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The synthesis of four novel amide compounds (R1C(O)NHR2) is reported, which contain both bulky (R1=phenyl and adamantyl) and hydrophilic (R2=hydroxyl, methoxyl) groups. The incorporation of such substituents provides compounds with unique properties that combine steric hindrance and hydrophilicity. The synthesized amides were fully characterized by 1H and 13C nuclear magnetic resonance (NMR) and analysed using infrared (IR) and Raman spectroscopy to investigate their vibrational properties in the solid phase, specifically focusing on the amide‐type normal modes of vibrations. Furthermore, the crystal structures of three derivatives were determined by single‐crystal X‐ray diffraction, which provided insights into their molecular arrangements. The occurrence of N−H⋅⋅⋅O=C hydrogen bonding intermolecular interaction is clearly observed and characterized by Hirschfeld surface analysis. Topology analysis using the Quantum Theory of Atom in Molecules and Crystals (QTAIM−C) were employed to investigate the electronic properties of the isolated amide molecules and to analyse the intermolecular interactions within the crystalline structure. The periodic calculations for the crystal revealed a higher electronic density in the C−N bond, indicating an increased covalent character in this bond compared with the C=O bond. This observation indicates the presence of resonance‐assisted hydrogen bonds within the amide core, leading to π electronic delocalization. [ABSTRACT FROM AUTHOR]

A series of 2-(haloalkyl)-3-azidomethyl and 6-azido chromones has been synthetized, characterized and studied by theoretical (DFT calculations) and spectroscopic methods (UV-Vis, NMR). The crystal structure of 3-azidomethyl-2-difluoromethyl chromone, determined by X-ray diffraction methods, shows a planar framework due to extended π-bond delocalization. Its molecular packing is stabilized by F···H, N···H and O···H hydrogen bonds, π···π stacking and C–O···π intermolecular interactions. Moreover, AIM, NCI and Hirshfeld analysis evidenced that azido moiety has a significant role in the stabilization of crystal packing through weak intermolecular interactions, where analysis of electronic density suggested closed-shell (CS) interatomic interactions. [ABSTRACT FROM AUTHOR]

Two new transition metal complexes with 1-methylimidazole (1-MeIm) and azide as ligands, namely, [Co(1-MeIm)4(N3)2] (1) and [Ni(1-MeIm)4(N3)2] (2), have been synthesized and characterized by IR, Raman, UV-Vis and XPS spectroscopy. Their crystal structures were solved by single-crystal X-ray diffraction. The supramolecular self-assembly of the two complexes is governed by non-classical C–H⋯N hydrogen bonds and C–H⋯π interactions. Lattice energies and intermolecular interaction energies for various molecular pairs are quantified using the PIXEL method. DFT computational studies to assess the binding energy through modern tools like non-covalent interaction (NCI plots) analysis and reduced density gradient (RDG) analysis have also been carried out. A detailed analysis of geometric descriptors revealed the existence of quasi-isostructural pairs or 'main-part' isostructuralism in a series formed by 1, 2, and a related cadmium complex, being more evident in the 1/2 pair. DFT studies using theoretical models have been used to disclose the relative importance of the H-bond and C–H⋯π noncovalent interactions. Magnetic measurements for compound 1 show weak ferrimagnetic coupling between adjacent M(II) centers, mediated by H-bonding and C–H⋯π non-covalent interactions. [ABSTRACT FROM AUTHOR]

The compound 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-9-ol (9-hydroxyeucaliptol) has been prepared and characterized by single-crystal X-ray diffraction analysis, infrared, Raman, and UV-visible spectroscopies. The molecular geometry of the title compound was also investigated theoretically by density functional theory (DFT) calculations to compare with the experimental data. The substance crystallizes in the trigonal crystal system, space group P32 with Z = 9 molecules per unit cell. There are three independent molecules in the crystal asymmetric unit having the same chirality and showing some differences in the orientation of the H-atom of the hydroxyl group. The crystal structure of 9-hydroxyeucaliptol shows that the hydroxyl group presents an anti-conformation with respect to the O-atom of the ether group. The crystal packing of 9-hydroxyeucaliptol is stabilized by intermolecular O-H···O hydrogen bonds involving the hydroxyl groups of different molecules, which play a decisive role in the preferred conformation adopted in solid state. The intermolecular interactions observed in solid state were also studied through the Hirshfeld surface analysis and quantum theory of atoms in molecules (QTAIM) approaches. Energy framework calculations have also been carried out to analyze and visualize the topology of the supramolecular assembly, and the results indicate a significant contribution from electrostatic energy over the dispersion. [ABSTRACT FROM AUTHOR]

