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The crystal structures of bis[1-ethyl-6-fluoro-4-oxo-7-(piperazin-1-ium-4-yl)-1,4- dihydroquinoline-3-carboxylato]copper(II) sulfate heptahydrate, [Cu(C16H18FN3O3) 2]SO4.7H2O or [Cu(nor)2]SO4.7H2O (nor is norfloxacin), and bis{1-[2- (ethylsulfonyl)ethyl]-2-methyl-5-nitroimide}dinitratocopper(II), [Cu(NO3)2- (C8H13N3O4S)2] or [Cu(NO3)2(tnz)2] (tnz is tinidazole), were solved by X-ray diffraction. Both complexes crystallize in the space group P21/c, with Z = 4 (for nor) and Z = 2 (for ntz) molecules per unit cell. In [Cu(nor)2]SO4.7H2O, the CuII ion is at the centre of a square-planar environment, trans coordinated to two independent norfloxacin molecules in the zwitterionic form acting as bidentate ligands through one of the carboxyl (cbx) and the carbonyl (cb) O atoms. The solid is further stabilized by an extensive network of N--H. . .O(sulfate), N--H. . .O(cbx), N--H. . .OW, OW--H. . .O(sulfate) and OW--H. . .OW hydrogen bonds. The [Cu(NO3)2(tnz)2] complex is centrosymmetric, with the CuII ion in a square planar environment, coordinated to a tinidazole molecule acting as a monodentate ligand through its imidazole N atom and to one nitrate O atom. The vibrational FT-IR absorption spectra and thermal behaviour of the complexes were also studied and are briefly discussed based on the crystal structures. [ABSTRACT FROM AUTHOR]

We report here the synthesis, crystal structure, characterization and anticancer activity of a copper(II)-hydrazone complex, [Cu(MeBHoVa)(H2O)2](NO3) (for short, CuHL), against human breast cancer cells on monolayer (2D) and spheroids/mammospheres (3D). The solid-state molecular structure of the complex has been determined by X-ray diffraction methods. The conformational space was searched and geometries were optimized both in the gas phase and including solvent effects by computational methods based on DFT. The compound has been characterized in the solid state and in solution by spectroscopic (FTIR, Raman, UV-vis) methods. The results were compared with those obtained for the hydrazone ligand and complemented with DFT calculations. Cell viability assays on MCF7 (IC50(CuHL) = 1.7 ± 0.1 μM, IC50(CDDP) = 42.0 ± 3.2 μM) and MDA-MB-231 (IC50(CuHL) = 1.6 ± 0.1 μM, IC50(CDDP) = 131.0 ± 18 μM) demonstrated that the complex displays higher antitumor activity than cisplatin (CDDP) on 2D and 3D human breast cancer cell models. Molecular docking and molecular dynamics simulations showed that CuHL could interacts with DNA, inducing a significant genotoxic effect on both breast cancer cells from 0.5 to 1 μM. On the other hand, CuHL increases the ROS production and induces cell programmed death on breast cancer cells at very low micromolar concentrations (0.5–1.0 μM). Moreover, the compound decreased the amount of breast CSCs on MCF7 and MDA-MB-231 cells reducing the percentage of CD44+/CD24−/low cells from 0.5 to 1.5 μM. In addition, CuHL overcame CDDP with an IC50 value 65-fold lower against breast multicellular spheroids ((IC50(CuHL) = 2.2 ± 0.3 μM, IC50(CDDP) = 125 ± 4.5 μM)). Finally, CuHL reduced mammosphere formation capacity, hence affecting the size and number of mammospheres and showing that the complex exhibits antitumor properties on monolayer (2D) and spheroids (3D) derived from human breast cancer cells. [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]

We present the selective synthesis of novel aminooxy glycosyl derivatives bearing hydroxy phenyl moieties. A strict control over the anomeric and E/Z configurations has been achieved. The products obtained are α‐glycosides and the aromatic moiety substitute the Schiff's base trans to the O‐glycosidic bond. Single crystal X‐ray diffraction and NMR spectral data are reported and analysed. [ABSTRACT FROM AUTHOR]

