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Treatment of [CuCl2(PPh3)2] with N‐heterocyclic thiols, i. e. 4,6‐dimethyl pyrimidine‐2‐thiol (dmpymSH), pyridine‐2‐thiol (pySH), resulted partially substituted product [CuCl(L)(PPh3)2] (L=C5H4NSH (pySH), SC4H(4,6‐Me2N2H) (dmpymSH). However, similar reaction with [CuI(PPh3)]4 yielded a products [CuI(pySH)(PPh3)2] (py=C5H4N) and [CuI(dmpymSH)(PPh3)2] (dmpym=C4H(4,6‐Me2N2); respectively. The molecular structure of complex [CuCl(dmpymSH)(PPh3)2].CH3CN (1 b) has been determined through the single crystal X‐ray crystallography technique. All the synthesized complexes were fully characterized through various spectroscopic techniques (IR, 1H, 13C{1H}, 31P{1H} NMR). The complexes 1 a, 1 b, 2 a and 2 b showed excellent catalytic activities for azide‐alkyne cycloaddition reaction in water as green solvent upto 90 % yield with 0.5 mol % of catalyst loading. Among all the synthesized complexes, compound [CuI(pySH)(PPh3)2] (2 a) turned up as a better catalyst with 90 % yield, applying 0.5 mol % catalyst. [ABSTRACT FROM AUTHOR]

In the title compound, C24H29F2NO4, which crystallizes in the ortho­rhom­bic Pca21 space group with Z = 4, the 1,4-di­hydro­pyridine ring adopts a distorted boat conformation, while the cyclo­hexene ring is in a distorted half-chair conformation. In the crystal, the mol­ecules are linked by N—HO and C—HO inter­actions, forming supra­molecular chains parallel to the a axis. These chains pack with C—Hπ inter­actions between them, forming layers parallel to the (010) plane. The cohesion of the crystal structure is ensured by van der Waals inter­actions between these layers. Hirshfeld surface analysis shows the major contributions to the crystal packing are from HH (56.9%), FH/HF (15.7%), OH/HO (13.7%) and CH/HC (9.5%) contacts. [ABSTRACT FROM AUTHOR]

Tetramethyl-(p-tolyl)-hexahydro-1H-xanthene-1,8(2H)-dione (P-TX) was synthesized and characterized experimentally using X-ray diffraction, FT-IR, 1H, 13 C N.M.R. and UV-Vis spectra, and theoretically using DFT calculations. The most stable optimized structure was discovered utilizing the B3LYP/6-311++G(d,p) basis set, followed by FTIR and N.M.R. investigation. The researched chemical's ideal structure corresponds to the findings of the X-ray analysis. TD-DFT analysis also shed more light on how the electronic transitions in the UV–Vis spectra were estimated. The Hirshfeld surface analyses were presented and discussed, as well as the energy framework calculations. Other topics included topological and Mulliken charge distribution studies. The vibrational assignments were completed using individual vibrational modes, then compared to experimental data. The docking studies were utilized to investigate the interactions of the ligand (P-TX) with specific protein targets, suggesting that P-TX could be employed as a potential cytotoxic and antibacterial agent. P-TX may be considered a potential medicinal molecule due to the current research. The experimental and theoretical results were highly similar in geometric and spectroscopic characteristics. [ABSTRACT FROM AUTHOR]