M(II) complexes with sulfadiazine (SDZ) and imidazole (Im) acting as co‐ligand, [M(SDZ)2(Im)2] (M=Co, Ni, Cu and Zn), have been synthesized and characterized. The crystal structure of Co(II) complex (1) is reported, and a similar structure for the other three complexes is inferred by elemental analysis, IR and electronic spectra. The Co(II) complex is stabilized by intermolecular N–H⋅⋅⋅N, N–H⋅⋅⋅O and C–H⋅⋅⋅O hydrogen bonds, as well as C–H⋅⋅⋅π interactions. An investigation of those structural motifs via Hirshfeld surface analysis has been performed. Energy framework calculations have been carried out to analyze and visualize the 3D topology of the crystal assembly, indicating that the electrostatic energy is dominant over the dispersion one in the most energetic dimer (Motif 1), unlike two related cobalt‐sulfadiazine complexes with other co‐ligands where the dispersion component is more relevant. Further, the relative strength of the bifurcated N–H⋅⋅⋅N/O hydrogen bonds has been analyzed using the quantum theory of "atoms‐in‐molecules" (QTAIM) and molecular electrostatic potential (MEP) surface calculations. The strongest H‐bonds occurring with donor groups from co‐ligand species (Im, DMF and CH3OH) are found to be imperative in controlling the supramolecular architecture of the corresponding cobalt complex. [ABSTRACT FROM AUTHOR]

The reaction of N-phenyl-1-(pyridin-2-yl)methanimine with copper chloride dihydrate produced the title neutral complex, [CuCl2(C12H10N2)(H2O)]·H2O. The CuII ion is five-coordinated in a distorted square-pyramidal geometry, in which the two N atoms of the bidentate Schiff base, as well as one chloro and a water molecule, form the irregular base of the pyramidal structure. Meanwhile, the apical chloride ligand interacts through a strong hydrogen bond with a water molecule of crystallization. In the crystal, molecules are arranged in pairs, forming a stacking of symmetrical cyclic dimers that interact in turn through strong hydrogen bonds between the chloride ligands and both the coordinated and the crystallization water molecules. The molecular and electronic structures of the complex were also studied in detail using EPR (continuous and pulsed), FT-IR and Raman spectroscopy, as well as magnetization measurements. Likewise, Hirshfeld surface analysis was used to investigate the intermolecular interactions in the crystal packing. [ABSTRACT FROM AUTHOR]

The interaction of a poly-functional ligand derived from o-vanillin and 2-thiophenemethylamine (oVATPNH2) with transition metal ions Cu(ii) and Zn(ii) leads to the formation of stable coordination compounds, namely [Cu(oVATPNH2)2] and [Zn(oVATPNH2)2]. Their crystal structures have been determined by X-ray diffraction methods. Two molecules of the deprotonated ligand acting in a bidentate fashion build a nearly square planar environment around Cu(ii) and a distorted tetrahedral coordination arrangement for Zn(ii). The complexes were characterized by spectroscopic techniques, including solid state FTIR, Raman, EPR and diffuse reflectance and solution UV-vis and EPR. Their thermal behavior has been analyzed by means of TGA and DTA. DFT theoretical studies, using computational methods based on DFT, were employed to assist the interpretation and assignment of spectroscopic data. Cytotoxicity assays against two human breast cancer cell lines, namely MCF-7 and MDA-MB-231, revealed an enhancement of the effectiveness of the complexes as compared with both the ligand and the free metal ions. The results for the copper compound are promising, as its cytotoxic effect was stronger than the reference metallodrug cisplatin in both cancer cell lines tested. [ABSTRACT FROM AUTHOR]

Abstract Sulfadiazine Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized. The crystal structure of the cobalt(II) complex, for short [Co(SDZ) 2 (DMF) 2 ], was determined by X-ray diffraction methods. It crystallizes in the monoclinic space group P 2 1 / c with Z = 2 molecules per unit cell. The complex is centre-symmetric with the metal at the centre of a rectangular bi-pyramid environment (CoN 4 O 2 core), coordinated at the bi-pyramid base to two SDZ molecules and at the apices to two DMF solvent molecules. The crystal structure determination was combined with Hirshfeld surface analysis to obtain detailed information on the intermolecular interactions that stabilizes the crystal packing. The nature and strength of the Co N and Co O bonds were investigated by the natural bond orbital (NBO) analysis and the atoms in molecules (AIM) approach. Based on NBO and AIM analysis, the shorter Co N4 bonds are more covalent in nature than Co O bonds. The antibacterial assays of the metal complexes revealed lower activity than the free ligand, probably due to their low solubility in water. However, their low toxicity as compared with SDZ makes them potential alternatives against other microorganisms, and/or biological targets. Graphical abstract Image 1 Highlights • Co(II), Ni(II) and Cu(II) ternary complexes with Sulfaziadine and dimethylformamide as ligands have been synthesized. • The crystal structure of the Co(II) complex was determined by XRD methods. • Antibacterial activity of the ligand and complexes was evaluated. [ABSTRACT FROM AUTHOR]

