Palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine) dihydrate solvates

The title compounds palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine (Hmtpo)) dihydrate solvates, have been synthesized by reacting thecis-[MCl₂(Hmtpo)₂] (where M=Pt(II), Pd(II)) complexes with an excess of thiourea (tu) and the structure of the palladium compound was solved by X-ray diffraction. Crystals of [Pd(tu)₄]Cl₂·2Hmtpo·2H₂O are triclinic with space groupP and unit cell dimensionsa=7.972(1),b=9.049(1),c=11.808(2)Å, =88.20(1), =75.15(1), =76.54(1)^o. The cation [Pd(tu)₄]²⁺ is centrosymmetric involving four sulfur thiourea atoms in a near square planar environment. The triazolopyrimidine molecules, chloride anions and water molecules do not take part in the metal center coordination but interact by hydrogen bonding between them and the thiourea moieties. A comparison between powder diffraction data of palladium(II) and platinum(II) compounds clearly indicates that both compounds are isomorphous.     

Crystal structures of the cobalt(III), nickel(II), copper(II), and zinc(II) complexes of 2-thio-6-picoline N-oxide

Structures of the following compounds have been solved: tris(2-thio-6-picoline N-oxide)cobalt(III), [Co(6MOS)₃], orthorhombic, Pca2₁, a = 17.871(3), b = 14.061(2), c = 15.964(2) Å, V = 4011(1) ų, Z = 8, and = 1.193 mm^–1; bis (2-thio-6-picoline N-oxide)nickel(II), [Ni(6MOS)₂], orthorhombic, Pbca, a = 15.602(8), b = 13.606(4), c = 13.348(8) Å, V = 2833(4) ų, Z = 8, and = 1.655 mm^–1; bis(2-thio-6-picoline N-oxide)copper(II), [Cu(6MOS)₂], orthorhombic, Pbca, a = 13.914(5), b = 12.984(5), c = 15.663(6) Å, V = 2830(2) ų, Z = 8, and = 1.836 mm^–1; and bis(2-thio-6-picoline N-oxide)zinc(II), [Zn(6MOS)₂], triclinic, P – 1, a = 7.9737(8), b = 11.7786(9), c = 7.9206(8) Å, = 104.502(7), = 104.495(8), = 93.445(8)°, V = 691.3(1) ų, Z = 2, and = 2.106 mm^–1. The steric effect of the methyl group in the six-position of the N-oxide ring is considered in comparing these structures to complexes of 2-thiopyridine N-oxide.     

Crystal and Molecular Structure of Bis{2,6‐bis(hydroxymethyl)pyridine‐O,O,N}{μ‐bis(2‐hydroxymethylpyridyl)methanolate‐O,N}dicopper(II)di(propionate). First example of non‐coordinate propionate anoins

Bis{2,6‐bis (hydroxymethyl) pyridine‐O,O,N} {μ‐bis(2‐hydroxymethylpyridyl) methanolate‐O,N} dicopper(II) di(propionate) (CCDC 143763) has been prepared and studied by single‐crystal X‐ray diffraction methods at 293(2) K. The crystal structure consists of dimeric complex cation, [Cu₂(μ‐bhmp)₂(bhmpH)₂]⁺² and propionate anions (bhmp ‐ 2,6‐bis(hydroxymethyl) pyridine; bhmpH ‐ 2‐(6‐hydroxymethylpyridyl) methanolate ) and propionate anions. The complex cation contains two neutral and two monodeprotonated bhmp molecules, each coordinate to one Cu(II) atom in a tridentate chelating manner, via two O atoms and N atom. The monodeprotonated bmph molecules are also tridentate coordinate via N atom and only one O atom, which serve as bridge between two CuO₄N₂ moieties. The propionate anions are “ fixed” to the complex by the hydrogen bonds.     