An N,N,O,O donor Schiff base blocking ligand [H2L = 6,6′-((1E,1′E)-(ethane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))bis(3-(diethylamino)phenol), 1] has been used to synthesize mononuclear [CuL]·H2O (2) and [VO(L)] (3) complexes. The ligand and complexes have been characterized by elemental, spectral (FTIR and UV-vis) and thermogravimetric analysis. The molecular structures of 1 and 2 have been confirmed by single crystal X-ray diffraction studies. The crystal structure of the ligand (1) indicates that the molecule is sited on a crystallographic inversion centre and the planar conformation of the salicylideneimine moiety is favored by two intramolecular O–H⋯N1 hydrogen bonds forming S(6) ring motifs. The copper(II) center in complex 2 is coordinated in a square planar fashion. The presence of an extended π-system in the complex (two chelate rings and two phenyl rings) facilitates the formation of chelate ring (CR)⋯π non-covalent interactions. DFT calculations have been performed to explore the energetic features of unconventional CR⋯π and hydrogen bonding interactions that are observed and described in the solid state of 2. Moreover, we have studied how the energy of the CR⋯π interaction is influenced by the substituent of the phenyl ring. In addition, the cytotoxic effect of the compounds has been tested against MG-63 (human osteosarcoma), HT-29 (human colorectal) and MCF7 (breast) cancer cell lines using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. [ABSTRACT FROM AUTHOR]

In the search for a more effective chemotherapy for the treatment of Chagas’ disease and human African trypanosomiasis, caused by Trypanosoma cruzi and Trypanosoma brucei parasites, respectively, the use of organometallic compounds may be a promising strategy. In this work, eight new heterobimetallic compounds are described including four 5-nitrofuryl containing thiosemicarbazones as bioactive ligands (HL1–HL4) and dppf = 1,1′-bis(diphenylphosphino) ferrocene as an organometallic co-ligand. Complexes of the formula [MII(L)(dppf)](PF6) with M = Pd or Pt were synthesized and fully characterized in the solid state and in solution, including the determination of the molecular structure of four of them by single crystal X-ray diffraction methods. Most compounds showed activity in the low micromolar or submicromolar range against both parasites, with the platinum compounds being more active than the palladium analogues. Activity was significantly increased by generation of the M-dppf compounds (3–24 fold increase with respect to free ligands HL for T. cruzi and up to 99 fold increase with respect to HL for T. brucei). The inclusion of the organometallic co-ligand also led to lower toxicity in mammalian cells and higher selectivity towards both parasites when compared to the free HL compounds. The complexes interact with DNA and affect the redox metabolism of the parasites. Furthermore, the most active and selective compound of the new series showed no in vivo toxicity in zebrafish embryos. [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]

A reference to the prior publication of one of the crystal structures reported by Tobón‐Zapata [Acta Cryst. (2022), B78, 490–498] is given. [ABSTRACT FROM AUTHOR]

The molecular structure of two mixed and closely related conformers of the title compound, C13H16O2, found in the solid with unequal occupancies has been determined by X-ray diffraction methods. The substance crystallizes in the monoclinic Pca21 space group with a =17.279(2), b =5.1716(7), c =12.549(2)Å, and Z = 4 molecules per unit cell. The structure was solved from 1314 reflections with I >2σ(I) and refined to an agreement R1-factor of 0.049. The minor conformer (34.7%) is nearly mirror-related to and extensively overlapped with the major one. The skeleton of the 4-hydroxyacetophenone molecular fragment and the prenyl group,—(CH2)—(CH) = C(CH3)2, pendant arm attached to it are both planar and perpendicular to each other. A strong intermolecular O—H···O bond links neighboring molecules in the lattice to produce a polymeric structure. The conformational structures of the compound in the gas phase have been calculated by the DFT method and the geometrical results have been compared with the X-ray data. These data allow a complete assignment of vibration modes in the solid state FTIR and Raman spectra. The calculated 1H and 13C chemicals shifts are in good agreement with the corresponding experimental NMR spectra of the compound in solution. [Copyright &y& Elsevier]