The crystal structure of pyridinium 6-methyl-1,2,3,-oxathiazine-4(3H)-one-2,2-dioxide [(C5NH6)(C4H4NO4S)], for short, pyH(ace), was determined by X-ray diffraction methods. It crystallizes as a twin in the monoclinic space group P21/c with a=6.9878(9), b=7.2211(7), c=21.740(2) Å, β=91.67(1)° and Z=4 molecules per unit cell. The structure was determined employing 1599 reflections with I>2σ(I) from one of the twin domains and refined employing 2092 reflections from both crystal domains to an agreement R1 factor of 0.0466. Besides electrostatic attractions, intermolecular pyH···O=C(ace) hydrogen bonds stabilize the acesulfamate anion and the pyridinium cation into planar discrete units parallel to the (100) crystal plane. The units form stacks of alternating ace− and pyH+ ions along the a axis that favors inter-ring π–π interactions. The Fourier transform-infrared (FT-IR) spectrum of the compound was recorded and is briefly discussed. Some comparisons with related pyridinium saccharinate salts are also made. [ABSTRACT FROM AUTHOR]

The term ‘organic minerals’ means naturally occurring crystalline organic compounds including metal salts of formic, acetic, citric, mellitic, methanesulfonic and oxalic acids. As for the rest of the (inorganic) minerals, the primary tool to disclose their crystal and molecular structure and therefore to understand their mutual relationship with each other and with synthetic analogues and also their physicochemical properties is X-ray diffraction crystallography ever since the dawn of this methodology in 1913. The structure of several synthetic organic minerals was solved well before the discovery of their natural counterpart. On the other hand, complete crystal structure determination of early discovered organic minerals had to await the advent of combined synthetic and advanced X-ray diffraction methods to fully unveil their crystal structures. We review here the crystal chemistry of organic minerals and show the importance of structural studies on their synthetic analogues. This will be highlighted by case studies on the recently reported synthetic novgorodovaite, Ca2(C2O4)Cl2·2H2O, and its heptahydrate analogue, Ca2(C2O4)Cl2·7H2O, and the isotypic to each other stepanovite, NaMg[Fe(C2O4)3]·9H2O, and zhemchuzhnikovite, NaMg[AlxFe1−x(C2O4)3]·9H2O. [ABSTRACT FROM AUTHOR]

Synthetic novgorodovaite analog Ca2( C2O4) Cl4·2H4O is identical to its natural counterpart. It crystallizes in the monoclinic I2/m space group with a = 6.9352(3), b = 7.3800(4), c = 7.4426(3) Å, β = 94.303(4)°, V = 379.85(3) Å3 and Z = 2. The heptahydrate analog, Ca2( C2O4)Cl4·7H4O, crystallizes as triclinic twins in the P1 space group with a = 7.3928(8), b = 8.9925(4), c = 10.484(2) Å, α = 84.070(7), β = 70.95(1), γ = 88.545(7)°, V = 655.3(1) Å3 and Z = 2. The crystal packing of both calcium oxalate-chloride double salts favors the directional bonding of oxalate, C2O4 2-, ligands to calcium ions as do other related calcium oxalate minerals. The π-bonding between C and O atoms of the C2O4 2- oxalate group leaves sp2-hydridised orbitals of the oxygen atoms available for bonding to Ca. Thus, the Ca-O bonds in both calcium oxalate-chloride double salts are directed so as to lie in the plane of the oxalate group. This behavior is reinforced by the short O...O distances between the oxygens attached to a given carbon atom, which favors them bonding to a shared Ca atom in bidentate fashion. Strong bonding in the plane of the oxalate anion and wide spacing perpendicular to that plane due to repulsion between oxalate π-electron clouds gives rise to a polymerized structural units which are common to both hydrates, explaining the nearly equal cell constants ~7.4 Å which are defined by the periodicity of Ca-oxalate chains in the framework (monoclinic b ≈ triclinic a). When compared with novgorodovaite, the higher water content of Ca2( C2O4) Cl4·7H4O leads to some major differences in their structures and ensuing physical properties. While novgorodovaite has a three-dimensional framework structure, in the higher hydrate, the highly polar water molecules displace chloride ions from the calcium coordination sphere and surround them through OwH···Cl hydrogen bonds. As a result, polymerization in Ca2( C2O4)Cl4·7H4O solid is limited to the formation of two-dimensional Ca2( C2O4)(H4O)5 slabs parallel to (001), inter-layered with hydrated chloride anions. This layered structure accounts for (001) being both a perfect cleavage and a twin interface plane. The infrared and Raman spectra of both salts are also briefly discussed. [ABSTRACT FROM AUTHOR]

4,7-Dimethyl-2H-chromen-2-one (1) and its novel sulfur analogue 4,7-dimethyl-2H-chromen-2-thione (2) were synthesized and fully characterized by spectroscopic methods and mass spectrometry. The crystal structure of compound 2 has been determined by X-ray diffraction methods, and it crystallizes in the monoclinic I2/m space group. The molecular skeleton lies in the crystallographic mirror plane, in agreement with the expected theoretical planarity enforced by extended π-bonding. The crystal packing of both compounds is characterized by the R22(8) motif formed by intermolecular C–H…X=C (X = O and S) hydrogen-bonding interactions involving the 1-benzopyran-2-one/thione moiety, as also identified by Hirshfeld surface analysis. The vibrational properties have been studied by infrared and Raman spectroscopy complemented by quantum chemical calculations and normal coordinate analysis of the potential energy distribution. The UV-Vis spectrum is interpreted in terms of TD-DFT quantum chemical calculations, showing a clear red-shift in the HOMO–LUMO electronic transition when the chromen-2-one ring is converted into chromen-2-thione. [ABSTRACT FROM AUTHOR]

