Theoretical study of mono- and dithiocarbazic acid derivatives (original) (raw)
Related papers
Inorganica Chimica Acta, 2018
Three dithiocarbazate complexes, CdL 2 (1), Cu 2 L 2 (OAc) 2 (2) and [CuLCl] n (3), are synthesized using S-allyl-3-[(2-pyridyl-methylene)]dithiocarbazate (HL) as tridentate ligand. All compounds are characterized by elemental analysis, molar conductance, FT-IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray diffraction. In all the complexes, the ligand (L¯) coordinates to the metal centers through the pyridine nitrogen, the azomethine nitrogen and the thiolate sulfur atoms. In compound 1, two ligand units encompass the cadmium(II) ion in bischelate distorted octahedral fashion. In the copper binuclear compound (2), each metal atom is coordinated to one L¯ ligand unit and the two copper atoms are held by two bridging acetate ligands. In the coordination polymer 3, copper has a distorted square pyramidal geometry in which L¯ holds three coordination positions and two chloride ligands complete the fivecoordinated arrangement, so that each chlorine atom links two adjacent Cu centers. Molecular geometries, vibrational frequencies and optimized structure energies are compared using the density functional method (B3LYP) with 6-311++G(d,p) basis set. Electronic absorption spectra of compounds are predicted with TD-DFT studies and compared with experimental ones. Natural bond orbital analysis (NBO) is performed for HOMO-LUMO, charge delocalization, intramolecular hydrogen bonding and orbital contributions.
CERN European Organization for Nuclear Research - Zenodo, 1984
Thiodlsucdnlc acid, (TDSA), forms stable complexes with cobalt(ll), nickel(II) and copper(II) of the type [M,L.XH 1 0J, (M=metal; L=Jigand; X =6 for cobalt(ll), nickelfll), and 4 for copper(ll)J and with cbromium(Ill) of the type IM.L.(OH).J-XH,O (X=2}. Their structures have been characterised on the basis ofelemental analysis, magnetic moment, electronic and ir spectral studies. Cobalt(ll) forms high• spin octahedral complex, nickel(ll} and copper(II) form distorted oclahedral complexes and chromium(lll) forms high-spin typically oxo-bridged octahedral complex. IR spectra show that coordination takes place through carboxylate groups of the ligand and their coordination polybedron must be completed either by water molecules or-OH bridges or by some intermolecular interactions, probably through free carboxylic oxygens. Relevant ligand field parameters have been calculated for these complexes. The nephelauxetfc effect seems to be more effective for cobalt(ll) than for nlckel(ll).
Synthesis and characterization of some transition metal chelates of 2, 2'-dithiobenzoic acid
Metal complexes of divalent copper (1-2), cobalt (3), and nickel (4) with mixed ligands acetylacetone (acac) and adenine were prepared and characterized by IR, mass spectra, elemental and thermal analysis. The X-ray crystal structures of {[Cu(acac) 2 (adenine)]ÁEtOH} complex (1) and {[Cu(acac) 2 (adenine)]ÁDMFÁH 2 O} (2) were determined. Compound (1) crystallizes in the triclinic space group P -1 with a = 7.547 Å , b = 7.828(3) Å , c = 17.791(6) Å , a = 79.538(6)°, b = 82.240(7)°, c = 86.010 (6)°, V = 1023.1(6) Å 3 , and Z = 2. Complex (1) forms a hydrogen bonded 2:2 complex {[Cu(acac) 2 (adenine)] 2 : [EtOH] 2 } arranged in bilayers. Complex (2) crystallizes in the triclinic space group P -1 with a = 7.828(2) Å , b = 8.095(2) Å , c = 16.995(5) Å , a = 78.508(5)°, b = 84.949(5)°, c = 89.285(5)°, V = 1051.2(5) Å 3 , and Z = 2.
Structure and stability of complexes of thiohydantoin derivative
Journal of Chemical Sciences, 1986
The formation constant of 4-phenylhydrazono-2-thiohydantoin with 3d transition metal ions has been determined. The factors affecting the stability of the metal chelates have been studied. Complexes of Ag(1), Cu(lI), Cd(lI) and Pd(II) with the ligand have been isolated and characterized by physico-chemical techniques. The ligand forms a 1 : 1 complex with Ag(l) and 1:2 complexes with the other metal ions. Keywords. 4-Phenylhydrazono-2-thiohydantoin; transition metal complexes with thiohydantoin; potentiometric studies; 1R spectra.