Crystal structure and EPR spectrum of dimeric di-μ-azide-bis[cyanide(N,N-diethylethylenediamine)]-copper(II), [Cu(N3)(NCO)(diEten)]2

The title compound, [Cu(N₃)(NCO)(C₆H₁₆N₂)]₂, crystallizes in the space groupP2₁/n, witha=8.336(1),b=17.405(3),c=8.376(1) Å, β=109.73(2)^o andZ=4. The molecules are arranged as centrosymmetric dimers in which two azide ligands bridge neighboring copper ions in an asymmetric head-on fashion. The Cu(II) ion is coordinated to five nitrogen atoms which form a distorted tetragonal pyramid. At the pyramid base are the two N atoms of a diEten molecule [Cu−N=2.00(1), 2.130(9) Å], an azide end atom [Cu−N=1.99(1) Å] and a NCO group [Cu−N=1.93(1) Å]. At the pyramid apex is the other, inversion related, azide N atom in the dimer [Cu−N=2.38(1) Å]. This Cu−N contact links the monomers within a dimer. Neighboring dimers are coupled by weak N−H…O contacts. Single crystal EPR data at X-band show that the pair of resonances expected for neighboring, magnetically nonequivalents dimers, collapse into a single line, a signature of inter-dimers superexchange coupling. The observed crystal gyromagnetic tensor is used to disclose the electronic and magnetic structure around Cu(II) ions.     

Synthesis and Crystal Structure of a Polymeric Cobalt(II) Complex with 1,2-bis(1,2,4-triazol-1-yl)ethane

Abstract The title complex [Co₂(bte)₃(NCS)₄(H₂O)₂] _n (bte = 1,2-bis(triazol-1-yl)ethane) has been prepared. Single-crystal X-ray analysis reveals that the complex crystallizes in space group P ī with a = 7.7962(2), b = 8.3407(4), c = 14.7735(5) ?, α = 86.835(2), β = 76.2031(9), γ = 80.583(3)°. The crystal consists of two discrete complexes, [Co(bte)(NCS)₂(H₂O)₂] and [Co(bte)₂(NCS)₂]. The structure of [Co(bte)(NCS)₂(H₂O)₂] consists of neutral chain containing Co(II) bridged by bte molecules. The six-co-ordination of Co²⁺ is achieved by means of two trans NCS⁻ ions and water molecules. The structure of [Co(bte)₂(NCS)₂] demonstrates a one-dimensional neutral chain through bte-bridge, in which the Co(II) atom is in a distorted octahedral environment formed by four nitrogen atoms of the triazoles and two nitrogen atoms from two trans thiocyanato liagnds. Index abstract Synthesis and Crystal Structure of a Polymeric Cobalt(II) Complex with 1,2-bis(1,2,4-triazol-1-yl)ethane This paper reports the synthesis and crystal structure of complex [Co₂(bte)₃(NCS)₄(H₂O)₂]_n (bte = 1,2-bis(triazol-1-yl)ethane), which consists two different neutral chains containing Co(II) bridged by bte molecules.      

Synthesis and crystal structure of bis(malonato)tetra (aqua)barium(II)cobalt(II): [BaCo(C<Subscript>3</Subscript>H<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]

The title compound [BaCo(C₃H₂O₄)₂(H₂O)₄] was synthesized and its crystal structure was determined. The compound is orthorhombic, space group Pccn with a = 18.974(3) Å, b = 6.783(2) Å, c = 9.394(4) Å. The structure is polymeric and consists of edge-sharing BaO₈ polyhedra and CoO₆ octahedra linked together by the malonate groups. The geometry around the Ba(II) centres is a slightly distorted square-antiprism with Ba–O distances ranging from 2.789(4) to 2.843(4) Å. Around the Co(II) centres, the coordination forms a distorted octahedron with Co–O bonds between 2.040(3) and 2.238(4) Å.     

Crystal of catena-(μ2-terephthalato)-bis (N-methylimidazole)-copper(II)

A new one-dimensional chain complex [Cu(ta) (N-MeIm)₂]n (where ta = terephthalic acid dianion,N-MeIm =N-methylimidazole) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the Monoclinic space groupP2₁/c with the parameters:a = 5.2930(11)Å,b = 14.679(3)Å,c = 11.007(3)Å, β = 104.84(3)^°,V = 826.7(3)ų, withZ = 4 formula units. In the structure, each Cu atom is coordinated by a pair ofN-methylimidazole ligands and a pair of monodentate carboxylate groups, affording a square planar N₂O₂ geometry. Both carboxylate groups of the terephthalate dianion coordinate in a monodentate mode bridging two Cu(II) ions with formation of 1D zigzag chain along thec axis. This supramolecular compound exhibits a three-dimensional solid state structure constituted by hydrogen bonds and C–H–π stacking interactions.     

