THE POLYMERIC COMPLEX 1, 10-PHENANTHROLINE-N,N'-(μ-NICOTINATO-N,O)DIAQUACOPPER(II) NITRATE DIHYDRATE

Abstract

The title complex has been prepared and its structure determined by X-ray diffraction methods. The complex crystallizes space group P2₁/a with a = 12.833(3), b = 10.443(2), c = 16.628(2)Å, β = 111.686(9)°. The nicotinate anions bridge adjacent Cu(II) atoms through both the pyridine N atom and the carboxyl O atom to form zigzag polymeric chains along the b axis. The carboxyl group of the nicotinate anion coordinates to the Cu(II) atom as a unidentate. Based on the molecular structure the infrared spectrum is discussed.     

THE POLYMERIC COPPER COMPLEX 2,2′-BIPYRIDINE-N,N′-(μ-MALEATO-O,O′:O″)COPPER(II) DIHYDRATE

Abstract

Preparation and isolation of the polynuclear copper(II) complex, {[Cu(bipy)(maleato)] · 2H₂O} _n , was accomplished by reaction of an aqueous solution containing sodium maleate and an ethanolic solution of Cu(NO₃)₂·4H₂O and bipy. The crystal structure of the title complex was determined by single-crystal X-ray methods. The structure consists of one-dimensional infinite chains. The copper atom is five-coordinate and presents a square-pyramidal coordination sphere, which consists of the two imine N atoms of bipy and two terminal carboxylate O atoms of a maleate^2- ligand in the basal plane with Cu-N bond distances of 2.016(3) and 1.987(3) A and Cu-O distances of 1.909(2) and 1.947(2) Å, respectively. In the apical site an O atom of the maleate^2- ligand from an adjacent complex coordinates to copper (2.264(2) Å). The coordination fashion of the maleato ligand is also confirmed by the IR spectrum.     

A NOVEL BINUCLEAR COPPER(II) COMPLEX: BIS[1,10-PHENANTHROLINE-N,N′-MALEATO- O,O′-COPPER(II)] DIMETHANOL TETRAHYDRATE

Abstract

A novel binuclear Cu(II) complex, [Cu₂(mal)₂(phen)₂]. 4H₂O. 2MeOH (phen= 1,10-phenanthroline, mal = maleato dianion), has been synthesized and characterized by elemental analysis, IR spectroscopy, solid-state ESR analysis and X-ray single crystal study. The complex consists of [Cu(mal)(phen)] subunits with two water and one methanol solvate molecules. The subunits show a distorted planar arrangement, existing in centrosymmetrically related pairs in the crystal packing. They have a distorted four-coordinate square-planar arrangement of N and O atoms about the central Cu atom; pairs of these [Cu(mal)(phen)] subunits form dimers by interaction of the fifth position on each Cu center with an O atom of a maleato ligand of the associated subunit with a Cu-Cu distance of 3.3425(9) å. The coordination around each Cu atom is best described as distorted square-pyramidal. The lattice water and methanol molecules are also confirmed by the TG study and IR spectra. The X-band solid-state ESR spectrum at room temperature exhibits an anisotropic feature with g′ = 2.24, g′ = 2.06.     

THE CRYSTAL,MOLECULAR STRUCTURE AND LIGAND BONDING IN TETRAKIS (N,N′-DIMETHYLTHIOUREA) NICKEL (II) BROMIDE DIHYDRATE

Abstract

The crystal structure of tetrakis(N,N′-dimethylthiourea)nickel(II) bromide dihydrate has been determined by three-dimensional x-ray diffraction from 1916 counter-data reflections collected at room temperature.

The structure consists of Ni[SC(NH)₂(CH₃)₂]²⁺ ₄ molecular ions, Br^? ions and waters of hydration. The nickel is located on a center of symmetry and is coordinated to four sulfur atoms in a square planar configuration. The waters of hydration and the bromide ions are involved in hydrogen bonding to the N,N′-dimethylthiourea (dmtu) groups. The orientation of the dmtu groups is such that two bond through the sulfur sp² orbital and the others bond through the π-orbitals of the dmtu group. The Ni-S distances are 2.204 ± 0.002 Å and 2.230 ± 0.002 Å, and the Ni-S-C angles are 106.2 ± 0.2Å and 110.3 ± 0.3°. The dmtu groups are planar except for methyl hydrogens.

