Molecular structure and spectral characteristics of bis(S-methyl-N-(2-pyridyl)methylendithiocarbazato)nickel(II), (Ni(NNS)2)

A nickel(II) complex of the pyridine-2-aldehyde Schiff base of S-methyldithiocarbazate (HNNS) has been synthesized and characterized by means of elemental analysis, IR and UV-vis spectra. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic, space P2₁/c, with a = 14.092(2), b = 16.886(2), c = 8.857(2)Å; = 105.78(3) °, V = 2028.2(6) ų, and Z = 4. The nickel atom is octahedrally coordinated by two uninegatively charged tridentate Schiff base in a mer-configuration via the pyridine nitrogen atom, azomethine nitrogen atom, and mecaptide sulfur atom.     

Synthesis and Crystal Structures of Bromo(1,10-phenanthroline- N , N ′)tris(2-cyanoethyl)phosphinocopper(I) and Bromo(2,2′-bipyridine- N , N ′)tris(2-cyanoethyl)phosphinocopper(I)

The two new complexes bromo(1,10-phenanthroline-N,N′)tris(2-cyanoethyl)phosphinocopper(I) and bromo(2,2′-bipyridine-N,N′)tris(2-cyanoethyl)phosphinocopper(I) were synthesized and their X-ray crystal structures were determined. The first complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 7.7596(7) ?, b = 11.470(1) ?, c = 12.803(1) ?, α = 78.884(1)^°, β = 79.759(1)^°, γ = 86.867(1)^°, V = 1100.0(2) ?³ and Z = 2. The second complex crystallizes in the orthorhombic space group Pbca with the crystal cell parameters a = 10.614(1) ?, b = 12.345(1) ?, c = 31.903(3) ?, V = 4180.3(7) ?³ and Z = 8. In both compounds, the copper(I) ion is four-coordinate with a distorted tetrahedral geometry. In the 1,10-phenanthroline complex, an intermolecular dipole–dipole interaction between two cyano groups stabilizes an unfavorable synclinal conformation of one cyanoethyl group of the phosphine ligand.     

Structure of bis(dipropyldithiocarbamate) cadmium(II), [Cd2(n-Pr2dtc)4] (dtc = dithiocarbamate)

The cadmium complex of bis(dipropyldithiocarbamate), [Cd₂(n-Pr₂dtc)₄] (dtc = dithiocarbamate) was crystallized from ethylether. It crystallizes in the monoclinic system, space group P _2I/c, with lattice parameters, a = 8.2532(1), b = 19.4519(1), c = 13.4163(2) Å, = 99.243(1)°, and Z = 4. The X-ray single-crystal structure of [Cd₂(n-Pr₂dtc)₄] reveals that the complex is binuclear in the solid state and the Cd atom has a distorted square-pyramidal coordination environment and four equatorial donors are the two bidentate chelate sulfur atoms from two dtc ligands, of which the sulfur atom from the bridging dtc ligand occupies the apical position of the symmetry-related Cd atom in the dimer structure.     

Synthesis, Crystal Structure and Cytotoxic Property of Bis(4-chlorobenzoato)bis[1-(2-aminoethyl)piperidine]disilver(I)

Abstract  

4-Chlorobenzoic acid reacts with silver oxide and 1-(2-aminoethyl)piperidine to give a dinuclear silver(I) complex, [Ag₂(C₇H₄ClO₂)₂(C₇H₁₆N₂)₂]. The complex was characterized by elemental analysis and X-ray diffraction. The complex crystallizes in the triclinic space group P−1 with unit cell dimensions a = 6.8550(10), b = 8.7370(10), c = 13.859(2) ?, α = 73.213(3), β = 87.945(3), γ = 77.050(3)°, V = 774.09(18) ?³, Z = 1, R ₁ = 0.0386, and wR ₂ = 0.0791. The dimeric Ag complex is located on an inversion center. The Ag atom in the complex is three-coordinated by two N atoms from two 1-(2-aminoethyl)piperidine ligands and by one O atom of a 4-chlorobenzoate ligand, forming a triangular coordination. In the crystal structure, the molecules are linked through intermolecular N–H···O hydrogen bonds, forming chains running along the a axis. The complex shows high cytotoxic property to both normal and carcinoma cells.     