In this study 2-(2′-furyl)-4,5-1H-dihydroimidazole (1) was prepared and then characterized by infrared, Raman, and multidimensional nuclear magnetic resonance (NMR) spectroscopies. The crystal and molecular structures of 1 were determined by X-ray diffraction methods. The density functional theory (DFT) and second-order Møller–Plesset theory (MP2) with Pople's basis set show that there are two conformers for the title molecule that have been theoretically determined in the gas phase, and that only one of them, conformer I, is present in the solid phase. NMR spectra observed for 1 were successfully compared with the calculated chemical shifts at the B3LYP/6-311++G** level theorized for this conformer. The harmonic vibrational frequencies for the optimized geometry of the latter conformer were calculated at the B3LYP/6-311++G** level in the approximation of the isolated molecule. For a complete assignment of the IR and Raman spectra in the solid phase of 1, DFT calculations were combined with Pulaýs scaled quantum mechanics force field (SQMFF) methodology to fit the theoretical frequency values to the experimental ones. Copyright © 2009 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The main goal of this work was to report the synthesis, characterization, and cytotoxicity study of a novel copper(II)-sunitinib complex, CuSun. It has been synthesized and characterized in solid state and in solution by different methods (such as DFT, FTIR, Raman, UV-vis, EPR, NMR, etc.). The solid-state molecular structure of trichlorosunitinibcopper(II), where sunitinib: N-[2-(diethylamino)ethyl]-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide, for short Cu(Sun)Cl3, was determined by X-ray diffraction. It crystallizes in the triclinic space group P-1 with a = 7.9061(5) Å, b = 12.412(1) Å, c = 13.7005(8) Å, α = 105.021(6)°, β = 106.744(5)°, γ = 91.749(5)°, and Z = 2 molecules per unit cell. Also, we have found π-π interactions and classic and non-classic H-bonds in the crystal structure by using Hirshfeld surface analysis. In the speciation studies, the complex has dissociated in protonated sunitinib and chlorocomplex of copper(II), according to 1HNMR, EPR, UV-vis and conductimetric analysis. Molecular docking of the complex in both, ATP binding site and allosteric site of VEGFR2 have shown no improvement in comparison to the free ligand. Besides, cytotoxicity assay on HepG2 cell line shows similar activity for complex and ligand in the range between 1–25 μM supporting the data obtained from studies in solution. [ABSTRACT FROM AUTHOR]

Reaction of trans-Ru(DMSO)4C12 with DMAP (DMAP = 4-dimethylaminopyridine) yields the yellow [Ru(DMAP)6]2~ cation in good yield. The crystal and molecular structure of [Ru(DMAP)6]Cl2.6CH3CH2OH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal F~3 space group with a = b = 16.373(1), c = 20.311(1) A, y = 120°, and Z = 3 molecules per unit cell. The reaction of [Ru(DMAP)6]2~ in aerobic water gives the red [Ru'°(DMAP)5(OH)]2~ cation. This complex shows a chemical behavior similar to [Ru'°(NH3)5Cl]2~ and allows the preparation of a family of [Ru(DMAP)5L]'~ complexes. Their electronic properties indicate that the {Ru°(DMAP)5} fragment is a weaker 7r-donor than {Ru"(NH3)5}. Our density functional theory (DFT) calculations show that in {RuH(DMAP)5} the DMAP ligands can compete for the ~r electron density of the ruthenium making the fragment a weaker ir-donor. [ABSTRACT FROM AUTHOR]

Abstract: A series of indazole N 1-oxide derivatives has been spectroscopically studied in solution using 1H, 13C, and 15N NMR based on pulsed field gradient selected PFG 1Hsp sp="0.25" />= 13C and 15N) gHMQC and gHMBC experiments. Some indazoles were prepared using a new methodology to compare its spectral and structural data with the indazole N 1-oxide parent compounds. The 13C resonances of the indazole N 1-oxide carbon 3 and 7a demonstrate the N-oxide push-electron capability. The 15N resonances of the indazole N-oxide, nitrogen 1, are near to 30ppm more shielded than the corresponding values in the indazole heterocycle (deoxygenated form). Moreover, the structures of one indazole and one indazole N-oxide were unambiguously confirmed by X-ray crystallography. The solid state structures were contrasted with the theoretical ones obtained in vacuo at different calculus level. The aromaticity of the derivatives was studied analyzing the Hg constants of indazole’s aromatic hydrogens and measuring Ces in the solid state. The fragmentation that takes place in EI/MS was gathered for all the indazole N-oxide derivatives and the general fragmentation pattern analyzed. [Copyright &y& Elsevier]