Synthesis and structural characterization of dihexamethylenetetraminetetraaquocobalt(II) hexaaquocobalt(II) sulfate hexahydrate

The synthesis and crystal structure of a new three dimensional cobalt(II) complex [Co(C₆H₁₂N₄)₂(H₂O)₄Co(H₂O)₆][SO₄]₂.6H₂O are reported. It crystallizes in the triclinic space group P-1 with a = 13.394(3), b = 16.077(3), c = 9.282(2) Å, = 89.71(2), = 90.42(2), = 114.02(2)°, V = 1825.6(7)ų and Z = 2. The structure is comprised of [Co(C₆H₁₂N₄)₂ (H₂O)₄Co(H₂O)₆][SO₄]₂ units and H₂O molecules. Two molecules of ligand and four molecules of water chelate one type of Co^II in an octahedral fashion through two N and four O atoms: the four O atoms form the equatorial plane and the two N atoms occupy the apical positions. The other type of Co^II cation is chelated by six water molecules.     

Hydrothermal synthesis and characterization of (N(C2H5)4)4[VMo12V2O44]

The hydrothermal reaction of a mixture of Na₂MoO₄·2H₂O, V₂O₅, pyromellitic acid (1,2,4,5‐C₆H₂(COOH)₄), (C₂H₅)₄NCl and 0,1 M H₂SO₄ for 88 h at 180°C gives blue needle‐like crystals of [V^IV₂O₂(H₂O)₂ (C₆H₂(COO)₄)] in 20% yield (based on V) and dark blue prismatic crystals of the title compound, mixed‐valance (N(C₂H₅)₄)₄[VMo₁₂V₂O₄₄], 1, in 12% yield (based on Mo). 1 was investigated by means of elemental analysis, thermogravimetry, Fourier Transform Infrared Spectroscopy and Single Crystal X‐ray Diffraction Methods. Crystal data for the compound: monoclinic space group P2₁/c (No:14), a=13.7815(12) b=13.0271(9) c= 21.189(2) Å, β= 113.909(7)°, Z=2. Although [XM₁₄O₄₂]^‐n (X=P, Si, Ge, V and M=Mo and/or V) cores have been previously determined, this is the first time that [VMo₁₂V₂O₄₄]^‐4 core is synthesized and characterized. The structural difference between 1 and these HPOMs is the coordinational geometry of the central metal atoms. The central vanadium in 1 has an octahedral coordination geometry, whereas in literature, the central V, P, Si and Ge atoms in [V₁₅O₄₂]^‐9 / [SiM₈V₆O₄₂]^‐4 / [PM₈V₆O₄₂]^‐5 / [GeM₈V₆O₄₂]^‐4 have tetrahedral coordinational geometry. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic and crystal structure analysis of diamminebis(2,4,6‐triiodophenolato‐O) copper(II)

The crystal structure of [Cu(C₆H₂I₃O)₂(NH₃)₂] (CCDC 238896) has been determined by x‐ray diffraction. This monomeric centrosymmetric Cu(II) complex crystallizes in the monoclinic system. The CuO₂N₂ coordination sphere is trans ‐planar, [Cu–O: 1.943(5) Å and Cu‐N: 1.972(7)] with the fifth and sixth coordination sites occupied by I atoms from the phenoxide ions [Cu–I₁: 3.3552(8) Å] to form a tetragonally elongated octahedral structure for CuO₂N₂I₂ coordination. The complex molecules hold together in a one dimensional chain true [100] direction by intermolecular hydrogen bonds. Differantial scanning calorimeter, FTIR and magnetic susceptibility measurements were also performed in order to identify the title complex. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Isolation and Crystal Structure of [Cu(L1)(O2CH)](ClO4)?·?H2O: Hydrolysis of DMF ( N , N -Dimethylformamide) by a Copper(II) Tetraazamacrocycle

The tetraazamacrocyclic copper(II) complex, [Cu(L)](ClO₄)₂ (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14.4.0^1.18.0^7.12]docosane), hydrolyzes DMF at room temperature. The formate anion which is one of the hydrolyzed species of DMF coordinates to the copper(II) ion to form [Cu(L1)(O₂CH)](ClO₄) · H₂O (1). The crystals of the complex 1 were isolated and structurally characterized by a combination of analytical, spectroscopic, and crystallographic methods. In 1, the macrocyclic ligand contains two trans fused cyclohexane rings, and the coordination geometry about the copper(II) ion adopts a square pyramid with four equatorial nitrogen atoms from the macrocycle and an oxygen atom from the formato ligand with an uncoordinated perchlorate ion.     

