Navegando por Autor "Janczak, Jan"

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Hydrogen-bonding network in the crystal of bis[1-(diaminomethylene)thiouron-1-ium] oxalate.
(2012) Perpétuo, Genivaldo Julio; Janczak, Jan
The single crystals of bis[1-(diaminomethylene)thiouron-1-ium] oxalate were grown using a solution growth technique. The compound crystallises in the centrosymmetric C2/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but twisted. Both arms of the cation are oppositely rotated by 5.0(1)_ around the C–N bonds involving the central N atom. The centrosymmetric oxalate(2-) anion is planar. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and oxalate(2-) anions in the crystal is mainly determined by ionic and hydrogen bonding interactions forming three-dimensional network. The compound was also characterised by the FT-IR and Raman spectroscopy. The characteristic bands of the NH2, C=S and COO_ groups as well as of C–N–C, N–C–N and C–COO skeletal groups are discussed.
Hydrogen-bonding one-dimensional arrangement in the crystal of N-phenyl-2-hydroxyacetamide.
(2009) Perpétuo, Genivaldo Julio; Janczak, Jan
The N-phenyl-2-hydroxyacetamide was obtained in crystalline form by a direct reaction of aniline with glycolic acid. The whole molecule in the crystal is non-planar, but the planar 2-hydroxyacetamide group is inclined by 7.8(1)_ to the plane of the phenyl ring that is cis located to the carbonyl oxygen atom. The hydroxyl group is in trans position to the carbonyl oxygen atom. The molecules are linked by the N--H_ _ _O and O--H_ _ _O hydrogen bonds into one-dimensional chains along the a-axis. Additionally, the C--H_ _ _p interactions interconnect the chains stabilizing the crystal structure. The X-ray geometry of the N-phenyl- 2-hydroxyacetamide molecule has been compared with that obtained by the ab-initio molecular orbital calculated results that represents the geometry in the gas-phase.
NLO crystals of bis[1-(diaminomethylene)thiouron-1-ium] tartate(2 -) hemihydrate and deuterated [1-(diaminomethylene)thiouron-1-ium] tartate(- ).
(2013) Perpétuo, Genivaldo Julio; Janczak, Jan
The protiated single crystals of bis[1-(diaminomethylene)thiouron-1-ium] tartate hemihydrate were grown using a solution growth technique. The deuterated single crystals of [1-(diaminomethylene)thiouron-1-ium] tartate(_) were obtained by threefold recrystallisation of protiated crystals. The protiated and deuterated compounds crystallise in the non-centrosymmetric space groups P21212 and P21 of the orthorhombic and monoclinic systems, respectively. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation in both structures is very similar and is almost planar. The double deprotonated tartate(2_) dianion in protiated crystals exhibits C2 symmetry, while tartate(_) monoanion in deuterated crystals has C1 symmetry. The oppositely charged components of the crystals, i.e. 1-(diaminomethylene)thiouron-1-ium cation and tartate(2_) dianion in protiated and 1-(diaminomethylene)thiouron-1-ium cation and tartate(_) monoanion, interact via different hydrogen bonding motifs: R12 (6) and R22 (8) in protiated and R21 (5) and R12 (6) in deuterated crystals forming 2:1 and 1:1 supramolecular complexes. These supramolecular complexes interact each other via NAH_ _ _O or OAH_ _ _O hydrogen bonds forming the 2D-layered structures. Both compounds were also characterised by IR-spectroscopy. The SHG efficiency relative to potassium dihydrophosphate (KDP) was found to be 0.77 and 0.82 for protiated and deuterated crystals, respectively.
Structural and spectroscopic characterization of 1-(diaminomethylene) thiouron-1-ium benzoate and bis(1-(diaminomethylene)thiouron-1-ium) phthalate trihydrate.
