonal orientation of their indole ring systems and sulfonyl-bound phenyl rings. The sulfonyl moieties adopt the anti-periplanar conformation. For both compounds, the crystal packing is dominated by C-H⋯O bonding [C⋯O = 3.312 (4)-3.788 (8) Å], with the structure of II exhibiting a larger number, but weaker bonds of this type. Slipped π-π inter-actions of anti-parallel indole systems are specific for I, whereas the structure of II delivers two kinds of C-H⋯π inter-actions at both axial sides of the indole moiety. These findings agree with the results of Hirshfeld surface analysis. The primary contributions to the surface areas are associated with the contacts involving H atoms. Although II manifests a larger fraction of the O⋯H/H⋯O contacts (25.8 versus 22.4%), most of them are relatively distal and agree with the corresponding van der Waals separations.

Synthesis, structural studies and Hirshfeld surface analysis of 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridin-1-ium hexa-kis-(nitrato-κ2 O,O')thorate(IV).

Reaction of thorium(IV) nitrate with 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)meth-yl]pyridine (L) yielded (LH)2[Th(NO3)6] or (C14H13N4)2[Th(NO3)6] (1), instead of the expected mixed-ligand complex [Th(NO3)4 L 2], which was detected in the mass spectrum of 1. In the structure, the [Th(NO3)6]2- anions display an icosa-hedral coordination geometry and are connected by LH+ cations through C-H⋯O hydrogen bonds. The LH+ cations inter-act via N-H⋯N hydrogen bonds. Hirshfeld surface analysis indicates that the most important inter-actions are O⋯H/H⋯O hydrogen-bonding inter-actions, which represent a 55.2% contribution.

Synthesis, crystal structure and Hirshfeld surface analysis of [1-(4-bromo-phen-yl)-1H-1,2,3-triazol-4-yl]methyl 2-(4-nitro-phen-oxy)acetate.

The title compound, C17H13BrN4O5, was synthesized by a Cu2Br2-catalysed Meldal-Sharpless reaction between 4-nitro-phen-oxy-acetic acid propargyl ether and para-bromo-phenyl-azide, and characterized by X-ray structure determination and 1H NMR spectroscopy. The mol-ecules, with a near-perpendicular orientation of the bromo-phenyl-triazole and nitro-phen-oxy-acetate fragments, are connected into a three-dimensional network by inter-molecular C-H⋯O and C-H⋯N hydrogen bonds (confirmed by Hirshfeld surface analysis), π-π and Br-π inter-actions.

Crystal structures, phase transition, and Hirshfeld surface analyses of the bromide and chloride congeners of aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) halide.

During the course of exploring crystallization conditions in generating metal-organic frameworks (MOFs) for use in the crystalline sponge method, two discrete metal-organic complexes, namely, aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) bromide, [Zn(C18H12N6)(H2O)]Br2, and aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) chloride, [Zn(C18H12N6)(H2O)]Cl2, were encountered. Structures in the orthorhombic space group Pnma (No. 62) for the bromide congener at 299 K and the chloride congener at 100 K were obtained. A phase transition for the bromide congener occurred upon cooling from 299 to 100 K, yielding a crystal polymorph with four domains that exhibits monoclinic P21/m space-group symmetry (No. 11), which arises from conformational changes. The main intramolecular contacts that contribute to the crystal packing in all observed structures are H...H, Halide...H/H...Halide, C...H/H...C, and N...H/H...N. Intramolecular hydrogen bonding between the Zn-bound water and non-Zn-bound pyridyl N atoms is a prominent feature within the three-dimensional networks. Aromatic π-stacking between the non-Zn-bound pyridine rings and contacts involving the halide ligands further stabilize the crystal packing.

A novel one-dimensional thiocyanate-bridged cobalt(III) complex: synthesis, crystal structure characterization and Hirshfeld surface analysis.

