Synthesis, structure and properties of two bimetallic compounds [Co(bpy)2 (NiL)] (ClO4)2 and {[Co(phen)3](NiL)}(ClO4)2 containing a macrocyclic oxamide ligand

Two compounds, [Co(bpy)₂(NiL)](ClO₄)₂ (1)and {[Co(phen)₃](NiL)}(ClO₄)₂ (2), have been synthesized: (H₂L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacylotetradeca-7,12-diene, bpy=2,2-bypyridine and phen = 1,10-phenanthroline). Compound (1) contains a discrete binuclear [Co(bpy)₂(NiL)]²⁺ cation, while compound (2) is composed of [Co(phen)₃]²⁺ cations and NiL neutral fragments. The magnetic properties of compound (1) have been dealt with by isotropic one-ion approximation of the Co^II ion with a spin--orbit coupling in an O_h symmetry environment. The electronic spectra of these two compounds have also been discussed.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Syntheses and characterization of mixed-anion cadmium(II) complexes,structural characterization of [Cd(phen)2(NO2)1.65(NO3)0.35], as a new eight-coordinate Cd(II) complex

New mixed-anion cadmium(II) complexes of 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) ligands, [Cd(phen)₂(NO₂)_1.65(NO₃)_0.35] and Cd(bpy)(ClO₄)(CH₃COO) have been synthesized and characterized by elemental analysis, IR-, ¹H NMR-, ¹³C- NMR and ¹¹³Cd NMR spectroscopy. The single crystal X-ray data of [Cd(phen)₂(NO₂)_1.65(NO₃)_0.35] show the complex to be a monomer and that the Cd atom has an unsymmetrical eight-coordinate geometry, being coordinated by four nitrogen atoms of ‘phen’ ligands and four oxygen atoms of the nitrite and nitrate anions. There is a short π–π stacking interaction between parallel aromatic rings.     

Crystal Structures of [Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O and [Mn(H2O)2(bpy)(C8H12O4)2/2] · H2O with bpy = 2,2′‐bipyridine

Reaction of MnSO₄ · H₂O, 2,2′‐bipyridine (bpy), suberic acid and Na₂CO₃ in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] · 2 H₂O ( 1 ) and [Mn(H₂O)₂‐ (bpy)(C₈H₁₂O₄)_2/2] · H₂O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H₂O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] complex molecules in 1 and 1D [Mn(H₂O)₂(bpy)(C₈H₁₂O₄)_2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H₂O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H₂O molecules located in tunnels along [010]. Crystal data for 1 : P2₁/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P2₁/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8.     

Syntheses,Crystal Structures,and Thermal Behavior of Co(phen)(HL)2 and [Co2(phen)2(H2O)4L2]·H2O with H2L = Pimelic Acid

Two Co^II complexes, Co(phen)(HL)₂ ( 1 ) and [Co₂(phen)₂(H₂O)₄L₂]·H₂O ( 2 ) (H₂L = HOOC‐(CH₂)₅‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co₂(phen)₂(H₂O)₄L₂] molecules and hydrogen bonded H₂O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H₂O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N₂ atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)ų, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)ų, Z = 2.     

Synthesis and Single-crystal Structures of Two Copper(II) Complexes and One Iron(II) Complex Prepared by in situ Ligand Substitution at Room Temperature

Two hexa-coordinate copper(II) complexes formulated as [Cu(phen)(4-dmampy)₂(ClO₄)₂] and [Cu(bpy)(3-ampy)₂(ClO₄)₂] · 0.5CH₃OH · 0.5H₂O (phen = 1,10–phenanthroline bpy = 2,2′-bipyridine, 3-ampy = 3-aminopyridine, 4-dmampy = 4-dimethylaminopyridine), and one low-spin ferrous complex formulated as [Fe(dmbpy)₃](ClO₄)₂ · H₂O (dmbpy = 4,4′-dimethyl-2,2′-bipyridine), were synthesized by in situ ligand substitution at room temperature, and characterized by X-ray single-crystal diffraction. This is the first structural report where either 4-dmampy and phen molecules, or 3-ampy and bpy molecules, are located simultaneously around one metal center.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Hydrothermal Synthesis and Structures of Two New Molybdenum Phosphate Compounds based on Keggin Cluster Units