Amino-N-cyclopropyl-5-heptylthiophene-3-carboxamide (ACPHTC) and its functional derivatives were synthesized and analyzed via single-crystal X-ray diffraction at 296 K, 1H,13C NMR, UV–Vis, FT-IR, and ESI-MS spectral analysis. ACPHTC crystallizes in a tetragonal crystal system, space group I-4 with Z = 16 and the following unit cell dimensions: a = 19.2919(4) Å, b = 19.2919(4) Å, c = 17.1515(5) Å. Using HF and DFT, B3LYP methods with the 6-311++G(d,p) basis established by the GAUSSIAN 16 program, the optimized molecular geometric parametersof ACPHTC and its derivatives were computed. The ACPHTC molecule hyper conjugative interactions are revealed by the NBO analysis, which has been carried out. Electrophilic and nucleophilic sites have been identified throughMEP. The first-order hyperpolarizability, dipole moment, and polarizability of the ACPHTC were taken into account when analyzing its NLO behavior. Additionally, the energies of ACPHTC HOMO and LUMO were found. The TD-DFT has been used to determine the UV-Vis spectra and electronic features such as frontier orbitals and band gap energies. The GIAO method was used to determine the 1H and 13C NMR chemical shifts of ACPHTC molecule and compare them to experimental results. Fingerprint plots,Hirshfeld surface are used to evaluate the properties of intermolecular interactions. Finally, docking studies were used to examine the binding affinity,of ACPHTC and its derivatives. [ABSTRACT FROM AUTHOR]

A potassium 4-(pyridyl)-1,3,4-oxadiazole-2-thione was isolated in a basic medium, and its complexes [Cu(en)2(pot)2] (1) and [Zn(en)2(pot)2]HBr·CH3OH (2) containing ethylenediamine (en) as secondary ligand were synthesized and fully characterized. Upon changing the reaction conditions, the Cu(II) complex (1) adopts an octahedral geometry around the metal center. The cytotoxic activity of ligand (Kpot·H2O) along with complexes 1 and 2 was tested, and their anticancer activity against MDA-MB-231 human breast cancer cells was demonstrated, with complex 1 exhibiting superior cytotoxicity against these cells as compared to Kpot·H2O and complex 2. According to the DNA nicking assay, the ligand (Kpot·H2O) was found to be more potent to scavenge hydroxyl radicals even at a lower concentration (50 μg mL−1) than that of both complexes. The wound healing assay revealed that ligand Kpot·H2O and its complexes 1 and 2 attenuated the migration of the above-mentioned cell line. The loss of cellular and nuclear integrity and induction in the activity of Caspase-3 suggest the anticancer potential of ligand Kpot·H2O and its complexes 1 and 2 against MDA-MB-231 cells. [ABSTRACT FROM AUTHOR]

O,O'-Diethyl-S-(N-phthalimidomethyl) dithiophosphate was synthesized and characterized by different spectroscopic methods (UV, IR, 1H, 13C, 31P, and 15N NMR) as well as DTA, TGA, DSC, and ESI techniques and single crystal X-ray diffraction. The compound exhibits fluorescence behavior and can serve as an antimicrobial agent. The crystal structure of O,O′-diethyl-S-(N-phthalimidomethyl) dithiophosphate displays the monodentate nature of the alkyl dithiophosphate moiety. [ABSTRACT FROM AUTHOR]

The development of a potent metallodrug to prevent the progression of cancer is needed urgently. Here, three new complexes [Mn(pfth)2(o-phen)] (1), [Co(pfth)2(en)] (2) and [Ni(pfth)2(en)] (3) based on a 4-phenyl-(2-furoyl)-thiosemicarbazide (Hpfth) ligand containing 1,10 phenanthroline (o-phen)/ethylenediamine (en) as secondary ligands have been synthesized. The synthesized complexes have been characterized by various analytical, spectroscopic (IR, UV-vis., NMR), and single-crystal X-ray diffraction techniques. The results obtained by quantum chemical calculations (DFT and TD-DFT) agree with the experimentally observed values. The tumoricidal potential of Mn, Co, and Ni salts, ligand Hpfth, and their coordinate complexes was evaluated against K562, MCF-7, and DL cancer cell lines. Both short-term (XTT and MTT assays) and long-term (clonogenic assay) treatment of the tumor cells studied through colorimetric, clonogenic, and fluorescence-based assays by the complexes demonstrated true anti-tumor effects against these cancer cells. The results suggest the significant antitumor potential of the metal–ligand complexes against the tumor cells in a dose-dependent manner with higher growth inhibition, apoptosis, and inhibition in colony formation in comparison to either metal salts or free ligands. Complexes 1 and 3 induce more growth inhibition as compared to complex 2 against all cancer cell lines. Complex 3 demonstrated impressive tumoricidal properties in a clonogenic assay in comparison to complexes 1 and 2. These studies establish the role of metal centers in antiproliferative activities and reveal that Ni(II) exhibits more potent anti-tumoricidal activity. Molecular docking studies of Hpfth and complexes 1–3 were also performed against three target proteins 6NE5: Myeloid Cell Leukemia-1 (Mcl-1), 6E91: Carbonic anhydrase IX (CA IX), and 6H0W: Lysine Demethylase 4D and the results displayed favorable binding interactions. [ABSTRACT FROM AUTHOR]