Synthesis and Crystal Structure Analysis of One Dimensional Supramolecular [Cd (Glu) (Tu)2]n

The complex of [Cd (C₅H₆O₄) (CH₄N₂S)₂]_n ( I ) has been synthesized and its X‐ray crystal structure determined at room temperature, M = 394.74, monoclinic, space group Pc (No. 7), with lattice parameters a = 7.683(3), b = 11.566, c = 16.00(1) Å, β = 100.32 (4)°, and Z = 4. There are two different Cd sites in this complex. Cd (1) coordinates to four oxygen atoms from Glutaric anion and two sulfide atoms from thiourea. Cd (2) coordinates to three oxygen and two sulfide atoms. The Cd atoms are linked by glutaric anion to form one‐dimensional chains. The adjacent chains are held together by hydrogen bonds to form a three dimensional network.     

Synthesis,Crystal and Molecular Structure of Cd2(sacch)4(Im)4

The title compound has been synthesized and its crystal structure determined at room temperature. Cd₂(Sacch)₄(Im)₄ F.W. = 1225.83, monoclinic. Space group: C2/c, Z = 4, a = 20.065(3) Å, b = 11.164(4) Å, c = 20.697(6) Å, β = 94.69(5)°, The coordination polyhedron of Cd(II) correspond to a five-coordinate trigonal-bipyramid. In the title complex, two of the saccharin groups act as monodentate ligands. The other two act as bidentate ligands. The two Cd(II) ions are bridged by the two bidentate saccharin groups and the distance is 4.75 Å.     

Crystal of Tetrakis(1-ethyl-1H-imidazole)diisothiocyanatocopper(II) bis(1-ethyl-1H-imidazole)diisothiocyanatocopper(II)

Abstract  A new complex [Cu(NCS)₄ (N-Eim)₄] [Cu(NCS)₂ (N-Eim)₂] (where N-Eim = N-ethylimidazole) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the Triclinic space group P−1 with the parameters: a = 8.7707(18) ?, b = 10.712(2) ?, c = 13.511(3) ?, α = 104.73(3)°, β = 104.84(3)°, γ = 102.52(3)°, V = 1131.54(3) ?³, with Z = 1 formula units. In the structure, the copper atoms all assume an elongated octahedral geometry with two distinct coordination environments; one is coordinated by four N-ethyl-imidazole ligands and two axial SCN groups, and another by two SCN groups and two N-ethyl-imidazole ligands. The two units form one infinite 1D zigzag chain along the [1 0 1] plane by two thiocyanate ligands from the [Cu(NCS)₄ (N-Eim)₄] units. Index Abstract  The title compound, tetrakis(1-ethyl-1H-imidazole)diisothio cyanatocopper(II) bis(1-ethyl-1H-imidazole)diisothiocyanatocopper(II) has been synthesized and structurally characterized by single-crystal X-ray diffraction. In the structure, the copper atoms all assume an elongated octahedral geometry with two distinct coordination environments. The two units form one infinite 1D zigzag chain along the [1 0 1] plane by two thiocyanate ligands from the [Cu(NCS)₄ (N-Eim) 4] units.      

Preparation and crystal structure of diaquabis(1,8-naphthyridine-N-monoxide)nickel(II)nitrate

The title compound [Ni(napyo)₂(H₂O)₂](NO₃)₂ was formed by the reaction of nickel(II) nitrate with 1,8-naphthyridine-N-monoxide (napyo) in ethanol medium. The complex crystallizes in the monoclinic, space groupP2₁/n withZ=2. Lattice parameters are:a=7.160(2),b=11.713(3),c=11.830(2) Å,=95.11(3)°. The structure was determined from 1399 observed reflections and refined toR=0.061. The Ni atom shows a slightly distorted octahedral coordination, being bonded to two oxygen atoms and two nitrogen atoms of two napyo ligands and to two oxygen atoms of two water molecules.     