A new general synthetic procedure for preparation of Na3[Fe(C2O4)3]·5H2O (1), Rb3[Fe(C2O4)3]·3H2O (2), and Cs3[Fe(C2O4)3]·2H2O (3) was developed. The crystal structures of these salts have been determined by single crystal X-ray diffraction. Salt1crystallizes in the monoclinic space group C2/cwithZ = 8, salt2in P21/cwithZ = 4, and salt3in P21/nwithZ = 4. The three new salts and K3[Fe(C2O4)3]·3H2O, prepared for comparative purposes, were further characterized by infrared and57Fe-Mössbauer spectroscopy. These spectra are discussed in comparison with those of related oxalato complexes. [ABSTRACT FROM AUTHOR]

Magnesium acesulfamate, Mg(C4H4NO4S)2·6H2O, was prepared by the reaction of acesulfamic acid and magnesium carbonate in aqueous solution, and characterized by elemental analysis. Its crystal structure was determined by single crystal X-ray diffraction methods. The substance crystallizes in the triclinic space group P1̅ with one molecule per unit cell. The FTIR spectrum of the compound was also recorded and is briefly discussed. Some comparisons with other simple acesulfamate and saccharinate salts are also made. [ABSTRACT FROM AUTHOR]

The crystal structure of sodium and magnesiumtris(oxalato)chromato(III) nona hydrate, NaMg[Cr(C2O4)3]·9H2O, has been determined by X-ray diffraction methods. It crystallizes in the trigonalP3c1 space group with (in the hexagonal setting)a = b = 16.9635(4),c = 12.5247(3) Å, andZ = 6 molecules per unit cell. The Cr(III) and sodium ions are in octahedral environments coordinated to three oxalate molecules and arranged in a honeycomb-like layered structure perpendicular to the crystalc-axis. There are three different octahedral [Mg(H2O)6]2+hydrated ions that fill the honeycomb holes giving rise to electrically neutral Na[Mg(H2O)6][Cr(oxalato)3] crystal slabs. Neighboring slabs are bridged by the remaining three water molecules through H-bonds and therefore the whole crystal can be more properly described as Na[Mg(H2O)6][Cr(oxalato)3]·3H2O. Also, the structure of isomorphous NaMg[Al(C2O4)3]·9H2O compound has been re-examined and compared with the chromium(III) complex. Infrared and Raman spectra of both complexes were also recorded and briefly discussed. [ABSTRACT FROM PUBLISHER]

Three new acesulfamate salts, NaC4H4NO4S, RbC4H4NO4S and CsC4H4NO4S, were prepared by reactions in aqueous solutions and thoroughly characterized. Their crystal and molecular structures were determined by single crystal X-ray diffraction methods. They crystallize in the monoclinic space group P21/a with a = 7.2518(2), b = 8.9414(4), c = 10.5929(4) Å, β = 99.951(3)°, V = 676.52(4) Å3 for the Na salt; a = 7.4663(3), b = 9.6962(4), c = 10.4391(4) Å, β = 95.150(3)°, V = 752.68(5) Å3 for the Rb salt and a = 7.5995(4), b = 9.9439(4), c = 10.8814(6) Å, β = 91.298(5)°, V = 822.08(7) Å3 for the Cs salt, and Z = 4 molecules per unit cell. The three compounds are isotypic to each other and to the previously reported potassium salt. The metal ions are in irregular polyhedral coordination with six neighboring acesulfamate anions through their nitrogen and carbonyl and sulfoxide oxygen atoms. The FTIR spectra of the compounds were also recorded and are briefly discussed. [ABSTRACT FROM AUTHOR]

The title compound was prepared by reaction, in aqueous solution, of Tl2CO3 and H2C2O4·2H2O in a molar ratio of 1:2. Its crystal structure was solved by X-ray diffraction methods. It crystallizes in the monoclinic space group P21/a with Z = 2 molecules per unit cell. The oxalic acid molecule and the oxalate anion are planar, residing on crystallographic inversion centers, and linked to each other by strong O–H···O hydrogen bonds giving rise to a polymeric structure. The Tl(I) ion is in a distorted polyhedral coordination with nine neighboring O atoms, five of oxalate anions and four others of oxalic acid molecules. The FTIR and FT-Raman spectra of the compound were also recorded and are briefly discussed. [ABSTRACT FROM AUTHOR]

Highlights: [•] The molecular structure of the compound has been determined by X-ray diffraction. [•] The substance crystallizes in the monoclinic P21/c space group with Z =8 molecules per unit cell. [•] The conformers are arranged in the lattice as center-symmetric N H⋯O(sulf) bonded dimers. [•] For NBO analysis, the hyperconjugative interactions are favored in conformer 2 than conformer 1. [•] Infrared and Raman spectra showed bands assignable to 34 of the 36 vibrational normal modes. [ABSTRACT FROM AUTHOR]

