Omer Andac

Different coordination modes of saccharin in the metal complexes with 2-pyridylmethanol: synthesis, spectroscopic, thermal and structural characterization

The reaction of [M(sac)2(H2O)4]/2H2O, where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), and sac is the saccharinate anion, with 2-pyridylmethanol (mpy) result in the formation of the new complexes, which have been characterized by elemental analyses, magnetic measurements, FT-IR spectroscopy, thermal analysis and X-ray diffraction methods. The [Co(sac)2(mpy)2 ]( 3) and [Ni(sac)2(mpy)2 ]( 4) complexes are isomorphous with the triclinic space group the two sac ligands in both 3 and 4 exhibit unusual and non-equivalent coordination. One of them coordinates to the metals through the imino nitrogen atom, while the other is bonded to the metals with the carbonyl oxygen atom behaving as an ambidentate ligand. The [Cu(sac)2(mpy)2 ]( 5) complex is centrosymmetric and crystallizes in orthorhombic space group and both sac ligands in (5) are N coordinated. [Hg2(sac)4(mpy)2 ]( 8) crystallizes in monoclinic space group P 21/n .I n8, the mpy ligands acts as a bridge between the mercury two mercury(II) centres and the complex 8 consists of one-dimensional chains in which dimeric [Hg2(sac)4(mpy)2] units are sequentially bridged by bis-bidentate sac ligands forming a coordination polymer. In all cases, the metal atoms are six-coordinate. The mpy molecules act as a bidentate N - and O-donor ligand in 1/7. Thermal decomposition of the complexes in air results in removal of mpy ligands and formation of stable metal saccharinates as intermediates, which also decompose at higher temperatures to give the corresponding metal oxides. # 2002 Elsevier Science Ltd. All rights reserved.

4‐Benzoyl‐1,5‐diphenyl‐1H‐pyrazole‐3‐carboxylic acid methanol solvate

In the title compound, C23H16N2O3·CH4O, the N—N bond distance in the pyrazole ring, which is planar within 0.008 A, is 1.3634 (18) A. The crystal packing is stabilized by O—H⋯O, O—H⋯N and C—H⋯O intermolecular hydrogen bonds.

Synthesis, molecular and crystal structure of bis(triethanolamine)manganese(II) saccharinate: a seven-coordinate manganese complex with tri- and tetradentate triethanolamine ligands

Abstract The synthesis, molecular and crystal structure of bis(triethanolamine)Mn(II) saccharinate, [Mn(tea) 2 ](sac) 2 are reported. The configuration of the tea ligands results in an unusual example of coordination number seven for the Mn(II) ion. The two triethanolamine (tea) ligands coordinate to the Mn(II) ion forming a monocapped trigonal prism geometry, in which one of the tea ligands behaves as a tridentate ligand, while the other one acts as a tetradentate donor. The free and coordinated hydroxyl hydrogens of the tea ligands are involved in hydrogen bonding with the amine nitrogen, carbonyl and sulfonyl oxygens of the neighbouring sac ions to form a three-dimensional infinite network. A weak π–π interaction between the phenyl rings of the sac ions also occurs.

Mono- and binuclear copper(II) complexes of saccharin with 2-pyridinepropanol synthesis, spectral, thermal and structural characterization

Mono- and binuclear copper(II) saccharinate (sac) complexes containing 2-pyridinepropanol (pypr) have been prepared and characterized by elemental analyses, i.r., u.v.–vis., magnetic measurements and single crystal X-ray diffraction. The copper(II) ion in trans-[Cu(pypr)2(sac)2] has −1 site symmetry and is octahedrally coordinated by two bidentate neutral pypr (N, O) and two sac (O) ligands. The binuclear copper(II) complex, [Cu2(μ-pypr)2(sac)2], is built up around a centre of symmetry and contains two strongly distorted square–planar coordinated copper(II) ions bridged by two alkoxo groups of the deprotonated pypr ligand, which also coordinates to the copper(II) ions through its nitrogen. In contrast to the mononuclear complex, the sac ligands in the binuclear complex is N-coordinated. The binuclear complex exhibits diamagnetic behaviour. The i.r. spectra and thermal decompositions of both complexes are described.

Crystal structure and physico-chemical properties of diaquabis(1,10-phenanthroline)manganese(II) disaccharinate monohydrate

Abstract A novel manganese complex, [Mn(phen) 2 (H 2 O) 2 ](sac) 2 ·H 2 O, was synthesized by the reaction of [Mn(sac) 2 (H 2 O) 4 ]·2H 2 O with 1,10-phenantroline in aqueous solution and characterized by elemental analysis, IR spectral evidence, magnetic measurements, thermal analysis and single crystal X-ray diffraction. The compound crystallizes in triclinic system, space group P -1, with Z =2. The saccharinate ions do not coordinate the central metal, instead are present as the complementary anions. In the complex cation, Mn(II) is coordinated by two phen and two aqua ligands, and exhibits a distorted octahedral coordination with a high-spin configuration. The presence of lattice and coordinate water molecules are also confirmed by thermal analysis and IR spectroscopy.