The crystals are monoclinic, P2₁/a with a = 13.424 ± 0.002 Å, b = 12.321 ± 0.005 Å, c = 8.460 ± 0.008 Å β = 107.07 ± 0.05°, ρ₀ = 1.67 g cm^?3, ρ_c = 1.66 g cm^?3 and Z = 2. The structure was refined by full-matrix least-squares to a conventional R of 0.0466.     

COPPER(II), NICKEL(II) AND COBALT(II) COMPLEXES WITH N,N′-BIS(2-N,N-DIMETHYLAMINOETHYL)PYRIDINE-2,6-DICARBOXAMIDE 1-OXIDE. BINUCLEATING BEHAVIOUR BY A DEPROTONATED PYRIDINE N-OXIDE LIGAND

Abstract

New copper(II), nickel(II), and cobalt(II) complexes are described with the potentially binu-cleating pyridine N-oxide ligand N,N′-bis(2-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide (medpco). Electronic spectra and X-ray powder diffraction measurements indicate that metal complexes of the type M(medpco)Hal₂(H₂O) _x (Hal = Cl, Br) are five-coordinate. Monomeric structures are proposed with ONN-bonded ligand and coordinated halide. This is analogous to the coordination to one of the coppers in the previously reported X-ray structure of Cu₂(medpco)Cl₄. Complexes of the type M′₂(medpco-2H)Hal₂(H₂O) _z (M′ = Ni, Co), involving deprotonated ligand, are reported. These appear to have N-oxide-bridged structures, involving binucleating ligand, analogous to the previously reported X-ray structure of Cu₂(medpco-2H)Cl₂. Variable temperature magnetic data for the complexes are discussed.     

Synthesis and crystal structure (1,10-diaza-18-crown-6-N,N′,O,O′)dichloromanganese(II)

A new crystalline complex (1,10-diaza-18-crown-6-N,N′,O,O′)dichloromanganese(II) [MnCl₂(DA18C6)] (I) is synthesized and studied by single-crystal X-ray diffraction. The structure of compound I (space group P2₁/c, a = 11.827 Å, b = 7.580 Å, c = 19.715 Å, β = 98.76°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.026 for all 3055 independent measured reflections (CAD4 automated diffractometer, λMoK _α radiation). The [MnCl₂(DA18C6)] complex molecule in I is of the host-guest type: its Mn²⁺ cation is asymmetrically arranged in the cavity of the DA18C6 ligand and coordinated by its four heteroatoms, namely, the two N atoms and two O atoms, and by the two Cl^? anions. The coordination polyhedron of the Mn²⁺ cation (six-coordination) may be described as a distorted pentagonal bipyramid with one unfilled vertex or as a distorted square pyramid with one split vertex at the two O atoms of the DA18C6 ligand. The DA18C6 ligand in I has an unusual asymmetric conformation. The complex molecules in a crystal of I are linked by a pair of N-H···Cl intermolecular hydrogen bonds into centrosymmetric dimers.     

REACTION OF BIS(β-ALANINATO)COPPER(II) WITH FORMALDEHYDE: X-RAY CRYSTAL STRUCTURE OF AQUABIS(N,N-DIMETHYL-β-ALANINATO)COPPER(II) HEXAHYDRATE

Abstract

The reaction of bis(β-alaninato)copper(II) with formaldehyde results in the formation of blue crystals of aquabis(N,N-dimethyl-β-alaninato)copper(II) hexahydrate, [Cu(C₅H₁₀NO₂)₂(OH₂)].6H₂O which crystallize in the monoclinic space group C2/c with unit cell dimensions a = 20.799(2), b = 8.112(1), c = 23.639(1)Å, β = 96.50(1)° and Z = 8. The structure has been refined to final R = 0.047 and R_w = 0.053 for 1690 reflections with I ≥ 2.55σ(I).     