A new one-dimensional thiocyanate-bridged cobalt(III) Schiff base complex, namely, catena-poly[[[4-bromo-2-((Z)-{[2-(thiophen-2-yl)ethyl]imino}methyl)phenolato-κ2N,O]cobalt(III)]-µ-thiocyanato-κ2N:S], [Co(SCN)(C13H11BrNOS)2]n or [Co(µ1,3-SCN)L2]n (1), where HL is 4-bromo-2-((Z)-{[2-(thiophene-2-yl)ethyl]imino}methyl)phenol, a bidentate Schiff base prepared from the condensation reaction of 5-bromosalicylaldehyde and 2-(thiophen-2-yl)ethylamine, has been synthesized by stirring Co(ClO4)2·6H2O, the Schiff base HL and ammonium thiocyanate (in a 1:2:1 molar ratio) in ethanol medium. The complex was characterized by FT-IR, electronic spectra and single-crystal X-ray diffraction (SC-XRD) studies. The SC-XRD data suggest that the compound crystallizes in the orthorhombic space group Pca21. The CoIII ion in 1 adopts a distorted octahedral geometry, the metal sites being six-coordinated by one thiocyanate N atom and one thiocyanate S atom in apical positions, and by two imine N atoms and two phenolate O atoms from two anionic L- ligands which form the basal plane. The thiocyanate ligand acts as a µ-1,3 bridge, joining neighbouring CoIII atoms and forming a uniform zigzag one-dimensional polymeric chain. The crystallographic data were also used in the Hirshfeld surface (HS) analysis, which aimed to investigate the nature and quantitative significance of any noncovalent intermolecular interactions inside the crystal lattice. The crystal void parameters have also been computed and show the molecules to be tightly packed.

Crystal structure and Hirshfeld surface analysis of two iHOFs based on CH...NC hydrogen bonding.

Two ionic hydrogen-bonded organic frameworks (iHOFs) assembled from 4-cyano-N-(4-cyanobenzyl)pyridinium, have been crystallized with Br- and antimony(III) pentabromide, [SbBr5]2-, as counter-ions and characterized. These are 4-cyano-N-(4-cyanobenzyl)pyridinium bromide, C14H10N3+·Br-, and bis[4-cyano-N-(4-cyanobenzyl)pyridinium] antimony(III) pentabromide, (C14H10N3)2[SbBr5]. The CH...NC interactions induced by templating anions construct disparate frameworks. Hirshfeld surface analysis indicated that these crystals exhibit two types of hydrogen-bonding interactions, specifically CH...NC and CH...Br. Consecutive reverse-parallel CH...NC hydrogen-bonding interactions in these crystals induced the formation of a large number of CH...NC bonds which exhibit both cis and trans configurations.

Crystal structure and Hirshfeld surface analysis of dimeth-yl(phen-yl)phosphine sulfide.

The title compound, C8H11PS, which melts below room temperature, was crystallized at low temperature. The P-S bond length is 1.9623 (5) Šand the major contributors to the Hirshfeld surface are H⋯H (58.1%), S⋯H/H⋯S (13.4%) and C⋯H/H⋯C contacts (11.7%).

Crystal structure and Hirshfeld surface analysis of 1-[6-bromo-2-(4-fluoro-phen-yl)-1,2,3,4-tetra-hydroquinolin-4-yl]pyrrolidin-2-one.

In the title compound, C19H18BrFN2O, the pyrrolidine ring adopts an envelope conformation. In the crystal, mol-ecules are linked by inter-molecular N-H⋯O, C-H⋯O, C-H⋯F and C-H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, C-H⋯π inter-actions connect mol-ecules into ribbons along the b-axis direction, consolidating the mol-ecular packing. The inter-molecular inter-actions in the crystal structure were qu-anti-fied and analysed using Hirshfeld surface analysis.

Crystal structure and Hirshfeld surface analysis of 6,6'-dimethyl-2,2'-bi-pyridine-1,1'-diium tetra-chlorido-cobaltate(II).