The crystal and molecular structure of dilapacholateaqua(dimethylformamide)nickel(II) was determined by X-ray diffraction. It crystallizes in the triclinic space group P1 with a = 9.8671(9) Å, b = 10.654(1) Å, c = 15.289(2) Å, α = 86.98(1)°, β = 79.32(1)°, γ = 87.031(8)°, and Z = two molecules per unit cell. The structure was solved from 5094 reflections with I>2σ(I) and refined by full matrix least-square to an agreement R1-factor of 0.0564. The nickel(II) is in a NiO6 octahedral environment, cis coordinated to two lapacholate anions through their adjacent carbonyl [Ni-O distances of 2.075(2) and 2.066(2) Å], and phenyl oxygens [Ni-O lengths of 2.011(2) and 2.021(2) Å], and to a water [d(Ni-Ow) = 2.073(2) Å] and a DMF [d(Ni-O) = 2.076(2) Å] at axial positions. Some physicochemical and spectroscopic properties of the complex are also reported. [ABSTRACT FROM AUTHOR]

The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I>2σ (I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results. [ABSTRACT FROM AUTHOR]

A new Cu(II) complex is synthetized by the reaction of copper nitrate and a N-acylhydrazone ligand obtained from the condensation of o-vanillin and 2-thiophecarbohydrazide (H2L). The solid-state structure of [Cu(HL)(H2O)](NO3)·H2O, or CuHL for simplicity, was determined by X-ray diffraction. In the cationic complex, the copper center is in a nearly squared planar environment with the nitrate interacting as a counterion. CuHL was characterized by spectroscopic techniques, including solid-state FTIR, Raman, electron paramagnetic resonance (EPR) and diffuse reflectance and solution UV-Vis electronic spectroscopy. Calculations based on the density functional theory (DFT) assisted the interpretation and assignment of the spectroscopic data. The complex does not show relevant antioxidant activity evaluated by the radical cation of 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) method, being even less active than the free ligand as a radical quencher. Cytotoxicity assays of CuHL against three human tumor cell lines, namely MG-63, A549 and HT-29, revealed an important enhancement of the effectiveness as compared with both the ligand and the free metal ion. Moreover, its cytotoxic effect was remarkably stronger than that of the reference metallodrug cisplatin in all cancer cell lines tested, a promissory result in the search for new metallodrugs of essential transition metals. [ABSTRACT FROM AUTHOR]

The habit and the infrared spectra of the crystals obtained below 15 ºC (K 3 [Cr(CN) 5 NO].2H 2 O) and above 20 ºC (K 3 [Cr(CN) 5 NO]). • Accurate metrics of [CrI(CN) 5 NO]3- complex in its dihydrate potassium salt. • Advanced X-ray data collection and space group and structure solution and refinement. • K 3 [Cr(CN) 5 NO].2H 2 O isomorphic to the Mn(I) analogue. • IR and Raman spectra with assignment of water modes assisted by deuterium-enrichment. Potassium pentacyanonitrosylchromate(I) dihydrate salt, K 3 [Cr(CN) 5 NO].2H 2 O, forms spontaneously from aqueous solution below about 15 °C while the anhydrous salt is obtained above 20 °C. The molecular structure of the dihydrate has been determined by X-ray diffraction, taking full advantage of modern data collection, advanced space group and structure solution and refinement. It crystallizes in the monoclinic space group Cc , is isomorphic to the Mn(I) analog, and shows the pseudo-symmetry of space super-group C 2/ c. The [Cr(CN) 5 NO]3− ion has an umbrella-like conformation with the equatorial Cr-CN bonds slightly bent away from the Cr-NO link. The crystallographic study fills a gap left in the literature on accurate structural data for alkaline and alkaline-earth salts of [M(CN) 5 NO] n- (M = V, Cr, Mn, Fe) series of coordination compounds. We also report here the solid-state vibration structure of the new compound, as probed by IR and Raman spectroscopy. Water mode assignments were assisted through deuterium enrichment. The thermal dehydration behavior complements structural and spectroscopic information on water molecules. [ABSTRACT FROM AUTHOR]

The crystal structure of tetraaqua-bis(6-methyl-1,2,3-oxathiazin-4(3H)-onato 2,2-dioxide) copper(II) complex, for short [Cu(ace) 2 (H 2 O) 4 , was determined by X-ray diffraction methods. The complex crystallizes in the monoclinic C2/c space group with a = 11.9838(4), b = 9.5240(3), c = 15.1686(6) Å, β = 102.975(4)° and Z = 4 molecules per unit cell. The structure was determined from 1609 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0345. [Cu(ace) 2 (H 2 O) 4 is a new member in the family of acesulfamate complexes of first row transition metals, namely [M(ace) 2 (H 2 O) 4 , M: Co, Ni, Zn. It differs from the other members in the bonding of acesulfamate to metal through one of its sulfoxide oxygen atoms. The new complex was further characterized by its infrared, Raman and electronic absorption spectra, which were discussed in comparison with those of other related species. Image 101 • A new Cu(II) acesulfamato complex, [Cu(acesulfamato) 2 (H 2 O) 4 , was obtained. • It crystallizes in the monoclinic C2/c space group with Z = 4. • Bonding of acesulfamate to Cu(II) occurs through one of its sulfoxide O-atoms. • FTIR, Raman and electronic spectra were recorded and discussed. • Comparisons with related complexes were made. [ABSTRACT FROM AUTHOR]