Cyano-complexes and salts with tetracyanonickellateII and N,N-bis(2-hydroxyethyl)-ethylenediamine: synthesis, IR spectra, magnetic properties, thermal analyses, and crystal structures

Four cyano complexes, [Ni(N-bishydeten)Ni(CN)4] n (c1), [Cu(N-bishydeten)2][Ni(CN)4] (c2), [Zn2(N-bishydeten)2Ni(CN)4] n (c3), and [Cd(N-bishydeten)2][Ni(CN)4] (c4), have been synthesized and characterized by FT-IR, elemental, and thermal analyses. The structures of c2 and c4 were determined by single-crystal X-ray diffraction studies; both structures contain isolated cations and anions. The c2 consists of [Cu(N-bishydeten)2]2+ with octahedrally coordinated CuII and diamagnetic [Ni(CN)4]2–, but c4 consists of [Cd(N-bishydeten)2]2+, in which CdII is eight coordinate with two tetradentate N-bishydeten and diamagnetic [Ni(CN)4]2–. The value of the shape measure S (o) indicates that the coordination geometry around CdII lies along D 2d [dodecahedron; (dd)], C 2v [bicapped trigonal prism; (btp)], and D 4d [square antiprism; (sap)] but close to D 2d and D 4d. Variable temperature magnetic susceptibility measurements of c1 and c2 show the presence of little antiferromagnetic interaction below 20 K. Thermal analyses reveal that first neutral N-bishydeten and then cyano ligands were liberated from the complexes.

Five complexes containing N,N-bis(2-hydroxyethyl)-ethylenediamine with tetracyanidopalladate(II): synthesis, crystal structures, thermal, magnetic, and catalytic properties

Five cyanide complexes, [Ni(N-bishydeten)Pd(CN)4] (1), [Cu(N-bishydeten)Pd(μ-CN)2(CN)2]n (2), [Cu(N-bishydeten)2][Pd(CN)4] (3), [Zn(N-bishydeten)Pd(CN)4] (4), and [Cd(N-bishydeten)2][Pd(CN)4] (5) (N-bishydeten = N,N-bis(2-hydroxyethyl)-ethylenediamine), have been synthesized and characterized using various techniques. Different structures were formed when the M : L ratio was varied in copper complexes. The single-crystal X-ray diffraction analysis reveals that 2, a 1-D cyanide-bridged complex with 2,2-CT-type zigzag chain, was obtained by using 1 : 1 M : L ratio whereas 3 was formed as a complex salt in a molar ratio of 1 : 2. The thermal stabilities determined from DTGmax values of the first decomposition stages change in the order 1 > 5 > 4 > 3 > 2. Although an EPR signal was not observed for 1, the g parameters obtained from the EPR spectra of 2 and 3 indicate that CuII ions are located in tetragonally distorted octahedral sites (D 4h), and the ground state of the unpaired electron is (2B1g). The magnetic behavior indicates a very small antiferromagnetic interaction below 10 K for 1–3. In 3, there is a temperature-independent paramagnetism (α) due to the orbital moments of the d electrons. 1–3 were tested as catalysts in Suzuki and Heck coupling reactions.

Mixed-Ligand Metal Succinate Complexes with 1,10-Phenanthroline and Ethylenediamine: Synthesis, Characterization, Spectroscopic and Thermal Studies. Crystal Structure of Succinatocobalt(II) Complex with Phenanthroline

The novel mixed-ligand metal succinate (suc) complexes with 1,10-phenanthroline (phen) and ethylenediamine (en) have been synthesized and characterized by elemental analyses, magnetic moments, UV-VIS and IR spectra. Thermal reactivity of the complexes was studied in air using DTA and TG, and decomposition of the complexes resulted in the formation of corresponding metal oxides. The crystal structure of the [Co(suc)(H2O)(phen)2]·1.5HCO·C4H10O complex was determined by x-ray diffraction. The Co(II) complex crystallizes as a monobutanol solvate. In the complex, the cobalt ion lies on an inversion center and displays a distorted octahedral coordination with one aqua, one suc and two phen ligands. The suc ligand acts as a monodentate ligand through one of the negatively charged O atoms, while phen behaves as N-donor bidentate ligand. The crystal also contains disordered lattice water molecules and the structure is stabilized by extensive hydrogen bonding to form a three-dimensional infinite network.

Synthesis and Structure of Trans‐bis(ethanolamine)bis(saccharinato)mercury(II)

Trans-bis(ethanolamine)bis(saccharinato)mercury(II), [Hg(ea) 2 (sac) 2 ], where ea and sac denote the ethanolamine molecule and the saccharinate anion, respectively, crystallizes in the triclinic space group P1 (No. 2) with a = 9.4651(5), b = 10.4365 (5), c = 11.9314 (6) A, a = 84.402(1)° β= 78.313(1)°, γ= 75.307(1)°, Z = 2, V= 1115.11(10) A 3 . The structure consists of isolated [Hg(ea) 2 (sac) 2 ] units in which the Hg(II) ion is octahedrally coordinated by two nitrogen and two oxygen atoms of two neutral ea ligands, and two nitrogen atoms of two sac ligands. The ea acts as a bidentate N- and O-donor ligand and occupies the trans positions of the equatorial plane of the coordination octahedron forming a five-membered chelate ring, while sac behaves as a monodentate N-donor ligand occupying the axial positions. The average Hg-N sac and Hg-N ea bond distances are 2.739(3) and 2.114(7) A, respectively. The crystal exhibits extensive hydrogen bonds between the hydroxyl and amine hydrogen atoms of the ea ligands and the sulfonyl, carbonyl and amine groups of the sac ligands.

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, β = 105.0230(10)°, Z = 2, and space group P21/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.