In the title mol-ecular salt, (C12H14N2)[CoCl4], the dihedral angle between the pyridine rings of the cation is 52.46 (9)° and the N-C-C-N torsion angle is -128.78 (14)°, indicating that the ring nitro-gen atoms are in anti-clinal conformation. The Cl-Co-Cl bond angles in the anion span the range 105.46 (3)-117.91 (2)°. In the extended structure, the cations and anions are linked by cation-to-anion N-H⋯Cl and C-H⋯Cl inter-actions, facilitating the formation of R 4 4(18) and R 4 4(20) ring motifs. Furthermore, the crystal structure features weak anion-to-cation Cl⋯π inter-actions [Cl⋯π = 3.4891 (12) and 3.5465 (12) Å]. Hirshfeld two-dimensional fingerprint plots revealed that the most significant inter-actions are Cl⋯H/H⋯Cl (45.5%), H⋯H (29.0%), Cl⋯C/C⋯Cl (7.8%), Cl⋯N/N⋯Cl (3.5%), Cl⋯Cl (1.4) and Co⋯H (1%) contacts.

Crystal structure of tris-{N,N-diethyl-N'-[(4-nitro-phen-yl)(oxo)meth-yl]carbamimido-thio-ato}cobalt(III).

The synthesis, crystal structure, and a Hirshfeld surface analysis of tris-{N,N-diethyl-N'-[(4-nitro-phen-yl)(oxo)meth-yl]carbamimido-thio-ato}cobalt(III) conducted at 180 K are presented. The complex consists of three N,N-diethyl-N'-[(4-nitro-benzene)(oxo)meth-yl]carbamimido-thio-ato ligands, threefold sym-metric-ally bonded about the CoIII ion, in approximately octa-hedral coordination, which generates a triple of individually near planar metallacyclic (Co-S-C-N-C-O) rings. The overall geometry of the complex is determined by the mutual orientation of each metallacycle about the crystallographically imposed threefold axis [dihedral angles = 81.70 (2)°] and by the dihedral angles between the various planar groups within each asymmetric unit [metallacycle to benzene ring = 13.83 (7)°; benzene ring to nitro group = 17.494 (8)°]. The complexes stack in anti-parallel columns about the axis of the space group (P), generating solvent-accessible channels along [001]. These channels contain ill-defined, multiply disordered, partial-occupancy solvent. Atom-atom contacts in the crystal packing predominantly (∼96%) involve hydrogen, the most abundant types being H⋯H (36.6%), H⋯O (31.0%), H⋯C (19.2%), H⋯N (4.8%), and H⋯S (4.4%).

Crystal structure and Hirshfeld surface analysis of 2-bromo-ethyl-ammonium bromide - a possible side product upon synthesis of hybrid perovskites.

This study presents the synthesis, characterization and Hirshfeld surface analysis of a small organic ammonium salt, C2H7BrN+·Br-. Small cations like the one in the title compound are considered promising components of hybrid perovskites, crucial for optoelectronic and photovoltaic applications. While the incorporation of this organic cation into various hybrid perovskite structures has been explored, its halide salt counterpart remains largely uninvestigated. The obtained structural results are valuable for the synthesis and phase analysis of hybrid perovskites. The title compound crystallizes in the solvent-free form in the centrosymmetric monoclinic space group P21/c, featuring one organic cation and one bromide anion in its asymmetric unit, with a torsion angle of -64.8 (2)° between the ammonium group and the bromine substituent, positioned in a gauche conformation. The crystal packing is predominantly governed by Br⋯H inter-actions, which constitute 62.6% of the overall close atom contacts.

Synthesis, structure and Hirshfeld surface analysis of 2-oxo-2H-chromen-4-yl penta-noate.

In the title compound, C14H14O4, the dihedral angle between the coumarin ring system (r.m.s deviation = 0.016 Å) and the penta-noate ring is 36.26 (8)°. A short intra-molecular C-H⋯O contact of 2.40 Šis observed. Hirshfeld surface analysis reveals that 46.1% of the inter-molecular inter-actions are from H⋯H contacts, 28.6% are from H⋯O/O⋯H contacts and 14.7% are from H⋯C/C⋯H.