• Novel poly-thiolactone synthesis with endocyclic ether, polyether, and lactone groups. • Controlled thioester bond formation using diacyl chlorides and organometallic tin compounds. • Preparation of diverse polythiolactones including cyclo and spiro compounds. • Single-crystal X-ray diffraction reveals structural characteristics based on ring size and functional groups. • Crystal packing governed by C-H···O hydrogen bonding and van der Waals interactions, forming unique tubular arrangements. The synthesis and isolation of new thiolactone species containing endocyclic ether, polyether, and lactone groups were designed using the reaction between diacyl chlorides with organometallic tin compounds as a template for controlled thioester bond formation. Thus, eight polythiolactones, including cyclo and spiro compounds with different ring sizes and functional groups were prepared, namely 1-oxa-4,9-dithiacycloundecane-5,8-dione (1a), 1-oxa-4,10-dithiacyclododecane-5,9-dione (1b), 1,4-dioxa-7,12-dithiacyclotetradecane-8,11-dione (2a), 1,4-dioxa-7,13-dithiacyclopentaecane-8,12-dione (2b), 2,15,19,32-tetraoxa-6,11,23,28-tetrathia-spiro[16.16]tritriacontane 3,7,10,14,20,24,27,31-octaone (3a), 2,16,20,34-tetraoxa-6,12,24,30-tetrathia-spiro[17.17]pentatriacontan-3,7,11,15,21,25,29,33-octaone (3b), 9,12,25,28-tetraoxa-6,15,22,31-tetratia-1(1,4),17(1,4)-diphenylcyclodotriacontane-5,16,21,32-tetraone (2c), and 2,17,21,36-tetraoxo-6,13,25,32-tetrathia-8(1,4)27(1,4)-diphenyl-spiro[18-18]heptatriacontane-3,7,12,16,22,26,31,35-octaone (3c). The structural characteristics of the eight closely related derivatives were determined by examining the impact of ring size and functional groups, through single-crystal X-ray diffraction techniques. The crystal packing of these polythiolactones was found to be mainly governed by weak C-H···O hydrogen bonding and van der Waals interactions, resulting in partially overlapping tubular arrangements. Hirshfeld analysis was performed to investigate the crystal packing and intermolecular interactions. The results of this study show the possibility of forming 3D tubular arrangements using polythiolactones with various endocyclic groups, including both flexible and rigid spacers. [Display omitted] [ABSTRACT FROM AUTHOR]

A new series of CuII, NiII, CoII, and MnIII complexes have been synthesised from the (6 Z)-6-(7-trifluoromethyl-1,2,3,4-tetrahydro-5 H -1,4-diazepin-5-ylidene)cyclohexa-2,4-dien-1-one (HDZP) ligand. These complexes were characterised by elemental, spectroscopic (IR and UV-vis), and thermal analysis. The crystal structure of Cu-DZP was solved by X-ray diffraction methods. The complex crystallises in the monoclinic P 21/ c space group, with two molecules per unit cell. The crystal lattice is stabilised by different intra and intermolecular interactions. Hirshfeld surface analysis was employed to obtain additional information about interactions that are responsible for the crystal packing. Quantitative examination of the fingerprint plots indicated the dominant contribution of H⋯H and H⋯X (X = O, F) interactions in the crystal packing. In addition, C–H⋯chelate ring (CR) and C–H⋯π interactions are described in detail and evaluated using DFT calculations. The antibacterial properties and the mechanism of inhibition of the main bacterial resistant mechanism, the biofilm, of the metal complexes and free ligand were investigated. [Mn(DZP)3]·2H2O was the most active complex against the Pseudomonas aeruginosa biofilm formation with an inhibition of 40 %. However, none of the complexes inhibit more than 25 % of the Gram negative bacteria microbial development. The most meaningful result was the bactericidal effect of [Co(DZP)2(H2O)2]·2H2O against the Gram positive bacteria, Staphylococcus aureus , which inhibits the bacterial development and significantly reduces the biofilm formation at low concentration. A new series of CuII, NiII, CoII, and MnIII complexes have been synthesised from the (6 Z)-6-(7-trifluoromethyl-1,2,3,4-tetrahydro-5 H -1,4-diazepin-5-ylidene)cyclohexa-2,4-dien-1-one (HDZP) ligand. These complexes were characterised by elemental, spectroscopic (IR and UV-vis), and thermal analysis. The crystal structure of Cu-DZP was solved by X-ray diffraction methods. [ABSTRACT FROM AUTHOR]