Synthesis and Crystal Structure of the Hydrated Nickel(II) Complex of Tartrate

Abstract  A new dinuclear hydrated nickel(II) tartrate has been isolated and structurally characterized by single-crystal X-ray diffraction. The title compound formulated as [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 (C₁₇H_55.5Ni₄O_42.75) crystallizes in monoclinic system, space group P2(1)/c with a = 13.684(5), b = 17.143(6), c = 18.586(6) ?, β = 96.638(6)°, V = 4331(3) ?³, Z = 4. The unit cell contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference, half of menthol molecule and ten and a quarter packing water molecules. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way. Each Ni(II) atom is six-coordinated by six O atoms from two tartrate units and two water molecules. Index Abstract  The crystal structure of complex [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way.      

The Crystal Structure of the Cluster Complex [{Co(phen)2}2V4O12] · H2O

The crystal structure of [{Co(phen)₂}₂V₄O₁₂] · H₂O consists of hexanuclear bimetallic clusters [{Co(phen)₂}₂V₄O₁₂]. The cyclic [V₄O₁₂]^4‐ anion acts as a bidentate bridging ligand between the two [Co(phen)₂]²⁺ cations. The π‐π stacking interactions between the parallel 1,10‐phenantroline (phen) groups play a significant role in stabilizing this structure. The title compound crystallizes in the P2₁/c space group.     

Synthesis,Properties, and Crystal Structures of Copper(II) Di-(2-picolyl)amine Complexes Containing Inorganic Salts

Abstract These complexes have been characterized by X-ray crystallography, spectroscopic, and cyclic voltammetry. In 1, the copper(II) ion has a distorted square-pyramidal geometry with three nitrogen atoms of the dpa ligand and two oxygen atoms of the nitrate anions. The crystal structure of 2 shows that the copper(II) ions are bridged by tp anion to form a dinuclear complex, in which each copper(II) ion exhibits a distorted square-pyramid with three nitrogen atoms of the dpa ligand, water molecule, and the oxygen atom of the bridging tp ligand. Cyclic voltammetric data indicate that 1 undergoes irreversible one-electron oxidation to the Cu^III and reversible one-electron reduction to the Cu^I, while 2 gives one reversible oxidation and two reversible and irreversible reduced processes. The electronic spectra and redox potentials of the complexes are influenced significantly by the anionic ligands. Graphical Abstract The reaction of [Cu(dpa)Cl₂] with K(NO₃)₂ and Na₂tp yields mononuclear and dinuclear copper(II) complexes [Cu(dpa)(NO₃)₂] (1) and [Cu₂(dpa)₂(H₂O)₂(μ-tp)](tp)·6H₂O (2) (dpa = di-(2-picolyl)amine, tp = terephthalate).      

Polymeric copper(II)-orotato complexes, [(C5H2N2O4)Cu(H2O)2]n

The compound [(C₅H₂N₂O₄)Cu(H₂O)₂]_n has been synthesized and its structure determined at room temperature. The primary coordination sphere at the Cu ion is square planar with the orotate dianion coordinating at the metal through heterocyclic nitrogen atom and adjacent oxygen of the carboxylate group, the remaining coordination sites are occupied by two water molecules. The orotate dianion is tricoordinated to one copper via N₁ and one oxygen of the carboxylato group and to another copper atom via the other oxygen of the carboxylato group. The coordination at copper is extended to five by the other oxygen of the carboxylate group of another orotate molecule. Thus, the molecules are associated to form chains, the carboxylato group acting as a bridge between the metal ions, the orotato-group being tridentate. The title compound crystallizes in the monoclinic space group. P2₁/n₁ with a = 9.515(5), b = 6.925(2), c = 11.861(6) Å, = 95.285(9)°, D _calc = 2.17 g cm^–3, and z = 4.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Structural features of a new [Fe(nicotinamide)2(H2O)4]·[Fe(H2O)6]·(SO4)2·2H2O complex