(2016) Perpétuo, Genivaldo Julio; Janczak, Jan
Two single crystals of 1-(diaminomethylene) thiouron-1-ium benzoate (1) and bis(1-(diaminomethylene) thiouron-1-ium) phthalate trihydrate (2) were grown using a solution growth technique. The compound 1 crystallises in the centrosymmetric P21/c space group of the monoclinic system, whereas the compound 2 in the centrosymmetric Pbcn space group of orthorhombic system. The solid-state organisation of 1 and 2 has been analysed with respect to cation-anion and hydrogen bonding interactions. The oppositely charged units interact via almost linear hydrogen bonds with the graphs of R2 2 (8) and R21(6) forming molecular complexes. In the crystal 1 the R2 2 (8) motif is formed by donation to the carboxylate group from amine group joined to C1 and from imine group and R2 1(6) motif is formed by donation to the O2 from amine group joined to C2 and from imine group, whereas in crystal 2 the graphs are formed oppositely. Interactions between the hydrogen-bonded molecular complexes in 1 lead to formation of layered 2D structure, whereas in 2, due to presence of hydrated water molecules lead to formation of 3D hydrogen-bonded supramolecular network. The obtained deuterated analogues of 1 and 2 crystallise similar as H-compound in the monoclinic and orthorhombic system with quite similar lattice parameters. The compounds were also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups are discussed.
Structural and spectroscopic characterization of bis[1- (diaminomethylene)thiouron-1-ium] naphthalene-1,5-disulfonate.
(2018) Felix, Marcela Campanha; Perpétuo, Genivaldo Julio; Janczak, Jan
Single crystals of bis[1-(diaminomethylene)thiouron-1-ium] naphthalene-1,5-disulfonate (1) are grown using growth solution technique. The compound crystallizes in the centrosymmetric C2/c space group of the monoclinic system with four molecules per unit cell. The arrangement of oppositely charged units, i.e. 1-(diaminomethylene)thiouron-1-ium cations and naphthalene-1,5-disulfonate anions in the crystal is mainly determined by the ionic and the NeH/O hydrogen bonding interactions. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both qualitatively and quantitatively interactions governing the supramolecular arrangement. The compound was also characterized by FT-IR and Raman spectroscopies. The vibrational assignment of the characteristic bands of the functional groups have been supported by the isotopic frequency shift.
Structural and vibrational characterization of 1-(diaminomethylene)-thiouron-1-ium 4-aminobenzoate.
(2021) Perpétuo, Genivaldo Julio; Janczak, Jan
The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-aminobenzoate, (C2H7N4S)-(NH2C6H4COO), (1) suitable for the X-ray analysis were grown using a solution growth technique room temperature. Recrystallization of 1 in heavy water (three-times) yield respective deuterated analogue, (C2D7N4S)(ND2C6H4COO), (1d). The X-ray single crystals analyses show that both, protiated and deuterated, compounds crystallize in the same crystal system with quite similar lattice parameters. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but slightly twisted. The 4-aminobenzoate(-) anion is also non-planar. The planar COO− group is inclined to the plane of aromatic ring by 5.2(2)o. In the crystal the oppositely charged units, i.e. 1-(diaminomethylene)thiouron- 1-ium cation and 4-aminobenzoate anion interact via two of almost linear N–H...O hydrogen bonds with a graph of R2 2(8), that are further interact each other forming three dimensional hydrogen-bonded net- work. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both quantitatively and qualitatively interactions governing the supramolecular assemblies. The compound was also characterised by the FT-IR and Raman spectroscopy. The vibrational assignments have been supported by the isotopic frequency shift as well as by the DFT calculations.
Supramolecular aggregation in new crystals with nonlinear optical properties : 2-aminophenol-HClO4, 3-aminophenol-HClO4 and 4-aminophenol-HClO4.
(2009) Janczak, Jan; Perpétuo, Genivaldo Julio
Three new hybrid crystals of 2-aminophenol-HClO4 (2-AP-HClO4,1), 3-aminophenol-HClO4 (3-AP-HClO4, 2) and 4-aminophenol-HClO4 (4-AP-HClO4, 3) were obtained and their crystal structures determined. The 1 crystallises in centrosymmetric space group C2/c of monoclinic system while the other two (2 and 3) crystallise in the non-centro symmetric space groupP21 andP212121, respectively. The oppositely charged units of the crystals, i.e. positively charged 2-APHþ, 3-APHþ and 4-APHþ and ClO4 , interact viaweak Nþ–H/O and O– H/O hydrogen bonds forming 3D-supramolecular network. Relative to KDP the SHG efficiencies are 0.62 for 2 and 0.33 for 3, measured at 1064 nm using the Kurtz–Perry method.
Supramolecular architectures in crystals of melamine and aromatic carboxylic acids.