SPECTRAL STUDY ON A NEW 3d_z~2 TYPE COPPER(Ⅱ)COMPLEX OF PHENOLIC POLYMERIC CROWN ETHER

ESR and IR measurements have been carried out for a copper(Ⅱ)complex ofphenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2ground state copper(Ⅱ)ions was first observed for the powder sample.It indicatedthat there existed intramolecular spin-spin interaction betweeen 3d_Z2 groundstate copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axialligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ)ions was also confirmed by IR spectra,All things considered,a possible structurefor the complex was proposed.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A BINUCLEAR COPPER (II) COMPLEX BRIDGED BY OXAMIDATO,Cu2(μ-CIS-OXPN)(PHEN)(NO3)2

Abstract

The complex [Cu₂(μ-cis-oxpn)(phen)(NO₃)₂], where oxpn = N,N′ -bis(3-aminopropyl) oxamidato and phen = 1,10-phenanthroline, has been synthesized and its crystal structure determined by X-ray methods. The structure consists of binuclear copper (II) molecules in which the Cu(II) atoms are bridged by oxamidato group in the cis conformation, the Cu—Cu distance being 5.205(10) Å. The coordination geometry around Cu (II) atoms is square pyramidal; the apex is occupied by a more weakly bonded O atom from a nitrate group. Electron delocalization is observed in the bridging oxamide moiety. The co-planarity of bridge ligand and basal plane around Cu (II) atoms may benefit spin super-exchange between two Cu (II) atoms. IR spectra of the binuclear complex are discussed.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A POLYMERIC 1,2,4,5-BENZENETETRACARBOXYLATO COMPLEX OF Cu(II) WITH IMIDAZOLE,Cu2(C10H2O8)(C3H4N2)6(H2O)4 · 4H2O

Abstract

The title complex, Cu₂(C₁₀H₂O₈)(C₃H₄O₂)₆(H₂O)₄ · 4H₂O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.     

AN ALKOXO-BRIDGED BINUCLEAR MANGANESE COMPLEX BIS(μ-PROPIONATO-O: O′)-BIS(μ-3-SALICYLIDENE-AMINO-PROPANOLATO-O″,O‴,N:O″) BISMANGANESE(III)

Abstract

The alkoxo-bridged binuclear complex of Mn^III, [Mn₂(salpa)₂(C₂H₅—COO)₂] (H₂salpa = 3-salicylidene-amino-1-propanol), has been prepared and its crystal structure has been determined by X-ray diffraction. The structure of the title complex consists of discrete binuclear manganese units in which the Mn^III atoms are bridged by two alkoxo ligands via oxygen atoms and supported by two carboxylato bridging ligands in the syn - syn fashion. The complex lies about a crystallographic inversion center. Each Mn^III atom is located in an elongated octahedral environment with one imino N, one phenolic O and two alkoxo O atoms coordinated in the equatorial plane and two O atoms from carboxylato groups at the apical positions. The remarkably longer coordination bond distances in the axial direction are attributed to Jahn-Teller distortion at the d ⁴ manganese center. The distance between the manganese atoms is 2.8662(9) Å. The asymmetrical and symmetric stretching vibrations for carboxylato groups found at 1550 and 1440 cm^?1, respectively, with a separation of less than 200 cm^?1 confirmed the bidentate mode of the carboxylato groups.     

Tetranuclear azido-bridged copper(II) complex [Cu4(μ-salpn)2(μ1,1-N3)2(N3)2(H2O)2]: Synthesis,characterization and crystal structure

The reaction of salpnH₂ Schiff-base ligand (salpnH₂ = N,N′-bis(salicylidene)-1,3-propylenediamine) with Cu(NO₃)₂·3H₂O and a large excess of NaN₃ (1:2:8 molar ration), lead to the formation of [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1), which has been successfully obtained and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The strong absorption band at about 2000–2100 cm^?1 and at 1597 cm^?1 regions of the IR spectrum of 1 clearly proves the presence of the both end-on (EO) bridging and terminal azido ions and CN (azomethine) groups, respectively. Single-crystal X-ray analyses revealed that the copper atoms are bridged alternately by end-to-on (EO) azido and phenoxo-salpn ligands in the prepared tetranuclear copper(II) complex [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1).     

STRUCTURES OF COPPER(I) AND ZINC(II) COMPLEXES WITH N,N′-BIS(2-PYRIDINYL)THIOUREA (BPT)