A new nicotinamide complex of Fe(II) cation was prepared by reaction between ferrous sulfate and nicotinamide in aqueous solution. The complex was characterized on the basis of elemental analysis, FT IR and UV–VIS spectroscopy, electrochemistry (cyclic voltammetry) and X–ray crystallography. The complex consists of the molecular composition of [Fe(nicotinamide)₂(H₂O)₄]· [Fe(H₂O)₆]·(SO₄)₂·2H₂O. The complex crystallizes in the monoclinic space group P 2₁/c [a = 12.862(3), b = 7.110(3), c = 16.382(3) Å; β = 95.79(2)°]. It has been proven that nicotinamide is coordinated to Fe(II) through the nitrogen atom of its heterocyclic ring. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Crystal structure of [Co(o-SC6H4NH2){P(OMe)3}3]PF6

A cobalt-thiolato-phosphite complex [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]PF₆ has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group with a = 10.590(4), b = 11.122(3), c = 13.577(5) Å, = 101.85(1), = 108.50(1), = 101.75(1)°, V = 1420.6(8) ų, and Z = 2. The structure comprises discrete [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]⁺ cations and PF ₆ ^– anions where the metal atom is coordinated in a highly distorted square-pyramidal environment by one chelate o-SC₆H₄NH ₂ ^– (abt) and two P(OMe)₃ ligands in the basal positions, and a third P(OMe)₃ in the axial site with Co–N,, 1.847(5), Co–S, 2.166(2), Co–P, 2.157(2), 2.147(2), and 2.125(2) Å.     

Crystal structures of two polymeric 1,5-naphthalenedisulfonate-coordinated transition metal complexes

Two 1,5-naphthalenedisulfonate(1,5-nds)-coordinated polymeric complexes [Cu(1,5-nds) (H₂O)₄]_n and [Cd(1,5-nds)(H₂O)₂]_n were synthesized and their structures characterized by single-crystal structure analysis. The Cu(II) complex [Cu(1,5-nds)(H₂O)₄]_n is obtained both from CuCl or CuCl₂ reacting with 1,5-naphthalenedisulfonic acid at 80^∘C. It is a one-dimensional polymer in which Cu(II) is coordinated by four water molecules and two sulfonate oxygen atoms in the trans positions. The interaction between sulfonate and Cu(II) is different in complexes obtained from different reaction temperature. While the three-dimensional Cd(II) complex [Cd(1,5-nds)(H₂O)₂]_n is a polymorph of the reported two-dimensional layer structure, in which Cd(II) is coordinated by two water molecules in the trans positions and four different sulfonate groups, the same as that observed in the two-dimensional polymorph. However, the 1,5-nds ligands connect Cd(II) centers belonging to different layers, resulting in the three-dimensional framework.     

Atomic force microscopy studies on surface morphologies of CdHg(SCN)4 crystals grown in solutions containing excessive amount of Cd(II) cations

Surface morphologies of CdHg(SCN)₄ (CMTC) crystals grown from solutions with excessive amount of Cd(II) cations (5%, 20% and 50% in molar ratio) have been investigated by atomic force microscopy (AFM). [Cd(SCN)_n]^2‐n (n ≤ 4) complex anions formed by addition of excessive Cd(II) cations in the solutions have been found to act either as growth units or impurities during CMTC crystal growth. On the prismatic faces, incorporation of [Cd(SCN)_n]^2‐n (n ≤ 4) complex anions as growth units leads to the formation of well‐oriented protuberance trains at the step fronts, named as “locally anisotropic crystal growth”. These protuberances become fewer, less distinct and nearly disappeared with the increase of excessive Cd(II) cations in the solutions. The pyramidal face, however, varies from regular 2D nucleation growth at a low concentration of Cd(II) to much rougher growth surfaces at high concentrations, exhibiting typical surface morphologies where crystal growth is completely inhibited by impurities. Observations in this experiment provide a new picture of crystal growth.