(2008) Perpétuo, Genivaldo Julio; Janczak, Jan
Two crystals containing melamine (M), melaminium (MH+), and aromatic carboxylic acids are synthesized and characterized by single-crystal X-ray diffraction analysis: melamine–melaminium 3,4,5-trihydroxybenzoate (THB_) dihydrate (1), and melamine–melaminium 2-acetylbenzoate (AB_) dihydrate (2). In the crystal structures protonated (MH+) and non-protonated melamine (M) molecules are interconnected via NAH___N hydrogen bonds into a planar dimer in (1) and one-dimensional polymer in (2). The NAH___O hydrogen bonding interaction between the protonated nitrogen atom of MH+ and the carboxylate oxygen atom of the corresponding anion is observed in both structures. However, only in (1) it results in an almost planar ionic unit (THB_MH+) where additional p–p interactions between the anions appear, that are missing in (2). The water molecules act as donor and as acceptor of hydrogen bonds linking the substructures observed in the (1) and (2) crystals into 3D supramolecular networks.
Supramolecular hydrogen-bonding network in 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate crystal.
(2015) Perpétuo, Genivaldo Julio; Gonçalves, Rafael Silva; Janczak, Jan
The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate were grown using a solution growth technique. The compound crystallises in the centrosymmetric P21/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but twisted. Both arms of the cation are oppositely rotated by 8.5(1)_ around the CAN bonds involving the central N atom. The arrangement of oppositely charged components, i.e. 1-(diamino methylene)thiouron-1-ium cations and 4-hydroxybenzenesulfonate anions in the crystal is mainly determined by ionic and hydrogen-bonding interactions forming supramolecular network. The possible hydrogen bonding interactions between cation and anion units were analysed on the basis of molecular orbital calculations. The obtained deuterated analogue crystallises similar as H-compound in the monoclinic system (P21/c) with quite similar lattice parameters. The compound was also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups of the protiated and deuterated analogue of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate are discussed.
Supramolecular hydrogen-bonding networks in the 1-(diaminomethylenene)thiouron-1-ium 4-hydroxybenzoate, 3,4-dihydroxybenzoate and 3,4,5-trihydroxybenzoate monohydrate crystals.
(2013) Perpétuo, Genivaldo Julio; Janczak, Jan
Three crystals of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzoate (1), 1-(diaminomethylene)thiouron-1-ium 3,4-dihydroxybenzoate (2) and 1-(diaminomethylene)thiouron-1-ium 3,4,5-trihydroxybenzoate monohydrate (3) were grown using a solution growth technique. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation in these structures is very similar and exhibits twisting conformation. The planar COO- group of the oppositely charged components of the crystals, i.e. 4-hydroxybenzoate, 3,4-dihydroxybenzoate and 3,4,5-trihydroxybenzoate, are slightly inclined to the benzene ring. Both oppositely charged units, i.e. the 1-(diaminomethylene)thiouron-1-ium cation and respective mono- di- or trihydroxybenzoate anions, interact via R22(8) hydrogen bonding motif forming 1:1 supramolecular complexes. These supramolecular complexes interact each other via N--O or O—H---O hydrogen bonds forming the 3D-hydrogen bonding networks. These compounds were also characterised by the IR-spectroscopy. The characteristic bands of the NH2, OH,C=S, COO- as well as of the skeletal groups are discussed.
Syntheses, crystal structure and spectroscopic characterization of new platinum(II) dithiocarbimato complexes.
(2008) Amim, Raquel dos Santos; Oliveira, Marcelo Ribeiro Leite; Perpétuo, Genivaldo Julio; Janczak, Jan; Miranda, Liany Divina Lima
The reaction of 4-iodobenzenesulfonamide or 4-fluorobenzenesulfonamide with CS2 and KOH in dimethylformamide yielded the potassium N-R-sulfonyldithiocarbimates, K2(RSO2N@CS2) [R = 4-IC6H4 (1) and 4-FC6H4 (2)]. These salts reacted with K2[PtCl4] in water/methanol to yield complex anions bis(N-R-sulfonyldithiocarbimato) platinate(II), which were isolated as their tetrabutylammonium salts, (Bu4N)2[Pt(RSO2N@CS2)2] [R = 4-IC6H4 (3) and 4-FC6H4 (4)]. The structures of 2–4 were determined by X-ray crystallography. The Pt2+ in both complexes 3 and 4 lies at the inversion centre and the PtS4 moiety has a distorted square-planar configuration. The compounds were also characterized by IR, 1H NMR and 13C NMR spectroscopies, and elemental analyses. The molar conductance data are consistent with the fact that 3 and 4 are dianionic complexes.