Inorganica Chimica Acta, 1984
3,6_dithianoctanedioic acid forms a Cu(I) compound in which electrical neutrality is achieved by elaborate hydrogen bonding and sharing of protons. The title compound crystallizes in the monoclinic space group P2/n with Z = 2. Unit-cell parameters are a = 11.625(2), b = 7.664(l), c = 9.874(2) 4 0 = 95.16", D,,, = 1.80(2), D, = 1.83 g cmS3. The structure was solved by means of standard direct methods and refined with full-matrix least-squares techniques to an R-value of 0.026 (R, = 0.042). The &(I) ion is tetrahedrally coordinated by four thioether Satoms (Cu-S = 2.29-2.33 A). The molecules are linked by very strong hydrogen bonds between noncoordinating carboxylate groups in such a way that the average number of acidic hydrogens per molecule is ?hree. One of these hydrogens lies on a twofold axis and forms a short symmetrical hydrogen bond, with a O-O distance of 2.441(2) A Unusual features in the infrared spectrum of this compound can be interpreted on the basis of the observed crystal structure.
Inorganica Chimica Acta, 2015
a b s t r a c t By using g 3 -(SCH 2 CH 2 SCH 2 CH 2 S) (SSS), 2-thiocytosine (HL 1 ) and 5-amino-1,3,4-thiadiazole-2-thiol (HL 2 ) as S-donor ligands two '3 + 1' mixed ligand red oxorhenium(V) complexes of the type [ReO(SSS)(HL 1 )]Cl (1Cl) and [ReO(SSS)(L 2 )] (2) have been synthesized. Both 1Cl and 2 have been characterized by C, H and N microanalyses, 1 H NMR, FT-IR, UV-Vis spectra and conductivity measurements. The X-ray crystal structures of both 1Cl and 2 have been determined. Electrochemical studies of 1Cl in acetonitrile show four successive one-electron redox couples; while 2 in DMSO displays only two one-electron redox steps. A computational and conceptual Density Functional Theory (DFT) studies have been performed on various (3 + 1) complexes of Re(V). The fully-optimized complexes, 1Cl and 2, adopt geometries that satisfactorily corroborate the X-ray structures. Subsequently these optimized structures were employed to investigate systematically the relative stabilities of various Re(V) complexes with varying ligands having N, O and S donor atoms. The electronic properties of 1Cl and 2 were delved into employing the hybrid STMP TD-DFT method and the results were found to be in good harmony with the experimental observations.
Physicochemical Properties and Molecular Mechanics of Some Thiohydantoin Derivatives Complexes
The organic ligands Cinnamaldehydethiosemicarbazone(1), 3-(3-Phenyl-allylideneamino)-2-thioxoimidazolidine-4-one (2), [4-Oxo-3-(3-phenyl-allylideneamino)-2-thioxo-imidazolidin-1-yl]-acetic acid (3), 1-(1-aza-4-phenylbuta-1,3-dienyl)-2-methylthio-2-imidazolin-5-one (4) and 1-(1-aza-4-phenylbuta-1,3-dienyl)-2-methylthio-2-imidazolin-5-one (5) were prepared and characterized using spectroscopic and physico-chemical methods (Scheme 1). The modeling of the synthesized compounds (1 and 2) and the computation of the steric, Van der Waals, bending and stretching energy were calculated using the Molecular Mechanical method (MM2) using CS cheme Office program. For each conformation of the synthesized compounds (1, 2), the minimum energy one was determined and listed. The complexes of the compound 1 and 2 with Zn(II), Cu(II) and Ni(II) were prepared and characterized. The postulated spatial arrangements have been confirmed using the molecular modeling program, elemental analysis (CHNM %), conductance, IR, thermal analysis and mass spectra.
Tetrahedron, 1974
with compound (1) gave dibenzoyl, while 2 and 3 gave the corresponding 3_oxo(ZH)thiophenes 5. With copper-bronze I gave 2,2'-di-(thiobenzoate) (4), while 2 gave 2.7diphenylthiepin (6a) and 2,5_diphenylthiophene (7a), but 3 gave only 2,5-di-(pmethoxyphenyl)thiophene (7b). With Grignard reagents 1 gave the corresponding methanol derivative 14, while 2 gave the thiobenzoylethylenes 13s and b, but 3 gave 2.7 -di -(pmethoxyphenyl) -4,4,5.5tetraphenyl(4H)thiepin (IS). The reaction mechanisms are discussed.