Dodecylnicotinate bis-adducts of binuclear copper carboxylates, of the general formula Cu2(O2CCn - 1H2n - 1)4(C5H4N-COOC1H25)2, were synthesized for n = 10, 12, 14, 16, 18 and 20, and their crystal structure, thermal behavior and magnetic properties studied. The molecular structure of the decyl derivative has been determined from single-crystal X-ray diffraction data. The dimer is centrosymmetric with the CuII ions in a square-pyramidal coordination with four O-alkyl O atoms [average d(Cu-O) 1.960 (6) Å] in the basal plane and the nicotine N atom at apical positions [d(Cu-N) 2.183 (3) Å]. The copper ions, 1615 (1) Å apart, are bridged by four O-alkyl carboxylate groups. Both the n = 20 and n = 18 homologues exhibit lamellar phases, which can be related to the supramolecular arrangement found in the n = 10 derivative. The magnetic behavior of the decyl and octadecyl dimers was studied in the 2-300 K temperature range. They exhibit a strong intramolecular antiferromagnetic interaction (Cu-Cu superexchange coupling constant J = -347 cm-1 for the decyl derivative), which can be attributed to a large overlap of the metal 3d orbitals and the oxygen lone pair orbitals of the linking carboxylale groups. [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]

Five Schiff bases obtained from condensation of 4-methoxybenzohydrazide with related aldehydes, namely o -vanillin, vanillin, 5-bromovanillin, 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde were prepared. A detailed structural and spectroscopic study is reported. The crystal structures of four members of the family were determined and compared with one another. The hydrazones obtained from 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde resulted to be isomorphic to each other. The solid-state structures are stabilized by intra-molecular O H⋯N interactions in salicylaldehyde derivatives between the O H moiety from the aldehyde and the hydrazone nitrogen atom. All crystals are further stabilized by inter-molecular H-bonds mediated by the crystallization water molecule. A comparative analysis between experimental and theoretical results is presented. The conformational space was searched and geometries were optimized both in gas phase and including solvent effects. The structure is predicted for the compound for which the crystal structure was not determined. Infrared and electronic spectra were measured and assigned with the help of data obtained from computational methods based on the Density Functional Theory. [ABSTRACT FROM AUTHOR]

• Synthesis of three novel antipyrine-amide derivatives confirmed by spectroscopic analysis. • Molecular and crystal structures for the three compounds were established by single-crystal X- ray analysis. • Hirshfeld surface analysis shows dominance of hydrogen bonds promoted by the N H group. • FTIR, Raman, and DFT analyses describe vibrational properties of the compounds. • Topological QTAIM and NCIplot analysis reveal significant noncovalent C H···π and Cl···π interactions. In this study, we report the synthesis, structural characterization by X-ray diffraction, vibrational (Infrared and Raman) investigation, Hirshfeld surface analysis, and DFT calculations of three new antipyrine derivatives (1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1 H -pyrazol-4-yl) bearing amide groups (1–3). The compounds were synthesized in good yields and characterized spectroscopically. X-ray diffraction revealed that compound 1 crystallizes as a monohydrate in the monoclinic space group P 2 1 /c, while compound 3 also crystallizes as a monohydrate in the orthorhombic space group P ccn, exhibiting quasi-isomorphism with 1. Compound 2 crystallizes in the P 2 1 /c space group, forming H-bonded centrosymmetric dimers. The crystal packing is stabilized by N H···O and C H···O hydrogen bonds, along with C H···π interactions. FTIR and Raman spectroscopic analysis, supported by DFT calculations, identified key vibrational modes in the amide and pyrazole moieties. Hirshfeld surface analysis indicated that the molecular sheets are primarily formed by hydrogen bonds, with stabilization dominated by electrostatic energy contributions. DFT calculations (PBE0-D3/def2-TZVP) and QTAIM/NCIplot analyses revealed that the H-bonding interactions are energetically significant. [ABSTRACT FROM AUTHOR]