Syntheses, crystal structure and spectroscopic characterization of novel N-R-sulfonyldithiocarbimate and triphenylphosphine nickel(II) complexes.
(2002) Oliveira, Marcelo Ribeiro Leite; Vieira, Heulla Pereira; Perpétuo, Genivaldo Julio; Janczak, Jan; Bellis, Vito Modesto De
Three new complexes of the general formula: [Ni(PPh3)2(RSO2N_/CS2)] where R_/2-CH3C6H4 (1), 4-CH3C6H4 (2) and 4-BrC6H4 (3) were obtained in crystalline form by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimates (K2(RSO2N_/CS2)) and triphenylphosphine with nickel(II) chloride in ethanol_/water. The 1 complex crystallizes in the centrosymmetric space group of the triclinic system with two molecules per unit cell, while 2 and 3 complexes crystallize in the Pbca space group of the orthorhombic system with eight molecules per unit cell. The X-ray single-crystal analysis showed that all complexes present a similarly distorted square-planar configuration around the nickel atom due to the steric effect of the triphenylphosphine ligands and the didendate chelation by the two sulfur atoms of the dithiocarbimate ligand. The IR and UV_/Vis spectral data are consistent with the formation of almost square-planar nickel complexes. The 1H NMR, 13C NMR, 31P NMR spectra showed the expected signals for the triphenylphosphine and the dithiocarbimate moieties.
Syntheses, crystal structure and spectroscopic characterization of novel N-R-sulfonyldithiocarbimate zinc(II) complexes.
(2003) Perpétuo, Genivaldo Julio; Oliveira, Marcelo Ribeiro Leite; Janczak, Jan; Vieira, Heulla Pereira; Amaral, Fabiana Fonseca do; Bellis, Vito Modesto De
Two new compounds of the general formula: (Ph4P)2[Zn(RSO2N@CS2)2], where R¼C6H5 (1) and 4-CH3C6H4 (2) were obtained in crystalline form by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N@CS2K2) with zinc(II) acetate dihydrate in dimethylformamide. The compounds crystallise in the centrosymmetric space group of the triclinic system with Z ¼ 2. The single crystal X-ray analysis showed a similarly distorted tetrahedral configuration around the zinc(II) cation due to the bidentate chelation by two sulfur atoms of the N-R-sulfonyldithiocarbimate ligands. Ionic interaction between oppositely charged moieties, i.e., the bis(N-R-sulfonyldithiocarbimato)zincate(II) dianion [Zn(RSO2N@CS2)2]2_ and tetraphenylphosphonium cation Ph4Pþ and van der Waals interactions determine the crystal packing motif. The IR data are consistent with the formation of zinc–dithiocarbimate complexes. The 1H NMR and 13C NMR spectra showed the expected signals for the tetraphenylphosphonium cation and the dithiocarbimate moieties.
Syntheses, crystal structure, spectroscopic characterization and antifungal activity of new N-R-sulfonyldithiocarbimate metal complexes.
(2009) Alves, Leandro de Carvalho; Rubinger, Mayura Marques Magalhães; Lindemann, Renata Hernandez; Perpétuo, Genivaldo Julio; Janczak, Jan; Miranda, Liany Divina Lima; Zambolim, Laércio; Oliveira, Marcelo Ribeiro Leite
Five new compounds with the general formula of (Bu4N)2[M(RSO2N@CS2)2], where Bu4N = tetrabutylammonium cation, (M = Ni, R = 4-FC6H4) (1), (M = Zn, R = 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-IC6H4), (2), (3), (4) and (5), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N@CS2K2) with nickel(II) chloride hexahydrate or zinc(II) acetate dihydrate in metanol:water 1:1. The elemental analyses and the IR data are consistent with the formation of the expected bis(dithiocarbimato) metal(II) complexes. The 1H and 13C NMR spectra showed the signals for the tetrabutylammonium cation and the dithiocarbimate moieties. The compounds 1, 2 and 5 were also characterized by X-ray diffraction techniques. The nickel(II) is coordinated by two N-4-fluorophenylsulphonyldithiocarbimato(2-) ligands forming a planar coordination. The zinc(II) exhibits distorted tetrahedral configuration in compounds 2 and 5 due to the chelation effect of two sulfur atoms of the N-R-sulfonyldithiocarbimate ligands. The antifungal activities of the compounds were tested in vitro against Colletotrichum gloeosporioides, an important fungus that causes the plant disease known as anthracnose in fruit trees. All the complexes were active.