Crystal structure and Hirshfeld surface analysis of a halogen bond between 2-(allyl-thio)-pyridine and 1,2,4,5-tetra-fluoro-3,6-di-iodo-benzene.

The crystal structure of the title 2:1 mol-ecular complex between 2-(allyl-thio)-pyridine and 1,2,4,5-tetra-fluoro-3,6-di-iodo-benzene, C6F4I2·2C8H9NS, at 100 K has been determined in the monoclinic space group P21/c. The most noteworthy characteristic of the complex is the halogen bond between iodine and the pyridine ring with a short N⋯I contact [2.8628 (12) Å]. The Hirshfeld surface analysis shows that the hydrogen⋯hydrogen contacts dominate the crystal packing with a contribution of 32.1%.

Synthesis, spectroscopic and crystallographic characterization of various cymantrenyl thioethers [Mn{C5HxBry(SMe)z}(PPh3)(CO)2].

Starting from [Mn(C5H4Br)(PPh3)(CO)2] (1a), the cymantrenyl thioethers [Mn(C5H4SMe)(PPh3)(CO)2] (1b) and [Mn{C5H4-nBr(SMe)n}(PPh3)(CO)2] (n = 1 for compound 2, n = 2 for 3 and n = 3 for 4) were obtained, using either n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium tetramethylpiperidide (LiTMP) as base, followed by electrophilic quenching with MeSSMe. Stepwise consecutive reaction of [Mn(C5Br5)(PPh3)(CO)2] with n-BuLi and MeSSMe led finally to [Mn{C5(SMe)5}(PPh3)(CO)2] (11), only the fifth complex to be reported containing a perthiolated cyclopentadienyl ring. The molecular and crystal structures of 1b, 3, 4 and 11 were determined and were studied for the occurrence of S...S and S...Br interactions. It turned out that although some interactions of this type occurred, they were of minor importance for the arrangement of the molecules in the crystal.

Investigation of structural, optical and mechanical behaviour of pure and Cr doped L-asparagine monohydrate single crystals.

Pure and chromium (Cr) doped L-asparagine monohydrate (LAM) single crystals were grown by using evaporation controlled solution growth technique. XRD analysis confirmed the orthorhombic crystal system with space group P212121 of grown crystals. Cr-incorporation decreased the cell parameters and unit cell volume of the crystals. Intermolecular interactions were analysed through Hirshfeld and fingerprint studies. SEM analysis showed the appearance of pits on the smooth surface of pure crystal due to Cr-addition. UV-Vis analysis showed high transparency, low cut-off and direct band gap of 5.42 eV and 5.51 eV for pure and Cr doped crystals, respectively. Fundamental functional groups were identified by FTIR and Raman spectroscopy. The thermal stability and melting point of the crystals were investigated using TGA/DSC analysis. The dielectric constant for doped LAM was increased to 44 as compare to dielectric constant of pure crystal which was 32. Both crystals showed low dielectric loss, having values 0.04 and 0.006 for pure LAM and doped crystals, respectively. In Vickers microhardness test, Cr doping was found to change the nature of pure LAM crystal from 'soft' to 'hard' as Meyer's index changed from 2.48 to 1.24.

Structural Design, Anticancer Evaluation, and Molecular Docking of Newly Synthesized Ni(II) Complexes with ONS-Donor Dithiocarbazate Ligands.