Abstract

Copper(I) and zinc(II) complexes with N,N′-bis(2-pyridinyl)thiourea (BPT), [Cu(BPT)₂]ClO₄ (1) and [Zn(BPT)₂](ClO₄)₂ (2) were synthesized by reaction of M(ClO₄)₂ (M = Cu, Zn) with BPT in methanol solution. The crystal structures of complexes (1) and (2) were characterized by X-ray diffraction: (1) is triclinic, space group P, with a = 10.162(2), b=14.483(6), c = 9.496(2) Å, α = 105.80(2)°, β = 106.94(2)°, γ = 82.71(3)°, V = 1284.4(7) ų, Z = 2, and final R = 0.047, R _w = 0.061; (2) is monoclinic, space group C2/c, with a = 15.15(1), b = 6.299(3), c = 30.16(1)Å, β = 93.49(7)°, V = 2872(2)ų, Z=4, and final R = 0.049, R_w = 0.070. Both of the complexes exhibit novel structures. Two N atoms and two S atoms from two BPT groups coordinate to one M atom. The M atom shows distorted tetrahedral geometry. IR spectra and ther-moanalyses of BPT and its complexes (1) and (2) are briefly discussed.     

CYCLOADDITION REACTION OF THE AZIDO-BRIDGED CYCLOMETALLATED COMPLEX [Pd(dmba)N3]2 WITH CS2. CRYSTAL AND MOLECULAR STRUCTURE OF DI(μ, N,S-l,2,3,4-THIATRIAZOLE-5-THIOLATE)BIS[(N,N-DIMETHYLBENZYL-AMINE-C2,N)PALLADIUM(II)]

Abstract

The 1,3-dipolar cycloaddition of carbon disulfide to the coordinated azide in the cyclometal-lated compound [Pd(dmba)(N₃)]₂ (1), dmba = N,N-dimethylbenzylamine, was investigated. The compound obtained di(μ, N, S-l,2,3,4-thiatriazole-5-thiolate)-bis[(N,N-dimethylbenzylamine-C², N)palladium(II)] (2), was characterized by IR spectroscopy and X-ray diffraction. Complex (2) is dimeric with the two [Pd(N,N-dimethylbenzylamine)] moieties being connected by the two vicinal bridging N, S-l,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination for the palladium atoms.     

SEMICONDUCTOR COPPER(II) MACROCYCLIC COMPLEXES. SYNTHESIS,CHARACTERIZATION AND ELECTRICAL PROPERTIES OF COPPER(II) COMPLEXES OF THE TYPE [Cu(TAABL)](NO3) · nH2O WITH L = NH(CH2)2NH2, NH(CH2)4NH2, NH(CH2)12NH2, AND THE COMPLEX [Cu(TAAB(C14H9N2O2)2)] · 4H2O

Abstract

The complexes [Cu(TAABNH(CH₂)₂NH₂)](NO₃) · 2H₂O, (1) [Cu(TAABNH(CH₂)₄NH₂)] (NO₃)·4H₂O, (2), [Cu(TAABNH(CH₂)₁₂NH₂](NO₃)·4H₂O,(3) and [Cu(TAAB(C₁₄H₁₀ N₂O₂)₂]·4H₂O, (4) have been synthesized and characterized by IR, mass spectroscopy, electronic spectroscopy, thermogravimetric analysis and elemental analysis. Electrical conductivity and activation energy evaluation were obtained from study of the temperature dependence of the electrical current (in tablet and thin film). Refraction and reflectance indices, absorption coefficient and optical activation energy were established through ellipsometry and UV-Vis spectroscopy. The electrical conductivity values at room temperature were within the range of semiconducting molecular solids (10^?6?10¹Ω^?1cm^?1).     

1,3-DIPOLAR CYCLOADDITION OF CS2 TO THE COORDINATED AZIDE IN THE CYCLOPALLADATED [Pd(bzan)(μ-N3)]2. CRYSTAL AND MOLECULAR STRUCTURE OF DI(μ-N,S-1,2,3,4-THIATRIAZOLE-5-THIOLATE)BIS[(BENZYLIDENEANILINE-C2,N)PALLADIUM(II)]

Abstract

The compound [Pd(bzan)(μ-N₃)]₂ 1, bzan = benzylideneaniline, was prepared from [Pd(bzan) (μ-OOCCH₃)]₂ by an anion exchange reaction. The 1,3-dipolar cycloaddition of carbon disulfide to the bridged coordinated azide in the cyclometallated compound 1 was investigated. The species resulting from this reaction, di(μ-N,S-1,2,3,4-thiatriazol-5-thiolate)bis [(benzylidene-aniline)palladium(II)] 2, was characterized by IR spectroscopy and X-ray diffraction. The compound 2 is a dimer containing two [Pd(benzylideneaniline)] moieties connected by two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination geometry for the palladium atoms.     