Syntheses, structural and spectroscopic characterization of novel zinc(II)-bis(trithiocarbimato) complexes and bis(N-methylsulfonyldithiocarbimate)-sulfide.
(2012) Tavares, Eder do Couto; Oliveira, Marcelo Ribeiro Leite; Janczak, Jan; Vieira, Camila Grossi; Alves, Leandro de Carvalho; Castro, Rodrigo Antunes; Vieira, Lígia Maria Mendonça; Lindemann, Renata Hernandez; Perpétuo, Genivaldo Julio; Visconte, Leila Léa Yuan; Rubinger, Mayura Marques Magalhães
Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A2[Zn(RSO2N@CS3)2] [A= Ph4P+: R = CH3 (1), 4-CH3C6H4 (2); A = Bu4N+: R = CH3 (3), 4-CH3C6H4 (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph4P)2[(CH3SO2N@CS2)2S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, 1H NMR and 13C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS4) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P41212 of the tetragonal system.
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2.
(2006) Janczak, Jan; Perpétuo, Genivaldo Julio
Crystals of the new one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2 (Pc = C32H16N8) were grown directly from phthalonitrile and pure zirconium powder under the oxidation conditions of IBr at 220 _C. [ZrPc2]IBr2 crystallises in the space group P21/m of the monoclinic system, with lattice parameters of: a = 6.697(1), b = 25.483(5), c = 16.918(3)A ˚ , b = 100.03(3)_ and Z = 2. The crystals of [ZrPc2]IBr2 are built up from one-electron oxidized [ZrPc2]+ units that form stacks parallel to a axis of the crystal and mixed electron-rich trihalide ions of IBr2 _. The iodine atom of the IBr2 ions is located at the inversion center, so the IBr2 _ ions are linear and symmetrical. The mutual arrangement of [ZrPc2]+ and IBr2 _ ions is different to that found in the one-electron oxidized [ZrPc2]I3 Æ I2 complex as well as to that found in the tetragonal crystals of partially oxidized [ZrPc2](I3)2/3. EPR experiment shows that the oxidation of the diamagnetic ZrPc2 complex by IBr is ligand centered. The UV–Vis spectrum of [ZrPc2]IBr2 shows, besides the bands observed in the spectrum of ZrPc2, one additional band at _496 nm, which indicates the existence of the one-electron oxidized phthalocyaninato(1_)p-radical ligand and it is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data shows anisotropy and non-metallic character in conductivity (dr/dT > 0). The charge transport mainly proceeds along the stacks of one-electron oxidized [ZrPc2]+ units. The relatively high conductivity along the [ZrPc2]+ stack results from the staggered configuration of the Pc-rings (rotation angle 45.0(3)_) that makes short inter-ring Ca(pyrrole)–Ca(pyrrole) contacts (2.858(2)–3.017(3)A ˚ ) and greatest overlap of the HOMO orbitals that form the conduction band of the molecular materials.
Synthesis, structural and spectroscopic characterization of novel zinc(II) complexes with N-methylsulfonyldithiocarbimato and N-methylsulfonyltrithiocarbimato ligands.
(2007) Oliveira, Marcelo Ribeiro Leite; Perpétuo, Genivaldo Julio; Janczak, Jan; Rubinger, Mayura Marques Magalhães
Two new zinc(II)-complexes, dithiocarbimato (Ph4P)2[Zn(CH3SO2N@CS2)2] (1) and trithiocarbimato (Ph4P)2[Zn(CH3SO2N@CS3)2] (2), were obtained in the crystalline form by the reaction of potassium N-methylsulfonyldithiocarbimate (RSO2N@CS2K2) with zinc(II) acetate dihydrate and tetraphenylphosphonium chloride in dimethylformamide. Both complexes crystallize in the monoclinic system. The central Zn(II) ion has a distorted tetrahedral coordination in both compounds. In 1 the dithiocarbimato ligand coordinates via two S atoms while in 2 the trithiocarbimato ligand coordinates via S and N atoms. Both complexes were also characterized by IR, 1H NMR and 13C NMR spectroscopies. Compound 2 is the first example of a zinc(II)-trithiocarbimato complex.