A hydrogen sulfate salt, C15H18NSe+xHSO4 BH2O or [BnSeCH2CH(Ph)NH3+]-(HSO4 C), of a chiral selenated amine (R)-2-(benzylselanyl)-1-phenylethanamine (BnSeCH2CH(Ph)NH2) has been synthesized and characterized by elemental analysis, 1H and 13C{1H} NMR, FT-IR analysis, and single-crystal X-ray diffraction studies. The title salt crystallizes in the monohydrate form in the non-centrosymmetric monoclinic P21 space group. The cation is somewhat W shaped with the dihedral angle between the two aromatic rings being 60.9 (4)-. The carbon atom attached to the amine nitrogen atom is chiral and in the R configuration, and, the -C--C- bond of the -CH2--CH- fragment has a staggered conformation. In the crystal structure, two HSO4 C anions and two water molecules form an R4 4(12) tetrameric type of assembly comprised of alternating HSO4C anions and water molecules via discrete D(2) O--H...O hydrogen bonds. This tetrameric assembly aggregates along the b-axis direction as an infinite one-dimensional tape. Adjacent tapes are interconnected via discrete D(2) N--H...O hydrogen bonds between the three amino hydrogen atoms of the cation sandwiched between the two tapes and the three HSO4 -anions of the nearest asymmetric units, resulting in a complex two-dimensional sheet along the ab plane. The pendant arrangement of the cations is stabilized by C--H. ... interactions between adjacent cations running as chains down the [010] axis. Secondary Se...O [3.1474 (4) A ° ] interactions are also observed in the crystal structure. A Hirshfeld surface analysis, including dnorm, shape-index and fingerprint plots of the cation, anion and solvent molecule, was carried out to confirm the presence of various interactions in the crystal structure. [ABSTRACT FROM AUTHOR]

A quinoline-based Schiff base sensor, 6-methyl-2-oxo-1,2-dihydro-quinoline-3-carboxaldehyde-4(N)-phenylsemicarbazone (6MPS), has been developed for selective sensing of methionine and aspartic acid in aqueous medium through "on–off–on" type selective detection of copper ion. Fluorescence imaging of 6MPS, 6MPSC, 6MPSCN, 6MPSC-met, 6MPSCN-met, 6MPSC-asp and 6MPSCN-asp has been successfully demonstrated, in which the sensing probes 6MPSC-met, 6MPSCN-met, 6MPSC-asp and 6MPSCN-asp displayed bright green fluorescence in both in vitro and in vivo live cells. [ABSTRACT FROM AUTHOR]

Solvothermal reaction of cobalt nitrate/copper nitrate with a semi-rigid 1,1′-(anthracene-9,10-diylbis(methylene))bis(pyridin-1-ium-4-olate) (L = AHP) ligand and disulphonic acid [1,5-naphthalenedisulfonic acid (1,5-NDS)/2,6-naphthalenedisulfonic acid (2,6-NDS)] resulted in the formation Co(II)/Cu(II) containing metal–organic frameworks (MOFs). These MOFs have been structurally characterized by different methods including single crystal X-ray diffraction. The structural analysis revealed that the number of coordinated AHP ligands is different in different MOFs and each AHP ligand is actively involved in the formation of a one-dimensional chain. The presence of 1,5-NDS/2,6-NDS either in a coordinated or free form (lattice) plays an important role in increasing the dimensionality of the frameworks. The characterized MOFs have been tested for their proton conductivity and dye degradation properties. The presence of free water and 1,5-NDS in the cavity of MOF4 encouraged us to perform proton conductivity measurement. MOF4 seems to maintain its framework structure in various humid environments and ensures smooth conduction pathways mediated by water molecules. Depending on the temperature and humidity levels, this MOF showed moderate to high proton conductivity (6.96 × 10−4 to 1.95 × 10−3 S cm−1). The above synthesised MOFs show the degradation of methylene blue in the presence of hydrogen peroxide (H2O2). The increase of degradation activity in the presence of H2O2 indicates the formation of hydroxyl radicals in the reaction process. [ABSTRACT FROM AUTHOR]

Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (L1) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (L2), and their homoleptic ruthenium(II) complexes, [Ru(L1)2](PF6)2 (1) and [Ru(L2)2](PF6)2 (2), were synthesized and characterized by elemental analysis, 1H and 13C{1H} NMR spectroscopy, FT-IR spectroscopy and single crystal X-ray diffraction. The crystals of these compounds contain CH⋯F, OH⋯F, CH⋯O, CH⋯π and/or π⋯π intermolecular secondary interactions, resulting in supramolecular architectures. Hirshfeld surface analysis of all four compounds was also carried out to determine the intermolecular interactions. We investigated the photophysical properties of L1, L2, 1 and 2 by UV-Visible absorption and fluorescence emission spectroscopy and studied their electrochemical properties by cyclic voltammetry. In addition to n–π* and π–π* bands in the UV-Visible spectra of both ligands and complexes, a fairly strong and relatively broad 1MLCT band appeared at λmax ∼ 500 nm in complexes 1 and 2. The emission bands in ligands L1 and L2 appeared at λem 429 and 426 nm, respectively, whereas in the complexes 1 and 2, these bands showed red-shifts of 34 and 82 nm, respectively. Both L1 and L2 showed two oxidation peaks; however, only L2 showed a significant reduction peak. Complexes 1 and 2 showed two oxidation peaks and two reduction peaks. The effects of increasing scan rate (100 to 1000 mV s−1) on the electrochemical behaviour of complexes 1 and 2 were also investigated. The experimentally observed structural and photophysical properties were supported by DFT and TD-DFT calculations. [ABSTRACT FROM AUTHOR]

Various zinc and cadmium containing metal–organic frameworks using the semi-rigid 1,1′-(anthracene-9,10-diylbis(methylene))bis(pyridin-1-ium-4-olate) ligand (L = AHP) and various sulfonic acid analogs [1,5-naphthalenedisulfonic acid (1,5-NDS), 3-sulfobenzoic acid (3-SBA), 4-sulfobenzoic acid (4-SBA), 5-sulfosalicylic acid (SSA), 5-sulfoisophthalic acid (SIA) and 2,6-naphthalenedisulfonic acid (2,6-NDS)] have been synthesized by a hydrothermal method. They have been characterized by powder X-ray diffraction thermogravimetric analysis and single crystal X-ray diffraction methods. The X-ray studies showed that MOF2, 4, and 8 have two dimensional architectures whereas 1, 3, 5, 6 and 7 have three-dimensional structures. The topological analysis demonstrated that all the zinc-containing MOFs have a hexagonal (hcb) net topology with the point symbol of the framework being {63} whereas cadmium-containing MOF4 has an sql net topology with the point symbol of the framework being {44·62} and MOF5 has a hcb net topology with the point symbol of the framework being {63}. Since all synthesized MOFs have fluorescence properties, they have been used as imaging agents for MCF7 cells. The cytotoxic experiments show that more than 92% cells survive at the dose 100 μg ml−1. The cell imaging results show that the MOF particles were found in the cytoplasm rather than in the nucleus and these can be used further as a conjugate with any known anti-cancer drugs in cellular distribution. The emission properties of these MOFs have been utilized for the detection of a herbicide (simazine) as well as nitroaromatic compounds. The quenching constant for PA (picric acid) in MOF7 was found to be 5.01 × 104 M−1, which may be due to the interaction of picric acid and co-ligands present in MOF7. [ABSTRACT FROM AUTHOR]