Synthesis and Characterization of Binuclear (μ-Oxalato) Copper(II) Complexes with N,N′-Diethylethylenediamine or N,N,N′-Trimethylethylenediamine

Three new binuclear w -oxalato copper(II) complexes of composition [(Cu(N,N' -dieten) H₂O)₂ox](ClO₄)₂ ·H₂O (1) (N,N'-dieten = N,N'-diethylethylenediamine, H₂ox = oxalic acid), [(Cu(trimeen)H₂O)₂ox](ClO₄)₂·2H₂O (2) (trimeen = N,N,N'-trimethylethylenediamine) and [(Cu(trimeen)H₂O)₂ox](NO₃)₂ ·2H₂O (3) have been isolated from the reactions of Cu(ClO₄)₂ ·6H₂O (or Cu(NO₃)₂ ·3H₂O), the appropriate amine and Na₂ox in water and have been characterized by IR and electronic spectroscopy and magnetic measurements. The crystal structure of [(Cu(N,N' -dieten)H₂O)₂ ox](ClO₄)₂.H₂O (1) has been determined by single-crystal X-ray analysis. The structure of ( 1 ) consists of binuclear cations [(N,N'-dieten)H₂O)Cu(ox)Cu(N,N'-dieten)H₂O)]²⁺, perchlorate anions and water molecules of crystallization. The copper atom is coordinated by two oxygen atoms of the oxalato ligand, two nitrogen atoms belonging to N,N'-dieten and one oxygen atom of water in a distorted square-pyramidal arrangement. The temperature dependence of magnetic susceptibilities (78-293 K) was measured for 1-3 . Magnetochemical measurements show that copper(II) ions in these compounds are antiferromagnetically coupled with J = -172 cm^-1, -172 cm^-1 and -168 cm^-1 (H = -2JS ₁ S ₂, S ₁= S ₂ = 1/2) for 1, 2 and 3, respectively.     

Bis(μ3-barbiturato−O,O,O′)-(μ2-aqua)- aqua-barium(II): crystal structure,spectroscopic and thermal properties

A polymeric coordination compound, [Ba(H₂O) ₂(Hba)₂] (1) (H₂ba – barbituric acid, C₄H₄N₂O₃), was obtained. The structure of 1 was solved using powder X-ray diffraction methods. The Ba²⁺ ion in 1 formed a three-capped trigonal prism. The BaO₉ polyhedra, connected with each other by the edges and faces, formed a chain. Several 4- and 12-membered cycles due to the bridging μ₂-H₂O and bridging μ₃-Hba^– also formed implementing a 3-D polymer structure. The structures of 1 and other thiobarbiturate complexes were compared. The replacement of a S atom by an O atom in the heterocyclic ligand Htba^? (thiobarbiturate ion) of the compound Ba(H₂O)₂(Htba)₂ resulted in changes of the coordination number Ba(II) and supramolecular structure. The intermolecular hydrogen bonds O–H?O and N–H?O formed a 3-D net where pronounced 2-D layers of Hba^– ions could be found. A new topological net in 1 was observed. The IR and thermal stability were investigated.     

Two 2-D copper(II) azido compounds: catena -poly[ di -μ1,1- azido,di -μN,O-(quinolinecarboxylato)(aqua)copper(II)] and 1-D catena -poly[ di -μN,N′-(quinoxaline)copper(II)nitrate]

We synthesized three copper(II) complexes with two structurally related polydentate ligands, quinoline-4-carboxylic acid (quCOOH) and quinoxaline (qux). The structures of these complexes were determined using X-ray single crystal crystallography. Complex 1, [Cu(quCOO)(N₃)(H₂O)] _n , has a 2-D polymeric structure through di-μ_1,1 azido groups forming (Cu₂N₂) dimeric units and di-μ_N,O quinoline carboxylate bridging the binuclear copper units. [Cu(quCOO)(N₃)(H₂O)] _n · 0.87MeOH, (2), has the same structure as 1 in addition to MeOH molecules separating the 2-D sheets of [Cu(quCOO)(N₃)(H₂O)] _n . [Cu(qux)(NO₃)₂] _n , (3), has no coordinated azido groups, but the quinoxaline is a bidentate bridging ligand giving a 1-D chain, while the μ_O,O′ chelating nitrato groups stabilize the chain structure by forming a square planar coordination sphere around copper. IR and UV–Vis spectra of the complexes are in agreement with the crystal structures.