Copper(II) and lead(II) complexes of 4,4′-bipyridine-<Emphasis Type="Italic">N,N</Emphasis>′-dioxide

Cu(II) and Pb(II) complexes of 4,4′-bipyridine-N,N′-dioxide have been prepared using a solvent-layering system. [Cu₂Cl₄(bpdo)₃(H₂O)₂] . 2(CH₃)₂SO (1) crystallises in P-1, a=8.731(2), b=8.943(2), c=14.408(3) ?, α=102.85(3), β=97.49(3), γ=109.77(3)°. The Cu(II) complex is a z-shaped discrete molecule with a DMSO molecule hydrogen bonded to the host through coordinated water molecule. Crystallisation of PbCl₂, PbBr₂ and PbI₂ with bpdo afforded isostructural 2D coordination polymers. [PbCl₂(bpdo)]_n is monoclinic, C2/c with a=16.3274(7), b=4.0708(1), c=18.6146(8) ?, β=93.73(1)°; [PbBr₂(bpdo)]_n is monoclinic, C2/c with a=16.403(3), b=4.2412(8), c=18.846(4) ?, β=92.59(3)° and [PbI₂(bpdo)]_n is monoclinic, C2/c with a=16.438(3), b=4.538(1), c=18.973(4) ?, β=91.04(3)°. The adjacent metal centres of these polymers are bridged by coordinated Cl⁻, Br⁻ or I⁻ anions as well as by bpdo ligands. These polymers possess no conventional hydrogen bonds.     

Synthesis and Structure of the Dimeric Copper(II) Complex Tetrakis[<Emphasis Type="Italic">N</Emphasis>-thiazol-2-yl-(4-methylphenyl)sulfonamidate]dicopper(II)

Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of this complex was elucidated and is discussed. The compound crystallised in the monoclinic crystal system, P2₁/c space group with a = 17.3888(9), b = 16.3003(9), c = 18.3679(9) ? and β = 114.3640(10)°. Four bidentate sulfathiazolato anions bridge two metal centers in a paddle-wheel fashion, with the nitrogen atoms as donors to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?. Graphical Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of the product has been elucidated and is discussed. Sulfathiazolato anions act as bridging ligands to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?.      

Crystal structure and spectroscopic characterization of bis(N-phenylthiourea)

Bis(N-phenylthiourea) (BPTU) has been synthesized and characterized by means of X-ray, IR, Raman, UV-Vis, ¹H NMR, and FAB mass spectra. The BPTU crystal belongs to the monoclinic C2/c space group with the cell constants a = 26.992(8) Å, b = 6.336(3) Å, c = 9.463(3) Å, = = 90°, = 105.97(7)°, Z = 4. The compound has been found to exist in the thione form, with cis configuration of the thiosemicarbazone moiety and skew conformation of the molecule.     

The Preparation, Characterization and X-ray Structural Analysis of Tetrakis[1-Methyl-3-(2-Propyl)-2(3H)-Imidazolethione]Cadmium(II) Hexafluorophosphate

Abstract  A new compound, [Cd(mipit)₄][PF₆]₂ has been synthesized and characterized via standard solid and solution state methods including single crystal X-ray crystallography (mipit = 1-methyl-3-(2-propyl)-2(3H)-imidazolethione). The title compound crystallizes in tetragonal space group I4 ₁ /a with a = 12.478(2) ?, b = 12.478(2) ?, c = 28.806(6) ?, and Z = 4. The complex is a high melting, colorless solid that has a distorted tetrahedral CdS₄ coordination geometry. Thermogravimetric analysis results for the title compound as well as for another potential CdS synthon and two potential CdSe synthons are reported. Graphical Abstract  The synthesis and characterization of the title compound, a new ionic homoleptic cadmium complex, tetrakis[1-methyl-3-(2-propyl)-2(3H)-imidazolethione]cadmium(II) hexafluorophosphate is reported. The results of a single crystal X-ray diffraction analysis reveal a distorted tetrahedral CdS₄ coordination sphere about the cadmium. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal and molecular structure of a cobalt(II) complex with bis(benzimidazol-2-ylmethyl)-methylamine (L)

The reaction product of Co(II) chloride and the title ligand L, formulated as CoLCl₂·CH₃OH, was prepared and characterized by means of structural and spectroscopic measurements. The violet crystals are orthorhombic, (space groupP2₁2₁2₁) witha=8.093(2),b=14.883(3),c=16.831(3) Å, andZ=4. The structure consists of discrete molecules with pseudo-, noncrystallographic twofold symmetry in which the Co atom is coordinated in trigonal bipyramidal geometry by three nitrogen and two chlorine atoms. The ligand L is coordinated to the Co atom in afac mode and two chlorine atoms are incis-positions. The structure was confirmed by IR-spectra.     