Two new molybdenum phosphate complexes, [Cu₂(phen)₄(μ‐Cl)][PMo₁₂O₄₀]·H₂O (phen = 1,10‐phenanthroline) ( 1 ) and (Hbpy)[Cu^I(bpy)]₂[PMo^V₂Mo^VI₁₀O₃₉] (bpy = 4,4′‐bipyridine) ( 2 ), have been prepared under mild hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in triclinic system, space group , with a = 12.5458(7) Å, b = 13.4486(8) Å, c = 21.2406(12) Å, α = 99.7020(10)°, β = 94.2320(10)°, γ = 95.0890(10)°, V = 3504.2(3) ų and Z = 2 for 1 , and a = 10.7871(6) Å, b = 10.9016(6) Å, c = 12.7897(7) Å, α = 96.8500(10)°, β = 110.0850(10)°, γ = 103.5800(10)°, V = 1339.74(13) ų and Z = 1 for 2 . Compound 1 contains a [Cu₂(phen)₄(μ‐Cl)]³⁺ cation in which two similar [Cu(phen)₂] units are bridged by one chlorine atom. Compound 2 contains one‐dimensional straight chain of Keggin polyoxoanions [PMo^V₂Mo^VI₁₀O₃₉]_n^3? and two linear cationic chains of [Cu^I(bpy)]_nⁿ⁺. The molecular packing shows a two‐dimensional network, which is formed by the cross of the linear Keggin anions and Cu‐bpy cations.     

Hydroxo Bridged Dinuclear Rare Earth Complexes: Syntheses and Crystal Structures of [Ln2(phen)4(H2O)4(OH)2](NO3)4(phen)2 with Ln = Er,Lu

Reactions of phenanthroline (phen) and Er(NO₃)₃ · 5 H₂O or Lu(NO₃)₃ · H₂O in CH₃OH/H₂O yield [Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄(phen)₂ with Ln = Er ( 1 ), Lu ( 2 ). Both isostructural complex compounds crystallize in the triclinic space group P 1 (no. 2) with the cell dimensions: a = 11.257(2) Å, b = 11.467(2) Å, c = 14.069(2) Å, α = 93.93(2)°, β = 98.18(1)°, γ = 108.14(1)°, V = 1696.0(6) ų, Z = 1 for ( 1 ) and a = 11.251(1) Å, b = 11.476(1) Å, c = 14.019(1) Å, α = 93.83(1)°, β = 98.27(1)°, γ = 108.27(1)°, V = 1689.0(3) ų, Z = 1 for ( 2 ). The crystal structures consist of the hydroxo bridged dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cations, hydrogen bonded NO₃^– anions and π‐π stacking (phen)₂ dimers. The rare earth metal atoms are coordinated by four N atoms of two phen ligands and four O atoms of two H₂O molecules and two μ‐OH groups to complete tetragonal antiprisms. Via two common μ‐OH groups, two neighboring tetragonal antiprisms are condensed to a centrosymmetric dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cation. Based on π‐π stacking interactions and hydrogen bonding, the complex cations and (phen)₂ dimers form 2 D layers parallel to (1 0 1), between which the hydrogen bonded NO₃^– anions are sandwiched. The structures can be simplified into a distorted CsCl structure when {[Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄} and (phen)₂ are viewed as building units.     