Crystal Structure of bis(18-Crown-6)-bis(formato-O) dicaesium dihydrate

Abstract  The crystal structure of the title compound, [2Cs⁺(C₁₂H₂₄O₆)₂(CHO₂ ⁻)₂(H₂O)₂], was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁ /n with cell parameters a = 10.4278(7) ?, b = 10.0183(5) ?, c = 18.2383(12) ?, β = 93.723(5)°, V = 1910.3(2) ?³ and Z = 2. The Cs cations are bonded to each of the six O atoms of a crown ether ring, two water molecules, and one O atom of a formato anion. As a result of that, a centrosymmetric dimeric dinuclear complex is formed. The two halves of the dimer are connected by a ring of formato anions and water molecules which are linked by O–H···O hydrogen bonds. Index Abstract  The title compound, bis(18-crown-6)-bis(formato-O), caesium dihydrate, features a centrosymmetric dimeric dinuclear complex where two Cs cations are coordinated by six O atoms of a crown ether ring. The two halves of this complex are held together by a ring of formato anions and water molecules which are linked by hydrogen bonds.      

Crystal structure of bis(2,4-pentanedionato)copper(II)

The structure of bis(acetylacetonato)copper(II) has been redetermined from single crystal X-ray diffraction data. The unit cell parameters area=11.331(9),b=4.697(3),c=10.290(9) Å, and=91.84(7)dg. A finalR=0.056 for 727 observed reflections was obtained. The O-Cu-O chelate (bite) angle is 93.2(2)°. The two Cu-O bond lengths are 1.914(4) and 1.912(4) Å. The complex has a slight chair structure and a step angle of 7.05°.     

EPR spectra of (L-aspartate)di(2-pyridyl)aminezinc(II) hydrate substitutionally copper(II) doped complex

The [(L-aspartate)di(2-pyridyl)aminezinc(II)]hydrate doped with traces of copper was prepared. Electron paramagnetic resonance spectra of the polycrystalline sample were recorded at room temperature by using the X-band of the EPR spectrometer. The observedg factors for the complex areg _‖=2.258 andg _⊥=2.066. TheA _‖ value is 165.10⁻⁴ cm⁻¹. The crystal and molecular structure of the complex are also reported. The complex crystallizes in the monoclinic system; space groupP2₁ witha=7.2053(11),b=10.447(2),c=10.812(2) Å, β=108.489(14)° andZ=2. The structure can be described in the crystal lattice as polymeric chains.     

EPR spectra of (L-aspartate)di(2-pyridyl)aminezinc(II) hydrate substitutionally copper(II) doped complex

The [(L-aspartate)di(2-pyridyl)aminezinc(II)]hydrate doped with traces of copper was prepared. Electron paramagnetic resonance spectra of the polycrystalline sample were recorded at room temperature by using the X-band of the EPR spectrometer. The observedg factors for the complex areg _‖=2.258 andg _⊥=2.066. TheA _‖ value is 165.10⁻⁴ cm⁻¹. The crystal and molecular structure of the complex are also reported. The complex crystallizes in the monoclinic system; space groupP2₁ witha=7.2053(11),b=10.447(2),c=10.812(2) Å, β=108.489(14)° andZ=2. The structure can be described in the crystal lattice as polymeric chains.     

X-ray crystal structure of trans-bis(monoethanolamine) bis(saccharinato)nickel(II)

The crystal structure of trans-bis(monoethanolamine)bis(saccharinato)nickel(II), [Ni(C₇H₄NO₃S)₂(C₂H₇NO)₂], has been determined from X-ray diffraction data. The metal complex is monoclinic, with a = 11.0555(5), b = 8.9103(4), c = 11.3890(5) Å, = 105.0230(10)°, Z = 2, and space group P2_1/c . The structure consists of individual molecules. Two monoethanolamine molecules and two saccharinate anions coordinate the nickel atom forming a distorted octahedron. The monoethanolamine molecules act as a bidentate ligand and form five-membered trans chelate rings, which constitute the plane of the coordination octahedron, while two saccharinate ions behave as a monodentate ligand occupying the axial positions. Intermolecular hydrogen bonds link the molecules to form a three-dimensional infinite structure.     