The title compound C24H18N4O2S2 is synthesized via the azide method and its structure is redetermined at 100(2) K. The title structure, N,N′-(disulfanediyldibenzene-2,1-diyl)dipyridine-2-carboxamide is redetermined from the data published by Lumb, Hundal, and Hundal (Inorg. Chem., 2014, 53, 7770-7779). The redetermination is of significantly higher precision than a previous low-temperature structure and the improvement of the present redetermination consists in a released geometry of the 1,2-diphenyldisulfane group. The molecular structure crystallizes in the triclinic space group, P-1, with a = 7.3492(3) Å, b = 11.6753(5) Å, c = 13.1814(6) Å, α = 95.077(4)°, β = 105.316(4)°, γ = 100.759(4)°, and V = 1060.28(8) Å3. The S-S bond length of 2.0758(4) Å and S-C distances of 1.7818(13) Å and 1.7767(13) Å for this redetermination are much closer to those observed in comparable structures. Intraand intermolecular N-H...S, N-H...N, C-H...O, C-H...S hydrogen bonds are present in the crystal structure. The molecular geometry of the title compound is optimized by the DFT method and the calculated geometrical parameters are compared with experimental ones. The NBO analysis of possible intramolecular hydrogen bonds is made on the optimized structure for comparison. [ABSTRACT FROM AUTHOR]

The crystal structure of a mononuclear Ni(II) complex [Ni(bqenH2)(bpy)](ClO4)2·0.125H2O 1 (where bqenH2 is N,N′-bis(8-quinolyl)ethane-1,2-diamine, bpy = 2,2′-bipyridine) is reported here. The crystallographic data for 1 are as follows: monoclinic crystal system, P21/n space group, a = 17.3255(11), b = 10.6110(7), c = 34.328(2) Å, α = 90°, β = 93.9480(13)°, γ = 90°, V = 6295.8(7) Å3, Z = 4, dx = 1.541 mg/m3. The nickel(II) ion coordinates four N atoms of the tetradentate ligand bqenH2 and two N atoms of the auxiliary bidentate 2,2′-bipyridine ligand, resulting in a slightly distorted NiN6 octahedron with two perchlorates serving as charge balancing counter anions. The overall structure of 1 is stabilized by the presence of water of crystallization in the crystal lattice. The crystal structure shows two symmetrically identical octahedral NiN6 units in its asymmetric unit. The extensive hydrogen bonding network resulting in a supramolecular architecture is observed due to the N-H⋯O, O-H⋯O, O-H⋯Cl, and N-H⋯Cl interactions. [ABSTRACT FROM AUTHOR]

The synthesis of five N,N″-substituted thiocarbamides, namely N-(naphthyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L1), N-(2-Chloro-4-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide(H2L2), N-(2-methoxy-4-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L3), N-(3-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L4) and N-(naphthyl)-N″-(2, 2, 2-trichloroethoxycarbonyl) thiocarbamide (H2L5) was performed by the reaction of pentoxycarbonyl chloroformate with naphthyl amine, 2-chloro-4-nitroaniline, 2-methoxy-4-nitroaniline, 3-nitroaniline, respectively, for the first four and by the reaction of 2, 2, 2-trichloroethoxycarbonyl chloroformate with naphthyl amine for the last compound. These compounds were fully characterized by using various spectroscopic (FT-IR, 1H and 13C NMR) and single crystal X-ray studies of H2L1 and H2L5. In the crystal structure of both the compounds the (C˭S) and (C˭O) groups are trans to each other across the C−N bond. The crystal packing of H2L1 shows that the molecules form centrosymmetric dimers connected by N2−H····S hydrogen bonds. In H2L5 an offset face-to-face π-π stacking is observed between two naphthalene rings of two molecules. In vitro cytotoxicity of synthesized compounds was evaluated using five human carcinoma cell lines 2008, C13* (cervical carcinoma), A2780, A2780/CP and IGROV-1 (ovarian carcinoma). The IC50 values of compounds H2L2 ─ H2L4 demonstrated them to be very promising anticancer agents. [ABSTRACT FROM AUTHOR]