Three novel zinc and cadmium complexes with 1-methylimidazole and 2-methylimidazole as ligands, mono-nuclear dichloro-bis(1-methylimidazole) zinc(II) and dibromo-bis(2-methylimidazole)cadmium(II) monohydrate complexes, and poly-nuclear bis(1-methylimidazole)-di-(μ2-bromo)cadmium(II) complex, namely, compounds 1 – 3 , respectively, have been synthesized. The complexes were characterized by IR and Raman spectroscopies, thermal analysis and fluorescence. All the compounds exhibit interesting luminescent properties in solid state originated from intra-ligand (π→π*) transitions. Crystal structures of 1 – 3 were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in P 2 1 / n space group, the Zn(II) ion lies at a crystal general position in a tetrahedral environment, and the mono-nuclear units are weakly bonded to one another by C H ⋯ Cl hydrogen bonds. Compound 2 crystallizes in Pnma space group, and mirror-related tetrahedral units around Cd(II) ion are H-bonded through a water molecule. Compound 3 crystallizes in P 2 1 / c space group, and the Cd(II) ion presents a centrosymmetric octahedral coordination. Neighboring and equatorial edge-sharing octahedra conform a polymeric arrangement that extends along the crystal a -axis. Weak hydrogen bonds are the major driving forces in the crystal packing of the three complexes. Hirshfeld surface analysis reveals a detailed scrutiny of intermolecular interactions experienced by each complex. The surfaces mapped over d norm property highlight the X···H (X = Cl, Br) as the main intermolecular contacts for the three complexes, being also relevant the presence of O ⋯ H contacts for complex 2 . The surfaces mapped over Shape index and curvedness properties for the two Cd complexes allow identify π … π stacking interactions which are absent in the Zn complex. 2D fingerprint plots have been used to quantify the relative contribution of the intermolecular contacts to crystal stability of compounds, showing the crucial importance of weak interactions in building different supramolecular architectures. Furthermore, molecular electrostatic potentials for visualizing and quantifying the attractive character of interactions were calculated. [ABSTRACT FROM AUTHOR]

A family of hydrazones of isoniazid and a group of hydroxybenzalaldehydes (vanillin, 5-bromovanillin, 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde) were obtained and fully characterized. The results, including theoretical data, are comparatively analyzed along with the already reported hydrazone of o -vanillin. The crystal structures of three compounds were determined. The hydrazones obtained from halogenated aldehydes are isomorphic and chiral to each other. Structures are further stabilized by (pyr)NH + ⋯Cl − and OwH⋯Cl − bonds. The vanillin hydrazone shows a conformer that differs from the previously reported. Neighboring molecules are linked to each other through OH⋯N(pyr) bonds, giving rise to a nearly planar polymeric structure. The conformational space was searched and geometries were optimized both in the gas phase and including solvent effects by DFT. Results are extended to describe the 5-bromovanillin hydrazone. FTIR, NMR and electronic spectra were measured and assigned with the help of computational calculations. [ABSTRACT FROM AUTHOR]

Highlights: [•] Disulfide Schiff base from condensation of 2-aminothiophenol and o-vanillin. [•] X-ray diffraction crystal structures of the anhydrous and monohydrate forms. [•] Vibrational and electronic spectra assigned with the help of DFT calculations. [Copyright &y& Elsevier]

Two new copper(II)-hydrazone complexes with 2,2́ bipyridine or 1,10 phenanthroline as coligands were synthesized and characterized by spectroscopic methods. Their molecular structures were confirmed by single crystal X-ray diffraction. Both complexes were evaluated as antitumour agents. They showed higher cytotoxic activity against lung, bone and breast cancer cells lines than cisplatin. [Display omitted] • Two ternary Cu(II) hydrazone complexes were synthesized and characterized. • The complexes crystallize in a CuO 2 N 3 distorted square pyramidal environment. • The hydrazone adopts different tautomeric forms in the environment of each compound. • EPR data are consistent with the dx2-y2 ground state determined by XRD. • They are more cytotoxic than cisplatin on lung, bone and breast cancer cells lines. Two new penta-coordinated copper(II) hydrazone coordination compounds with 2,2́ bipyridine (I) or 1,10 phenanthroline (II) as coligands are synthesized and characterized in the solid state and in solution by spectroscopic methods (FTIR, Raman, UV–vis, EPR). Single crystal X-ray studies show that they have closely related molecular structures with the copper center in a distorted square pyramidal O 2 N 3 environment. The N -acylhydrazone, 4-hydroxy-NŃ-(E)2-hydroxy-3-methoxybenzylidene]benzohydrazide, H 2 L, coordinates tridentate through its ONO donor atoms as monoanion (HL-) in the cationic complex (I) , [Cu(HL)(bipy)](NO 3). During the period that takes the synthesis reaction of compound (II) , [Cu(L)(o -phen)] to complete, keto-amine to enol-imine tautomerization of H 2 L occurs and the hydrazone coordinates tridentate as dianionic ligand (L2-). The fivefold coordination sphere of the complexes is completed with the nitrogen atoms of the respective coligands. Cytotoxicity studies against bone (MG-63, IC 50 (I) = 5.6 ± 1.0 , IC 50 (II) = 3.5 ± 0.3), breast (MCF7, IC 50 (I) = 10.8 ± 1.9, IC 50 (II) = 4.0 ± 1.3), (MDA-MB-231, IC 50 (I) = 11.4 ± 0.6, IC 50 (II) = 5.3 ± 0.2) and lung cancer cells (A549, IC 50 (I) = 7.7 ± 0.7, IC 50 (II) = 7.0 ± 0.4) reveals increased effectiveness of both complexes compared with the free ligand, the copper nitrate salt and the reference metallodrug cisplatin (CDDP). [ABSTRACT FROM AUTHOR]