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]

Abstract: Structural and conformational properties of 1H-Isoindole-1,3(2H)-dione, 2-[(methoxycarbonyl)thio] (S-phthalimido O-methyl thiocarbonate) are analyzed using a combined approach including X-ray diffraction, vibrational spectra and theoretical calculation methods. The vibrational properties have been studied by infrared and Raman spectroscopies along with quantum chemical calculations (B3LYP and B3PW91 functional in connection with the 6-311++G** and aug-cc-pVDZ basis sets). The crystal structure was determined by X-ray diffraction methods. The substance crystallizes in the monoclinic P21/c space group with a =6.795(1), b =5.109(1), c =30.011(3)Å, β =90.310(3)° and Z =4 molecules per unit cell. The conformation adopted by the Nh name="sbnd" />Cs syn (Cbond in synperiplanar orientation with respect to the Nbond). The experimental molecular structure is well reproduced by the MP2/aug-cc-pVDZ method. [Copyright &y& Elsevier]

Abstract: Structural and conformational properties of S-benzyl ferrocenecarbothioate (I) and S-(2-methoxyphenyl) ferrocenecarbothioate (II) are analyzed using data obtained from X-ray diffraction, vibrational data and theoretical calculations. According to chemical quantum calculations, the synperiplanar and antiperiplanar forms are found as the first and second more stable conformations, respectively, for the title compounds. The geometric parameters and normal modes of vibration were calculated using a density functional theory method (B3LYP) and the 6-31+G∗∗ basis set for all atoms except for iron. For this atom the calculations were carried out with the Lanl2dz basis set. The calculated parameters are in good agreement with the corresponding X-ray diffraction values. The combined experimental and theoretical approach allows a consistent assignment for most of the fundamental modes. [Copyright &y& Elsevier]

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: Pure O-methyl N-methoxycarbonyl thiocarbamate CH3OC(S)N(H)C(O)OCH3 (I) and O-ethyl N-methoxycarbonyl thiocarbamate, CH3CH2OC(S)N(H)C(O)OCH3 (II), are quantitatively prepared by the addition reaction between the CH3OC(O)NCS and the corresponding alcohols. The compounds are characterized by multinuclear (1H and 13C) and bi-dimensional (13C HSQC) NMR, GC–MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach involving crystallographic data, vibration spectra and theoretical calculations. The low-temperature (150K) crystal structure of II was determined by X-ray diffraction methods. The substance crystallizes in the monoclinic space group P21/n with a =4.088(1)Å, b =22.346(1)Å, c =8.284(1)Å, β =100.687(3)° and Z =4 molecules per unit cell. The conformation adopted by the thiocarbamate group –OC(S)N(H)– is syn (Cbond in synperiplanar orientation with respect to the N–H single bond), while the methoxycarbonyl Cbond is in antiperiplanar orientation with respect to the N–H bond. The non-H atoms in II are essentially coplanar and the molecules are arranged in the crystal lattice as centro-symmetric dimeric units held by N−H···Sn bonds [d(N···S)=3.387(1)Å, ∠(N−H···S)=166.4(2)°]. Furthermore, the effect of the π electronic resonance in the structural and vibrational properties is also discussed. [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]