Synthese und Kristallstruktur von [Na3(H2O)6,5(EtOH)][PhSnS3] · 3 EtOH

Synthesis and Crystal Structure of [Na₃(H₂O)_6,5(EtOH)][PhSnS₃] · 3 EtOH Ph₄Sn₄S₆ reacts with Na₂S · 5 H₂O in aqueous acetone to form Na₃[PhSnS₃]. Recrystallization of the crude product from ethanol leads to colourless needles of [Na₃(H₂O)_6,5(EtOH)][PhSnS₃] · 3 EtOH 1 . The crystal structure of 1 was determined by X-ray diffraction. 1 consists of [PhSnS₃]^3– anions and sodium cations which are coordinated by water, ethanol and sulfur atoms of the [PhSnS₃]^3– anions. The [PhSnS₃]^3– anion contains a tin atom which is coordinated nearly tetrahedrally by a phenyl group and three sulfur atoms. The Sn–S bonds are 237,4(2)–238,4(2) pm.     

Synthesis and Crystal Structure of [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O with phen = 1,10‐phenanthroline

The blue copper complex [Cu₂(H₂O)₂(phen)₂(OH)₂][Cu₂(phen)₂(OH)₂(CO₃)₂] · 10 H₂O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl₂ · 2 H₂O and Na₂CO₃ in the presence of succinic acid in CH3OH/H₂O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) ų, Z = 1. The crystal structure consists of dinuclear [Cu₂(H₂O)₂(phen)₂(OH)₂]²⁺ complex cations, dinuclear [Cu₂(phen)₂(OH)₂(CO₃)₂]^2– complex anions and hydrogen bonded H₂O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H₂O molecule or one CO₃^2– anion to complete distorted [CuN₂O₃] square‐pyramids with the H₂O molecule or the CO₃^2– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN₂O₃] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.     

Synthesis and Crystal Structures of Manganese(II) and ­Cobalt(II) Complexes with 2, 6‐Dimethoxybenzoic Acid and Additional N‐Donor Ligands

Three coordination compounds [Mn₃(dmb)₆(H₂O)₄(4, 4′‐bpy)₃(EtOH)]_n ( 1 ) and [M(dmb)₂(pyz)₂ (H₂O)₂] [M^II = Co ( 2 ), Mn ( 3 )] (Hdmb = 2, 6‐dimethoxybenzoic acid, 4, 4′‐bpy = 4, 4′‐bipyridine, pyz = pyrazine) were synthesized and characterized by single‐crystal X‐ray diffraction analysis. Compound 1 consists of infinite 1D polymeric chains, in which the metal entities are bridged by 4, 4′‐bpy ligands. There are four crystallographically independent Mn^II atoms in the linear chain with different coordination modes, which is only scarcely reported for linear polymers. The isostructural crystals of 2 and 3 are composed of neutral mononuclear complexes. In crystal the complexes are combined into chains by intermolecular O–H ··· N hydrogen bonds and π–π interactions between antiparallel pyrazine molecules.     

Synthesis, Crystal Structure and Optical Properties of Europium Trifluoroacetate Complexes with 1,10-Phenanthroline and 2,2-Bipyridine

Two europium trifluoroacetate complexes, Eu(CF₃COO)₃·phen ( 1 ) and Eu(CF₃COO)₃·bpy ( 2 ) (where phen=1,10‐phenanthroline, bpy=2,2′‐bipyridine), were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) spectroscopy and thermogravimetric analysis (TA). Single‐crystal X‐ray structure has been determined for the complex [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH. The crystal structure of [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH shows that two different coordination styles with europium ions coexist in the same crystal and have entirely different coordination geometries and numbers. This crystal can be considered as an 1:1 adduct of [Eu(CF₃COO)₃·(Phen)₂·H₂O]·EtOH (9‐coordination part) and Eu(CF₃COO)₃·phen·H₂O (8‐coordination part). The excitation spectra of the two complexes demonstrate that the energy collected by "antenna ligands" is transferred to Eu³⁺ ions efficiently. The room‐temperature PL spectra of the complexes are composed of the typical Eu³⁺ ions red emission, due to transitions between ⁵D₀→⁷F_J(J=0→4). The lifetimes of ⁵D₀ of Eu³⁺ in the complexes were examined using time‐resolved spectroscopic analysis, and the lifetime values of Eu(CF₃COO)₃·phen and Eu(CF₃COO)₃·bpy were fitting with bi‐exponential (2987 and 353 µs) and monoexponential (3191 µs) curves, respectively. In order to elucidate the energy transfer process of the europium complexes, the energy levels of the relevant electronic states had been estimated. The thermal analyses indicate that they are all quite stable to heat.     