Crystal and molecular structure oftrans-dichlorobis(oxazole)palladium(II)

The crystal and molecular structure oftrans-dichlorobis(oxazole)palladium-(II), Pd(C₃H₃ON)₂Cl₂, has been determined by single-crystal X-ray diffraction techniques using counter methods and has been refined by full-matrix least-squares procedures to a finalR index of 0.022. The complex crystallizes in the triclinic space groupP¯1 with unit cell dimensions ofa = 6.957(1),b = 7.506(1),c = 5.538(1) Å, = 109.22(1), = 91.37(1), and = 115.09(1) °, withZ = 1. The palladium(II) ion, located at an inversion center, is coordinated in a regular square-planar manner to two chloride ions at 2.293(1) Å and, at 2.016(2) Å, to the nitrogen atoms of two oxazole ligands. The planar oxazole rings are tilted 33 ° with respect to the PdN₂Cl₂ plane. Further verification of the presence of oxazole in the complex was obtained by high-resolution mass spectrometry. Crystals of Pd(C₃H₃ON)₂Cl₂ resulted irreproducibly from attempts to prepare single crystals of a previously reported dimeric palladium(II) disulfide complex by treating Pd(CH₃CN)₂Cl₂ with a slight excess of diphenyl disulfide in benzene in the atmosphere. The source of the oxazole is not understood.     

Synthesis,Characterization and X-ray Structures of 2,6-Diacetylpyridinebis(benzenesulfonylhydrazide) and its Zinc(II) Complex

Abstract  2,6-Diacetylpyridinebis(benzenesulfonylhydrazide) (2,6-DAPBSH) and its zinc(II) complex have been synthesized and characterized by X-ray crystallography. The ligand crystallizes in the monoclinic crystal system, space group Cc, with cell parameter = 16.808(2) Ǻ, b = 16.328(2) Ǻ, c = 8.2670(11) Ǻ, β = 91.869(9)°, while the zinc(II) complex crystallizes in the orthorhombic crystal system, space group Pbcn, with cell parameters a = 14.5927(3) Ǻ, b = 9.6502(2) Ǻ, c = 20.5610(5) Ǻ. The metal center is seven-coordinate, with an approximate pentagonal bipyramidal configuration of the chelating ligand and two apically coordinated DMSO molecules. Graphical Abstract  X-ray crystallographic study on the [2,6-diacetylpyridine—bis(benzenesulfonylhydrazonato-κ⁵ N′N′′N′′′O′O′′)]bis(dimethyl sulfoxide-κO)zinc(II) (Fig. 1) shows that the complex is a seven-coordinate, with an approximate pentagonal bipyramidal configuration where the ligand coordinates to the zinc(II) ion as a pentadentate chelate via the pyridine nitrogen atom, the two azomethine nitrogen atoms and the two sulfonyl oxygen atoms.      

X-ray crystal structure and spectroscopy of a pseudo-square pyramidal Cu(II) complex, trans-dinitratotetrakis (trans-4-styrylpyridine)copper(II)

Single crystals of the title Cu(II) complex, [Cu(stpy)₄(ONO₂)(ONO₂)] [stpy = trans-4-styryl-pyridine] have been prepared and characterized by elemental and thermal analyses, IR, electronic and EPR spectral measurements, and X-ray crystal structure determination. The complex crystallizes in the monoclinic space group P2₁/c with unit-cell parameters, a = 12.985(2), b = 22.865(8), c = 17.024(10) Å, = 112.29(3)°, and Z = 4. The structure consists of discrete monomeric units of [Cu(stpy)₄(ONO₂)(ONO₂)]. The equatorial positions of the Cu(II) polyhedron are occupied by nitrogen atoms of the four stpy ligands and the axial positions by the oxygens of two unidentate nitrate anions. One of these oxygens is at rather longer distance [2.609(3) Å] and may be considered to be semicoordinated. If this semibond is ignored, the coordination geometry lies closer to an idealized square pyramid than to the trigonal bipyramid geometry. IR spectra reveal nitrogen coordination from stpy and asymmetry in the monodentate oxygen binding of the two nitrate ligands. The optical reflectance band at 600 nm suggests pseudo-square-based pyramidal geometry around Cu(II). Well-resolved Cu(II) hyperfine features in the EPR spectra reveal the absence of exchange interactions between adjacent copper centers. Optical and EPR spectra of a methanolic solution of the complex indicate solvent interactions. Thermogravimetric analysis shows the complex to be stable up to 175°C.     