Through a redox process, an in situ transformation of propylthiouracil led to the formation of a trisulfur ligand forming with Cu(II) a lantern-like binuclear complex [Cu 2 (ptu-S-ptu) 2 ]. The complex behaves as a promiscuous promising catalyst. It possesses peroxidase-like activity catalyzing phenol red bromination, the oxidation of pyrogallol, and behaves as a superoxide dismutase (SOD) mimic compound. Insights into their reactivity are analyzed by comparison with a family of other sulfur-containing copper(II) metal complexes. [Display omitted] Through a redox process, an in situ transformation of propylthiouracil led to the formation of a trisulfur ligand that coordinates Cu(II) ion forming a lantern-like binuclear copper(II) complex [Cu 2 (ptu-S-ptu) 2 ]. The complex was characterized by elemental analysis, spectroscopic techniques (FTIR, UV–Vis, EPR, and Hirshfeld surfaces analyses.), single-crystal X-Ray analysis, and its optimized molecular structure was obtained by DFT calculations. It crystallizes as a twin in the space group P -1, with two different, though closely related, centrosymmetric binuclear complexes per unit cell. The (ptu-S-ptu)2− thiouracil rings are nearly perpendicular to each other and their N and O atoms equatorially cis -coordinate the two copper ions in a two-fold Cu-OCN-Cu bridging mode. The four-fold bridging configuration is completed by another (ptu-S-ptu)2− ligand, inversion-related through the middle of the Cu...Cu contact. The elongated octahedral coordination around each copper is completed by the linking S-atom of the ligand at the axial position. The crystallographic results point to a copper d(x2-y2) d -orbital for the electron (or hole) ground state and optimal overlap of this orbital with molecular electronic path bridging the two metal atoms, hence indicating a relatively large antiferromagnetic coupling between them. The designed complex behaves as a promiscuous promising catalyst. It possesses intrinsic peroxidase-like activity catalyzing phenol red bromination in the presence of H 2 O 2 at room temperature, and the oxidation of pyrogallol, and behaves as a superoxide dismutase (SOD) mimic compound acting on superoxide anion. Additionally, insights into their reactivity are analyzed by comparison with a family of other sulfur-containing copper(II) metal complexes in an attempt to explain the differences in catalytic properties and to determine the structural properties that affect the reactivity with substrates. Albumin interactions studies are also incorporated. [ABSTRACT FROM AUTHOR]

Abstract: Complexes [Zn2(HL1)2(CH3COO)2] (1) and [Zn2(L2)2] (2) were synthesized with salicylaldehyde semicarbazone (H2L1) and salicylaldehyde-4-chlorobenzoyl hydrazone (H2LASSBio-1064, H2L2), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn2(HL2)2(Cl)2] (3) in 1:9 DMSO:acetone crystals of [Zn2(L2)2(H2O)2]·[Zn2(L2)2(DMSO)4] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes. [Copyright &y& Elsevier]

Abstract: The “Ru(P–P)” unit (P–P=diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl2Ru-pz-RuCl2(CO)(dppb)] (pz=pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N–N)]PF6 (N–N=diimine). Complexes with the formula [RuCl(py)(dppb)(N–N)]PF6 were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl2(dppb)(N–N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and 31P{1H} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. [Copyright &y& Elsevier]

Abstract: The structural, spectroscopic and theoretical study of cyclocreatine (1-carboxymethyl-2-iminoimidazolidine, CyCre) has been performed prompted by the biological relevance of the molecule and its potential role as a ligand in biometalic compounds. The crystal structure of CyCre has been determined by X-ray diffraction methods. The compound crystallizes as a zwitterion in the monoclinic system, space group P21/c. The crystal is further stabilized by a network of N–H⋯O bonds. Infrared and Raman spectra of the solid, electronic spectra of aqueous solutions at different pH values and 1H and 13C NMR spectra have been recorded and analyzed. Band assignments were accomplished with the help of theoretical calculations. Optimized molecular geometries, harmonic vibrational frequencies and molecular electrostatic potentials were calculated using methods based on the density functional theory. [Copyright &y& Elsevier]

Abstract: 3′-Azido-3′-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis, X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT–O)2Cred by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C21H24N10O9, crystallizes in the tetragonal space group P41212 with a = b =15.284(1), c =21.695(1)Å, and Z =8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape. [Copyright &y& Elsevier]