Distortion Isomerism of Cu(II) Chloride Adducts with Bis(2-benzimidazolyl)ethane. Synthesis,Characterization, X-ray Structures and Spectroscopy of Four Different Isomers

3D structures and spectroscopic properties are reported of four compounds with the ligand bis(2-benzimidazolyl)ethane (hereafter abbreviated as dbz) attached to CuCl₂, all having the general formula [Cu(dbz)Cl₂](Hb) _x . (in which Hb = EtOH or MeOH and x = 1/2 or 1). The X-ray crystal structure has been solved from these four slightly different compounds, namely: green α-[CuCl₂dbz](C₂H₅OH)_1/2 (1), the red compound β-[CuCl₂dbz](C₂H₅OH)_1/2 (2), which both have two slightly different units in the unit cell, the red α-[CuCl₂dbz](CH₃OH) (3) and a blue–green compound β-[CuCl₂dbz](CH₃OH) (4). The geometry around the Cu(II) anion is distorted tetrahedral for all four compounds, with chromophores consisting of two nitrogen atoms of the bidentate chelating dbz molecule and two chloride anions. The unit cells of compound 1 and 2 consist of two chemically identical, but crystallographically different units, while compounds 3 and 4 each have only one independent CuCl₂-(dbz) unit. The major differences are observed in the dihedral angles NCuN–ClCuCl, which vary from 29.3 to 77.1° for the four compounds. The differences are related to different packing effects, ring–ring stacking and H-bond interaction, due to the two different alcohols used. In fact these four compounds represent a new range of examples of distortion isomerism in pseudo-tetrahedrally coordinated species. Characterisation of the four compounds has been completed by IR, EPR and LF spectroscopy.     

Self-assembly of a Cd(II) coordination polymer with the 3,5L2 topology: Synthesis,structure, and properties

A new cadmium(II) coordination polymer, [Cd(ntdc)(dps)·H₂O]_n, was synthesized using 3-nitro-thiophene-2,5-dicarboxylic acid (H₂ntdc) and 4,4´-dipyridylsulfide (dps) as organic linkers. In the complex, adjacent Cd²⁺ ions are linked by ntdc^2? anions adopting a new coordination mode to form a one-dimensional (1D) [Cd(ntdc)]_n chain. Then dps ligands further expand the 1D chain into a corrugated two-dimensional (2D) layer network by linking neighboring Cd²⁺ ions. Topologically, the 2D network can be rationalized to a 3,5-connected 3,5L2 topology. Moreover, solid state properties such as thermogravimetric analysis and photoluminescent property were also investigated.     

Crystal structure and characterization of 1,2-N,N-disallicydene-phenylamineato nickel(II) complex

A new complex has been synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray analysis. The crystal is orthorhombic and the space group is chiral (P2₁2₁2₁) with a = 6.620(3) Å, b = 17.300(4) Å,, c = 5.450(1) Å,, = 90°, = 90°, = 90°, z = 4. In the crystal lattice, the molecules create a two-dimensional network structure through hydrogen bonds. The C–HO intermolecular hydrogen bonds connect the title complex to form a supermolecular structure.     

Solvent-controlled structures. Synthesis and characterization of complexes Cu(L)2(CH3COO)2 and [Cu2(μ-CH3COO)4(L)2](L)2 [L = N-(4′-methylaniline)-4-pyridinecarboxamide]

Two complexes Cu(L)₂(CH₃COO)₂ (1) and [Cu₂(μ-CH₃COO)₄(L)₂](L)₂ (2) (L = N-(4′-methylaniline)-4-pyridinecarboxamide) have been prepared and their crystal structures have been determined by single-crystal X-ray diffraction. The complexes are obtained by using the same raw materials and reaction conditions except solvents. The presence or absence of water controls the coordination mode to give rise to different structures. The structure of 1 has a triclinic space group P-1 with a = 8.381(3) ?, b = 8.545(4) ?, c = 11.357(5) ?, α = 110.654(6)°, β = 102.388(7)°, γ = 97.889(7)°, V = 722.9(5) ?³, and Z = 1. The structure of 2 has a triclinic space group P-1 with a = 9.121(3) ?, b = 9.454(3) ?, c = 17.233(5) ?, α = 77.374(5)°, β = 89.827(6)°, γ = 74.342(6)°, V = 1393.8(7) ?³, and Z = 1. Supramolecular assemblies have also been found via noncovalent bonds such as hydrogen bonds, π–π stacking interactions.     