Enantiomerically pure chiral hybrid organotellurium ligands (R)-L1H, (S)-L2H and (R)-L3H have been synthesized via condensation of the chiral β-organotellurated amines 2a, 2b and 2c, respectively, with salicylaldehyde. When these chiral acyclic tellurated Schiff base ligands reacted with Na2PdCl4 in a 1 : 1 molar ratio, they afforded the corresponding orange-red asymmetric complexes [Pd(L1–3)Cl] (1–3). All these compounds were characterized by elemental analysis, polarimetry, and 1H, 13C{1H} NMR and FT-IR spectroscopies. The absolute structures of the complexes 1 and 2 were determined by single crystal X-ray diffraction, and the complexes 1 and 2 crystallized in the hexagonal and orthorhombic crystal systems with the space groups P65 and P212121, respectively. The characterisation data showed that the ligands coordinated in the deprotonated tridentate (Te, N, O−) mode and acquired a square planar geometry around the central palladium(ii) ion along with a monodentate chloro (Cl−) in 1–3. The Pd–Te, Pd–Cl, Pd–O and Pd–N bond lengths found were 2.5008(9), 2.3286(19), 2.037(6) and 2.009(6) Å, respectively, in 1 and 2.497(2)/2.506(3), 2.293(6)/2.326(6), 2.035(15)/2.030(2) and 1.949(17)/2.010(2) Å, respectively, in 2. There was intermolecular CH…Cl [2.81–2.96 Å] and CH…O [2.40–2.64 Å] hydrogen bonding in 1 and 2, which resulted in supramolecular structures. The Te…Cl [3.309–3.710 Å] secondary interactions resulted in the helical structure of 1 and dimeric structure of 2 with a short Pd…Pd [3.500(1) Å] distance. The Flack parameters (x) of 1 [0.02(3)] and 2 [0.024(12)] confirmed their absolute configurations. [ABSTRACT FROM AUTHOR]

Two novel square planar complexes [Ni(Hapt)2] (1) and [Ni(btsc)] (2) have been synthesized from acetone N4-phenyl-thiosemicarbazone (Hapt) and benzoyl-3-thiosemicarbazide (Hbtsc) by the reaction of nickel(ii) salt. The ligand and complexes have been characterized by various physicochemical methods. Complexes 1 and 2 crystallize in the monoclinic and orthorhombic systems with space group C2/c and Pbcn, respectively. In complexes 1 and 2 the nickel centre is coordinated through the nitrogen and sulphur atoms forming a square planar geometry. Complexes 1 and 2 are stabilized via various types of intermolecular interactions. The course of the thermal degradations of complexes 1 and 2 has been investigated by TGA which indicated that a metal sulphide/oxide is formed as the final residue. Cyclic voltammetric studies show that complex 1 exhibits a reversible Ni(ii)/Ni(iii) redox process at 0.525 V (E1/2 value at 20 mV s−1) while complex 2 shows reversible redox behavior with an E1/2 value of 0.43 V. Furthermore, efficient electrocatalytic properties of complexes 1 and 2 toward the oxidation of hydrazine and methanol are demonstrated after immobilizing the complexes into Nafion films. The electrocatalytic properties may find applications in industry, in methanol sensing and in methanol fuel cells. [ABSTRACT FROM AUTHOR]