Supramolecular Assembly of Triangulo Pd(II) Diimine Complexes Containing Triply‐Bridging Sulfide Ligands

We report here a substituent effect of diimines on the solid‐state assembly of interesting triangulo Pd(II) complexes, [(Pd(d‐t‐bpy))₃(μJ₃‐S)₂][NO₃]₂ 1 ·[NO₃]₂ and [(Pd(bpy))₃(μ₃‐S)₂][ClO₄]₂ 2 ·[ClO₄]₂ (d‐t‐bpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, bpy = 2,2′‐bipyridine). 2 ·[ClO₄]₂ shows the intermolecular π···π interactions leading to the formation of one‐dimensional frameworks, whereas 1 ·[NO₃]₂ only shows the discrete structure in the solid state, featuring an interesting herring‐bone arrangement. The variation in structural motifs from 1 ·[NO₃]₂ to 2 ·[ClO₄]₂ is expected to be dominated by the substituent's steric hindrance for the diimine ligand. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to a substituent's modification of the diimine ligand.     

Synthesis,Crystal Structures and Properties of Tetrametallic Complexes: [M2(phen)4(FCA)2](ClO4)2·(H2O)2 (M=Zn or Co,phen=1,10‐phenanthroline,FCA=anion of 3‐ferrocenyl‐2‐crotonic acid)

Two new complexes [Zn₂(phen)₄(FCA)₂](ClO₄)₂·(H₂O)₂ ( 1 ) and [Co₂(phen)₄ (FCA)₂](ClO₄)₂·(H₂O)₂ (2) (FCA=anion of 3‐ferrocenyl‐2‐crotonic acid, phen=1,10‐phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV‐Vis spectra, thermal analyses, and single‐crystal X‐ray diffraction. Two M(II) (M=Zn or Co) ions are bridged by two FCA anions with syn‐anti bridging ligands, leading to dimeric cores, [M₂(phen)₄(FCA)₂]²⁺, and each M(II) ion is six‐coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ₂‐carboxylate oxygen atoms from two FCA groups. The M(II)…M(II) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2 , respectively. Electrochemical properties of the complexes have been discussed.     

Syntheses and Crystal Structures of Ln(phen)2(NO3)3 with Ln = Pr,Nd, Sm,Eu, Dy,and phen = 1,10‐phenanthroline

Five new complex compounds of the formula Ln(phen)₂(NO₃)₃ were prepared. The X‐ray structural analyses indicate that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions for example for Pr(phen)₂(NO₃)₃: a = 11.194(1) Å, b = 18.095(2) Å, c = 13.101(2) Å, β = 100.52(1)°, V = 2609.1(6) ų, Z = 4. The crystal structures consist of [Ln(phen)₂(NO₃)₃] complex molecules. The rare earth atoms are coordinated by four N atoms of two phen ligands and six O atoms of three nitrato groups to complete a distorted bicapped dodecahedron. The [Ln(phen)₂(NO₃)₃] complex molecules are assembled via π‐π stacking interactions between the neighboring phen ligands to form 1D columnar chains, which are then arranged in the crystal structures according to pseudo 1D close‐packed patterns.     