Synthesis and X-ray crystal structure of a complex formed by reaction of 1,2-bis(2′-pyridylethynyl)benzene and mercury(II) chloride

The X-ray crystal structure of the complex formed between 1,2-bis(2′-pyridylethynyl) benzene and mercuric(II) chloride is described. The complex (C₄₀H₂₄Cl₆Hg₃N₄) crystallized in the triclinic space group P-1 with a=9.0414(6), b=9.4631(7), c=12.1134(9) ?, α=97.4680(10), β=94.8130(10), γ=105.4700(10)°. The structure reveals that the ligand is distorted from planarity to accommodate the mercury cation and a third mercuric chloride moiety is held between two ligand-mercury coordination complexes. The central mercury cation has octahedral coordination geometry surrounded by six chlorides while the other two mercury cations have distorted tetrahedral geometry each coordinated by two pyridyl nitrogen atoms and two chlorides.     

Structure of a five-coordinate mononuclear cobalt(II) complex: chlorobis([N,N-(1,1′-biphenyl-2,2′-dimethylene)]-2-aminomethyl) pyridine)cobalt(II) bromide

A penta-coordinate mononuclear cobalt(II) complex, [Co(BP)₂(Cl⁻)](Br⁻), 1 with a novel, biphenyl-appended N,N-bidentate ligand, BP ([N,N-(1,1′-biphenyl-2,2′-dimethylene)]-2-aminomethyl) pyridine) was synthesized and characterized by elemental analysis, UV-Vis, electro-spray ionization mass spectrum and single crystal XRD. The title complex crystallizes in the monoclinic space group C2/c with cell dimensions a = 11.389(2), b = 25.627(3), c = 12.276(3) Å, β = 100.419(18)° and Z = 2. The cobalt atom has a distorted trigonal bipyramidal (tbp) geometry and is surrounded by 4Ns of two BP, and a Cl⁻/Br⁻ at the 5th coordination site. This is the first report of a mononuclear tbp cobalt complex with biphenyl appended bidentate ligand containing amino-pyridyl moiety.     

Synthesis,spectroscopic characterization of thiosemicarbazone complexes of nickel(II) and X-ray structures of anisaldehyde thiosemicarbazone (ATSZH) and bis(tolualdehyde thiosemicarbazonato)nickel(II)

Complexes of nickel(II) with anisaldehyde (ATSZH), tolualdehyde (TTSZH), and vanillin (VTSZH) thiosemicarbazones have been synthesized and characterized by means of UV-Visible, I.R., Raman,¹H and¹³C NMR spectroscopy. The thiosemicarbazones have been found to exist in the thione form.¹H and¹³C NMR as well as electronic spectral data support a square planar structure for Ni(ATSZ)₂ and Ni(TTSZ)₂ complexes.¹H and¹³C NMR spectra indicate that the structure of Ni(VTSZ)₂ complex differs from the other two nickel(II) complexes and it may possibly consist of mixtures of isomers. The X-ray structures of Ni(TTSZ)₂ and ATSZH were determined: the nickel complex is monoclinic witha=26.412(6),b=12.135(3),c=6.888(1)Å,=95.41(5)°,Z=4,R=0.0647, space groupC2/c. The structure consists of discrete Ni(TTSZ)₂ molecules in which the metal, located on a symmetry centre, is N,S-chelated by two ligands forming two five-term chelate rings. The structure of ATSZH is also monoclinic:a=7.859(1),b=13.481(3),c=10.028(3) Å,=106.32(4)°,Z=4,R=0.0412, space groupP2₁/c. The molecules, connected by NO hydrogen bonds, reveal a considerable tilting of the aromatic ring in respect to the thiourea moiety if compared with the nickel structure.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).