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.     

A supramolecular structure of bis(1,3-diphenyl-1,3-propanedionato-O,O′) (1,10-phenanthroline-N,N′)cobalt(II) based on C–H…O, C–H…π and π…π interactions

The compound bis(1,3-diphenyl-1,3-propanedionato-O,O′) (1,10-phenanthroline-N, N′)cobalt(II) (Co(DBM)₂(1,10-phe)) was investigated as a potential host component for functional inclusion materials. The molecules of the complex in the crystal (a=21.015(5) ?, b=17.456(5) ?, c=9.503(3) ?, β=107.04(2)°, s.g. C 2/c) are centrosymmetric and assemble by way of C–H···O and C–H···π hydrogen bonds as well as π···π stacking interactions to provide a supramolecular ladder-like motif that is accompanied by a variant of the six phenyl-embrace synthon.     

Cu(II) Compounds with Pyrimidine-Based Chelating Ligands,Bridged by a Flexible Alkyl Spacer: Synthesis,Characterisation and X-Ray Structures of Methoxide-Bridged Dinuclear-Based Species

Abstract  The synthesis and full structural characterisation is described of 3 dinuclear-based Cu(II) compounds bridged by methoxide anions, and flexible linear bis(pyrimidine)-α,ω-diaminoalkane ligands. The structures are dinuclear based in all cases, in which the bis(pyrimidine)diaminoalkane ligand chelates to 2 Cu(II) ions in the same dinuclear unit (N–C–C–C–C–C–N linker), or to two different dinuclear units (with the short N–C–C–N linker), thereby generating a polymeric chain. The magnetic exchange in the compounds is dominated by the alkoxido-bridged ligands, which generate a very strong antiferromagnetic coupling between the Cu(II) ions, resulting in diamagnetism at room temperature and below, and EPR silent behaviour. Index Abstract  Dinuclear-based Cu(II) compounds with pyrimidine-based chelating ligands flexible linear bis(pyrimidine)-α,ω-diaminoalkane ligands are described, bridged by methoxide anions. The structures are dinuclear based in all cases, with the ligand chelating to 2 Cu(II) ions in the same dinuclear unit (N–C–C–C–C–C–N linker), or to 2 different dinuclear units (with short N–C–C–N linkers). The very strong antiferromagnetic magnetic exchange in all compounds is caused by the alkoxido-bridged ligands. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structures of bis(4-dimethylaminopyridinium) tetrachlorocobaltate(II) and bis-[1,3-di (ammoniummethyl)benzene]tetrachlorocobaltate(II)

The crystal structures consist of organoammonium cations hydrogen bonded to tetrahedral CoCl₄ ^2– anions. In the 4-dimethylaminopyridinium salt, [(CH₃)₂NC₅H₅NH]₂CoCl₄, pairs of cations hydrogen bond in an asymmetric fashion to two of the chlorines in each anion. The planar cations form two sets of – stacks, first parallel to the a axis and the second parallel to the b axis. The anions lie between these two nonintersecting sets of stacks. In contrast, for the second compound, [C₆H₄(CH₂NH₃)₂]CoCl₄, the tetrahedral CoCl₄ ^2– anions form layers lying parallel to the bc plane. The 1,3-di(ammoniummethyl)benzene cations crosslink adjacent anionic layers, forming a lamellar structure of alternating organic and inorganic layers.     

Synthesis,Characterization and Crystal Structure of Iridium(III)bis(2-<Emphasis Type="Italic">p</Emphasis>-tolyl-benzothiazolato-N,C<Superscript>2</Superscript>)(acetylacetonate)

Abstract  A novel thiazole-based iridium (III) complex (iridium(III)bis(2-p-tolyl-benzothiazolato-N,C²)(acetylacetonate)) has been prepared and fully characterized by EA, IR, ¹H-NMR and MS. The molecular structure of the complex has been determined by single crystal X-ray diffraction analysis. The iridium (III) center adopts a distorted octahedral geometry with cis-O–O, cis-C–C, and trans-N–N chelate disposition. The complex crystallizes in the orthorhombic Pbca space group with cell parameters a = 10.1388(7) ?, b = 18.3565(12) ?, c = 31.021(2) ?, α = β = γ = 90 ° and Z = 8. The electronic absorption and emission spectra of this complex have been investigated. Index Abstract  A novel thiazole-based phosphorescent iridium (III) complex (iridium(III) bis (2-p-tolyl-benzothiazolato-N,C²)(acetylacetonate)) has been prepared and fully characterized by EA, IR, ¹H-NMR, MS and X-ray diffraction analysis.