The current article reports the investigation of three new Ni(II) complexes with ONS-donor dithiocarbazate ligands: [Ni(L1)PPh3] (1), [Ni(L2)PPh3] (2), and [Ni(L2)Py] (3). Single-crystal X-ray analyses revealed mononuclear complexes with a distorted square planar geometry and the metal centers coordinated with a doubly deprotonated dithiocarbazate ligand and coligand pyridine or triphenylphosphine. The non-covalent interactions were investigated by the Hirshfeld surface and the results revealed that the strongest interactions were π⋅⋅⋅π stacking interactions and non-classical hydrogen bonds C-H···H and C-H···N. Physicochemical and spectroscopic methods indicate the same structures in the solid state and solution. The toxicity effects of the free ligands and Ni(II) complexes were tested on the human breast cancer cell line MCF-7 and non-malignant breast epithelial cell line MCF-10A. The half-maximal inhibitory concentration (IC50) values, indicating that the compounds were potent in inhibiting cell growth, were obtained for both cell lines at three distinct time points. While inhibitory effects were evident in both malignant and non-malignant cells, all three complexes demonstrated lower IC50 values for malignant breast cell lines than their non-malignant counterparts, suggesting a stronger impact on cancerous cell lines. Furthermore, molecular docking studies were performed showing the complex (2) as a promising candidate for further therapeutic exploration.

Crystal structure and Hirshfeld surface analysis of dimethyl 2-oxo-4-(pyridin-2-yl)-6-(thio-phen-2-yl)cyclo-hex-3-ene-1,3-di-carboxyl-ate.

In the title compound, C19H17NO5S, the cyclo-hexene ring adopts nearly an envelope conformation. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming a three-dimensional network. In addition, C-H⋯π inter-actions connect the mol-ecules by forming layers parallel to the (010) plane. According to the Hirshfeld surface analysis, H⋯H (36.9%), O⋯H/H⋯O (31.0%), C⋯H/H⋯C (18.9%) and S⋯H/H⋯S (7.9%) inter-actions are the most significant contributors to the crystal packing.

The crystal structures and Hirshfeld surface analysis of three new bromo-substituted 3-methyl-1-(phenyl-sulfon-yl)-1H-indole derivatives.

Three new 1H-indole derivatives, namely, 2-(bromo-meth-yl)-3-methyl-1-(phenyl-sulfon-yl)-1H-indole, C16H14BrNO2S, (I), 2-[(E)-2-(2-bromo-5-meth-oxy-phen-yl)ethen-yl]-3-methyl-1-(phenyl-sulfon-yl)-1H-indole, C24H20BrNO3S, (II), and 2-[(E)-2-(2-bromo-phen-yl)ethen-yl]-3-methyl-1-(phenyl-sulfon-yl)-1H-indole, C23H18BrNO2S, (III), exhibit nearly orthogonal orientations of their indole ring systems and sulfonyl-bound phenyl rings. Such conformations are favourable for inter-molecular bonding involving sets of slipped π-π inter-actions between the indole systems and mutual C-H⋯π hydrogen bonds, with the generation of two-dimensional monoperiodic patterns. The latter are found in all three structures, in the form of supra-molecular columns with every pair of successive mol-ecules related by inversion. The crystal packing of the compounds is additionally stabilized by weaker slipped π-π inter-actions between the outer phenyl rings (in II and III) and by weak C-H⋯O, C-H⋯Br and C-H⋯π hydrogen bonds. The structural significance of the different kinds of inter-actions agree with the results of a Hirshfeld surface analysis and the calculated inter-action energies. In particular, the largest inter-action energies (up to -60.8 kJ mol-1) are associated with pairing of anti-parallel indole systems, while the energetics of weak hydrogen bonds and phenyl π-π inter-actions are comparable and account for 13-34 kJ mol-1.

Crystal structure and Hirshfeld surface of a penta-amine-copper(II) complex with urea and chloride.

The reaction of copper(II) oxalate and hexa-methyl-ene-tetra-mine in a deep eutectic solvent made of urea and choline chloride produced crystals of penta-amine-copper(II) dichloride-urea (1/1), [Cu(NH3)5]Cl2·CO(NH2)2, which was characterized by single-crystal X-ray diffraction. The complex contains discrete penta-amine-copper(II) units in a square-based pyramidal geometry. The overall structure of the multi-component crystal is dictated by hydrogen bonding between urea mol-ecules and amine H atoms with chloride anions.