Hydrothermal Preparation,Crystal Structure and Properties of {[ZnTCPP(EtOH)][Zn(en)]2}n(EtOH)2n with a Novel Two‐Dimensional (2‐D) Motif

A novel zinc porphyrin, {[ZnTCPP(EtOH)][Zn(en)]₂}_n(EtOH)_2n ( 1 ) (TCPP=meso‐tetra(4‐carboxyphenyl)‐porphyrin; EtOH=ethanol; en=ethylenediamine) was obtained via a hydrothermal reaction and characterized by single‐crystal X‐ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinic system with eight formula units in a cell: a=32.465(4) Å, b=10.527(3) Å, c=31.845(3) Å, β=95.524(6) °, V=10832(4) ų, C₅₈H₅₇N₈O₁₁Zn₃, M_r=1238.23, D_c=1.518 g/cm³, S=1.005, µ(Mo Kα) =1.388 mm^?1, F(000) =5112, R=0.0650 and wR=0.1574. Complex 1 features a novel 2‐D layered motif. The spectral data of UV‐vis, FT‐IR and fluorescence are reported.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

Syntheses and Characterization of a New One-Dimensional Polymer Containing (µ-Thiocyanate)(bpy)Lead(II) Molecule and New Mixed-Anion Lead (II) Complexes: Crystal Structures of [Pb(bpy)(SCN)2] n (byp = 2,2'-Bipyridine) and [Pb(phen)2(NO3)0.7(ClO4)0.3](ClO4) (phen = 1,10-Phenanthroline)

Complexes [Pb(bpy)(SCN)₂] _n (bpy = 2,2′-bipyridine), [Pb (phen)₂(NO₃)_0.7(ClO₄)_0.3](ClO₄), Pb(phen)₂(SCN)-(NO₃), and Pb(phen)₂(SCN)(ClO₄) (phen = 1,10-phenanthroline)], have been synthesized using a direct reaction between Pb(NO₃)₂ and ligands. The complexes have been isolated and characterized by IR-spectra and CHN-elemental analysis. The structures of [Pb(bpy)(SCN)₂] _n and [Pb(phen)₂(NO₃)_0.7(ClO₄)_0.3](ClO₄) have been confirmed by X-ray crystallography. The single crystal X-ray crystallography of a new one-dimensional complex of Pb(II) with 2,2′-bipyridine, [Pb(bpy)(SCN)₂] _n , shows the complex to be polymeric as a result of thiocyanate ligand bridging. The Pb atom being in a unsymmetrical eight-coordinate, N₄S₄, environment and the arrangement of the 2,2′-bipyridine, thiocyanate anion suggest a gap in coordination geometry around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on lead (II) and the coordination around atoms is hemi-directed. There is a π-π interaction between the aromatic rings of the interchains in [Pb(bpy)(SCN)₂] _n , this stacking causes the complex to be more stable. An attempt to isolate single crystals of Pb(phen)₂(NO₃)(ClO₄) from water led to the isolation of [Pb(phen)₂(NO₃)_0.7(ClO₄)_0.3](ClO₄). The single crystal X-ray study shows the complex to be monomeric. The Pb atom lies in an unsymmetrical six-coordinate, N₄O₂, environment and the arrangement of the 1,10-phenanthrolines, suggest a gap in coordination geometry around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on lead (II) and the coordination around atoms is hemi-directed.     

Manganese(II)-phenanthroline-azide compounds: Versatile Precursors as Ligands in Designing Heteropolymetallic Systems

Two novel manganese(II) complexes, [Mn(phen)₂N₃·H₂O]ClO₄·H₂O and Mn(phen)₂(N₃)₂ have been synthesized by the reaction of Mn(ClO₄)₂·6H₂O and Mn(CH₃CO₂)₂·4H₂O with NaN₃ and phen in EtOH/H₂O solution, respectively (where phen = 1,10-phenanthroline). Their crystal structures have been determined by X-ray diffraction. Both complex molecules have distorted octahedral geometry and two 1,10-phenanthroline molecules chelate to a Mn(II) atom with a cis-configuration. To [Mn(phen)₂N₃·H₂O]ClO₄·H₂O, one nitrogen atom from an azide anion and one oxygen atom from a water molecule cis-coordinate to the Mn(II) atom while two nitrogen atoms occupy cis positions in Mn(phen)₂(N₃)₂. These complexes are versatile precursors for the design of heteropolymetallic systems.