Three new copper(ii) complexes, viz., [Cu(L)(NO3)(H2O)]H2O 1, [Cu(L)(H2O)2]NO32 and [Cu2(L)2(pyrazine)](ClO4)2·4H2O 3, were prepared using a biomimetic synthesis strategy [HL = 4-chloro-2-{(E)-[2-(pyridin-2-yl)hydrazinylidene]methyl}phenol]. Structural characterization revealed very different local geometries around copper(ii) ions, being square pyramidal for mononuclear complexes (τ5 = 0.021 for 1 and τ5 = 0.13 for 2) and square planar for homobinuclear pyrazine bridged complex 3 (τ4 = 0.06). In complex 3, stacking of chelate rings was observed. This insight was thought to provide new structural evidence for the stacking of the planar chelate rings. These π-interactions provide stability to the crystal structure of homobinuclear complex 3. Magnetic measurements of bulk materials 1, 2 and 3 revealed weak antiferromagnetic coupling in all complexes. The EPR spectra of complexes 1, 2 and 3 in polycrystalline state exhibited broad signals at g≅ 2.15 owing to spin–spin interactions between two copper ions. The cyclic voltammograms of mononuclear complexes (1 and 2) in DMSO gave one CuII/CuI irreversible wave. On the other hand, pyrazine bridged binuclear complex 3 exhibited two waves, which correspond to CuIICuII/CuIICuI and CuIICuI/CuICuI redox processes. Differential pulse voltammetry (DPV) experiments also exhibited the same reduction behavior. These complexes displayed effective antioxidant SOD activity and exhibit the outlines of a structure-based cyclic mechanism. On the basis of experimental and theoretical DFT studies, the structure–activity relationships of these complexes have also been discussed. [ABSTRACT FROM AUTHOR]

The synthesis of novel dithiophosphate derivatives has been achieved. TwoO,O′-alkanediylS-(N-phthalimidomethyl) dithiophosphates and two Zinc bis(O,O′-alkanediyl) dithiophosphates are synthesized by an easy and facile chemical synthetic route. Zinc bis[O,O′-(2-methylpentane-2,4-diyl) dithiophosphate]L1, Zinc bis[O,O′-(2-ethylhexane-1,3-diyl) dithiophosphate]L2,O,O′-(2-methylpentane-2,4-diyl)S-(N-phthalimidomethyl) dithiophosphateL3andO,O′-(2-ethylhexane-1,3-diyl)S-(N-phthalimidomethyl) dithiophosphateL4are synthesized from the respective ammonium salts. CompoundsL1,L2,L3, andL4are characterized by (CHN) elemental analysis, ESI mass, FT-IR,1H,13C, and31P NMR techniques. The crystal structure of ammoniumO,O′-(2-methylpentane-2,4-diyl) dithiophosphate is discussed.L1,L2,L3, andL4were evaluated for antimicrobial activity. It was found that the phthalimide derivativesL3andL4showed much better antifungal potential against some species of fungus. The Zinc dithiophosphatesL1andL2showed good antibacterial activity againstBacillus cereusandEscherichia coli. [ABSTRACT FROM PUBLISHER]

2-Chlorophenyl methanethiol undergoes air oxidation catalyzed by different selenides and yields the corresponding disulfide 1 in two polymorphic forms, 1a and 1b. In the molecular structures of the two new polymorphs of o,o'-dichloro dibenzyl disulfide, the dihedral angles between the dibenzyl groups are 82.0(1)°, (1a), and 73.7(4)°, (1b), respectively [(1a): P-1, a = 8.424(2) Å, b = 8.838(2) Å, c = 10.5823(19) Å, α = 90.122(18)°, β = 112.19(2)°, γ = 95.19(2)°, V = 725.9(3) Å3; (1b): P21/n, a = 10.5888(10) Å, b = 9.1590(6) Å, c = 15.2489(14) Å, β = 103.072(9)°, V = 1440.6(2) Å3]. MOPAC computational studies yield dihedral angles of 89.6(5)° and 71.9(9)°. Crystal packing is stabilized by weak π-ring (C-H···Cg) intermolecular interactions in both 1a and 1b and by additional weak Cg ··· Cg intermolecular interactions in 1b, which influence the bond distances, bond angles, and torsion angles of the dibenzyl groups in each polymorph. Additional characterization of each polymorph has been carried out by TEM, IR, 1H and 13C NMR spectroscopy, microanalysis, and by FAB mass spectrometry. TEM studies of a sample of 1a show that it contains cigar-shaped crystallites. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. [ABSTRACT FROM AUTHOR]