• Novel diselenide synthesized through bimolecular oxidation of selenourea intermediate. • Spectroscopy (FT-IR, Raman, NMR) confirms compound identity, revealing key signals. • X-ray diffraction unveils a centrosymmetric dimer with unique Se–Se bond arrangement. • Unusually wide open-book structure; aromatic rings in semiperpendicular arrangement. • Intriguing π···CH and C=O···Se interactions observed, influencing crystal packing. Acylselenourea diselenides, with the formula [RC(O)NC(Se)NR 2 ] 2 , are underexplored organoselenated compounds with potential applications in medicinal chemistry, coordination, and organic synthesis. This article presents a comprehensive study on the synthesis, spectroscopy, and structural characterization of the novel diselenide N,N '-diselanediyl-bis-((diphenylamino)methanylylidene)-dibenzamide, i.e., R = Phenyl. The compound was synthesized by a one-pot bimolecular oxidation between the tautomeric forms of the selenourea intermediate PhC(O)NHC(Se)N(Ph) 2. The total yield of the reaction was moderate (40 %), with losses attributed to the formation of amorphous red selenium. Spectroscopic analysis, including FT-IR, 1H NMR, and 13C NMR, confirmed the molecular identity of the compound. The crystal structure of diselenide was determined by single-crystal X-ray diffraction analysis, which revealed the formation of a centrosymmetric dimer through a bidirectional hydrogen bond of the C=O···H-Ph type. Hirshfeld surface (HS) analysis and topological study of electron density (ρ) provided detailed information on the strength of the intermolecular and intramolecular interactions in the crystal structure. [ABSTRACT FROM AUTHOR]

Abstract: Structural and conformational properties of the molecule bis[isopropoxy(thiocarbonyl)]sulfide, [(CH3)2CHOC(S)]2S, have been studied by vibrational spectroscopy (IR and Raman) and quantum chemical calculations (HF and B3LYP with 6-31+G∗ basis sets). The crystal and molecular structure of the title compound was determined by X-ray diffraction methods. It crystallizes in the monoclinic C2/c space group with a =8.4007(4), b =13.5936(5), c =10.3648(5)Å, β =106.024(4)° and Z =4 molecules per unit cell. The molecules are sited on a crystallographic twofold axis passing through the sulphide atom and arranged in layers perpendicular to the b-axis. The solid state IR and Raman spectra of the compound give no sign of any other rotamer. [Copyright &y& Elsevier]

Abstract: The synthesis and characterisation by solid-state 111Cd NMR of Cd(2,3-), Cd(2,4-), Cd(2,5-) and Cd(2,6-pyridinedicarboxylato)· xH2O is reported. Results indicate that the 111Cd NMR signal is very sensitive to the relative position of both carboxylates. Similar shifts (at 54.0 and 55.4ppm) are found for the 2,4- and the 2,6-isomers where the carboxylates groups are meta to each other. For the 2,3- and 2,5-derivatives (carboxylates in ortho and para positions), the signals are detected at 119.6 and 84.2ppm. The crystal and molecular structure of the seven-coordinated cadmium complex, [Cd(2,4-pyridinedicarboxylato)(H2O)3]·1/2H2O is also reported. This data allows a correlation between Cd–O and Cd–N coordination and geometry with 111Cd chemical shifts. Additional coupling between 111Cd and 14N in 2,3- (also found in 2,4-pydc) suggests only one N is coordinated to Cd. The anisotropy magnitude, Δσ, and the asymmetry parameter, η, are also analysed. [Copyright &y& Elsevier]

Abstract: The molecular structure of the title complex, [Cu(C6H14N4O2)2(H2O)]CO3 ·H2O, was determined by single crystal X-ray diffractometry. It crystallizes in the monoclinic space group P21, with Z =2. The Cu(II) ion is in a square pyramidal environment, trans coordinated at the basis by two argininate groups acting as bidentate ligands through their amino nitrogen and carboxylate oxygen atoms. The coordination around copper is completed by a water molecule at the pyramid apex. The infrared, Raman and electronic spectra are briefly discussed on the basis of the structural peculiarities of the complex. [Copyright &y& Elsevier]