Abstract: In the present work 2-formylpyridine-para-chloro-phenyl hydrazone (H2FopClPh) and 2-formylpyridine-para-nitro-phenyl hydrazone (H2FopNO2Ph) were obtained, as well as their copper(II) and zinc(II) complexes [Cu(H2FopClPh)Cl2] (1), [Cu(2FopNO2Ph)Cl] (2), [Zn(H2FopClPh)Cl2] (3) and [Zn(H2FopNO2Ph)Cl2] (4). Upon re-crystallization in DMSO:acetone conversion of 2 into [Cu(2FopNO2Ph)Cl(DMSO)] (2a) and of 4 into [Zn(2FopNO2Ph)Cl(DMSO)] (4a) occurred. The crystal structures of 1, 2a, 3 and 4a were determined. [Copyright &y& Elsevier]

Abstract: 2-Benzoylpyridine-methyl hydrazone (HBzMe) has been obtained as well as its copper(II) [Cu(HBzMe)Cl2] (1) and zinc(II) [Zn(HBzMe)Cl2] (2) complexes. Upon re-crystallization in 1 – 9 DMSO:acetone conversion of 1 into dimeric [Cu(BzMe)Cl]2 (1a) occurred. The crystal structures of HBzMe, 1, 1a, and 2 were determined. HBzMe adopts the ZE conformation in the solid. In all complexes the hydrazone adopts the E configuration to attach to the metal through the Npy ph name="sbnd" />O chelating system. In 1 and 2 a neutral hydrazone coordinates to the metal center while in 1a deprotonation occurs with coordination of an anionic ligand. 1a presents a dimeric structure, having two copper(II) ions per asymmetric unit. Two chlorides are also present in the copper coordination sphere, which act as bridging ligands and connect the copper centers to each other. [Copyright &y& Elsevier]

Abstract: Pure N,N′-di(methoxycarbonylsulfenyl)urea, [CH3OC(O)SNH]2CO, is quantitatively prepared by the hydrolysis reaction of CH3OC(O)SNCO and characterized by 1H NMR, GC–MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH3OC(O)SNH]2CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P21212 space group with a =9.524(2), b =12.003(1), c =4.481(1)Å, and Z =2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C 2) parallel to c and shows the anti–anti conformation (S–N single bonds antiperiplanar with respect to the opposite C–N single bonds in sulfenyl-ureasic group). Neighboring molecules are arranged in a chain motif that extends along the C 2-axis and is held by bifurcated NH⋯O⋯HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central –SN(H)C(O)N(H)S– skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N–H⋯On bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. [Copyright &y& Elsevier]

Abstract: Two Cu(II) complexes with cyanoguanidine (cnge) and o-phenanthroline, [Cu(o-phen)2(cnge)](NO3)2 ·2H2O (1) and [Cu(o-phen)(cnge)(H2O)(NO3)2] (2), have been synthesized using different experimental techniques and characterized by elemental analyses, FTIR, diffuse and UV–vis spectra and EPR and magnetic moment measurements techniques. The crystal structures of both complexes were solved by X-ray diffraction methods. Complex (1) crystallizes in the monoclinic space group C2/c with a =12.621(5), b =31.968(3), c =15.39(1)Å, β =111.68(4)°, and Z =8 and complex (2) in the monoclinic space group P21/n with a =10.245(1), b =13.923(2), c =12.391(2)Å, β =98.07(1)°, and Z =4. The environments of the copper(II) center are trigonal bipyramidal (TBP) for [Cu(o-phen)2(cnge)]2+ and an elongated octahedron for [Cu(o-phen)(cnge)(H2O)(NO3)2]. Solution studies have been performed to determine the species distribution. The superoxide dismutase (SOD) activities of both complexes have also been tested in order to determine if these compounds mimic the enzymatic action of the enzyme SOD that protects cells against peroxide radicals. [Copyright &y& Elsevier]

The molecular structure of [Cu(sulfadimet)2]·SO(CH3)2 (sulfadimet=sulfadimethoxine=4-p-aminobenzenesulfonamido-2,6-dimethoxypyrimidine) was determined by single crystal X-ray diffractometry. It crystallizes in the monoclinic space group P21/c with Z=4. The Cu(II) cation is in a distorted CuN5 square pyramidal coordination, involving four sulfadimethoxine molecules, one of them acting as a bidentate ligand. The infrared spectrum is briefly discussed on the basis of the structural peculiarities of the complex. [Copyright &y& Elsevier]