Reactions of copper(I) halides with a series of thiosemicarbazone ligands (Htsc) in the presence of triphenylphosphine (Ph3P) in acetonitrile have yielded three types of complexes: (i) monomers, [CuX(Β¹-S-Htsc)(Ph3P)2] [X, Htsc = I (1), Br (2), benzaldehyde thiosemicarbazone (Hbtsc); I (5), Br (6), Cl (7), pyridine-2-carbaldehyde thiosemicarbazone (Hpytsc)], (ii) halogen-bridged dimers, [Cu2(μ2-X)2(Β¹-S-Htsc)2(Ph3P)2] [X, Htsc = Br (3), Hbtsc; I (8), furan-2-carbaldehyde thiosemicarbazone (Hftsc); I (11), thiophene-2-carbaldehyde thiosemicarbazone (Httsc)], and (iii) sulfur-bridged dimers, [Cu2X2(μ2-S-Htsc)2(Ph3P)2] [X, Htsc = CI (4), Hbtsc; Br (9), Cl (11)), pyrrole-2-carbaldehyde thiosemicarbazone (Hptsc); Br (12), Httsc]. All of these complexes have been characterized with the help of elemental analysis, IR, ¹H, 13C, or 31P NMR spectroscopy, and X-ray crystallography (1–12). In all of the complexes, thiosemicarbazones are acting as neutral S-donor ligands in Β¹-S or μ2-S bonding modes. The Cu⋯Cu separations in the Cu(μ2-X)2Cu and Cu(μ2-S)2Cu cores lie in the ranges 2.981(1)–3.2247(6) and 2.813(1)–3.2329(8) Å, respectively. The geometry around each Cu center in monomers and dimers may be treated as distorted tetrahedral. Ab initio density functional theory calculations on model monomeric and dimeric complexes of the simplest thiosemicarbazone [H2C=N-NH-C(S)-NH2, Htsc] have revealed that monomers and halogen-bridged dimers have similar stability and that sulfur-bridged dimers are stable only when halogen atoms are engaged in hydrogen bonding with the solvent of crystallization or H2O molecules. [ABSTRACT FROM AUTHOR]

The crystal and molecular structures of the organomercury(II) complexes [Hg(C6H5)(chtsc)], 1 , and [Hg(C6H5C5H4N)(btsc)], 2 , obtained from the reaction of phenylmercury(II) acetate with cyclohexanone thiosemicarbazone (Hchtsc) and that of [2-(pyridin-2′-yl)]phenyl]mercury(II) acetate with benzaldehyde thiosemicarbazone (Hbtsc), respectively, are described. Both 1 and 2 are monoclinic, space group C 2/ c . Complex 1 has a distorted T-shaped geometry {C-Hg-S, 161.91(10)°} and 2 can be considered to have a distorted seesaw geometry {C-Hg-S, 171.2(10)°}. In both complexes the ligands act as bidentate chelating anions bonding through azomethine N 1 and thiolato S atoms. [ABSTRACT FROM AUTHOR]

A novel β-ketoimine, 4- N -(cyclohexylimino)-2-pentanone, was synthesized and reacted with dibutyl magnesium to afford the desired magnesium bis(β-ketoiminate). The complex, bis[4- N -(cyclohexylimino)-2-pentanonato]magnesium(II), has been structurally characterized by single-crystal X-ray diffraction methods. Crystallographic analysis shows the four-coordinate complex to be homoleptic and monomeric in the solid state. The geometry around the Mg(II) atom is a distorted tetrahedron. The bulky cyclohexyl groups provide enough steric bulk about magnesium to inhibit intermolecular interactions. The crystal structure of the complex is triclinic, space group , with a = 8.301(3), b = 11.301(4), c = 12.023(4) Å, α = 75.840(6), β = 88.867(6), γ = 84.611(6)°, Z = 2. The two normal Mg-O and Mg-N bond lengths are, respectively, 1.9162(11), 1.9265(11) and 2.0699(13), 2.0822(12) Å. [ABSTRACT FROM AUTHOR]