Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of Lithium Manganese Complex of Benzene-Hexacarboxylic Acid (Mellitic Acid)

Abstract  

A new mellitate complex LiMn[C₆(COO)₆]_0.5(H₂O)₂ (1) has been synthesized by the reaction of mellitic acid and Mn(OAc)₂·4H₂O in the presence of LiOH·H₂O. 1 was characterized by the elemental analyses, IR spectra, TGA and the single crystal X-ray diffraction. X-ray crystal structural analysis revealed that the Li cation has a distorted tetrahedral geometry, coordinated by three carboxylic oxygen atoms and one water molecule. The Mn cation is coordinated to one water molecule and five carboxylic oxygen atoms in a slightly distorted octahedral coordination geometry. The mellitate anions behave as a bridging ligand and link six lithium ions and eight manganese ions repeatedly to form an interesting three-dimensional metal–organic coordination polymer. Variable-temperature magnetic susceptibility measurements indicate the presence of antiferromagnetic behavior.     

Complexes Containing N-(2-hydroxyethyl)-ethylenediamine with Tetracyanometallate (II): Synthesis, IR Spectra, Thermal Behavior, Crystal Structure, Magnetic Properties and Catalysis

Two novel cyano-bridged Ni²⁺ and Cu²⁺ compounds, {[M²⁺(hydeten)₂(μ-CN)₂Ni(CN)₂] _n , M²⁺ = Ni²⁺ (c1) and Cu²⁺ (c2), N-(2-hydroxyethyl)-ethylenediamine (hydeten), were prepared and characterized by elemental analysis, IR spectroscopy and thermoanalytical measurements. The one-dimensional polymeric structure of c2, which was determined by X-ray diffraction techniques, was formed with a 2,2-TT-type chain, –Cu(hydeten)₂-NC-Ni(CN)₂-CN-Cu(hydeten)₂-, linkages. Also, while the EPR spectra and magnetic properties of complexes c1 and c2 with [Ni(hydeten)₂Pd(CN)₄] (c3) and [Cu(hydeten)₂Pd(CN)₄] (c4) [Karadağ, Z Kristallogr 222:39, 2007] were investigated, the catalytic activity of c3 and c4 was studied. The EPR spectra of c2 and c4 showed that Cu²⁺ was located in tetragonal distorted octahedral sites (D _4h ) and the ground state of the paramagnetic electron was d _{x² - y²} d_{{ x^{2} - y^{2} }} . The magnetic behavior exhibited weak antiferromagnetic interactions in all the complexes. Also, the catalytic properties of c3 and c4, which were assigned with Suzuki and Heck coupling reactions, showed that they did not have catalytic effects.     

Hydrothermal Syntheses,Crystal Structure and Luminescent Properties of Two New Zn(II) Coordination Polymers

Two new zinc(II) coordination polymers; namely, [Zn(BDC)(L)_0.5]_n (1) and {[Zn(BDC)(L)]·3H₂O}(2), were successfully synthesized by the assembly of Zn(II) ion, 1.2-benzene-dicarboxylate acid (H₂BDC) and 1,4-bis(2-methylimidazole-3-ium-1-yl) biphenyl (L). A change in the pH values resulted in complexes with different compositions and dimensionalities. Formed at the lower pH, 1 exhibits a three-dimensional structure with mab topology. At a higher pH, 2 shows a two-dimensional structure, which contains one-dimensional helical chains. The luminescent properties for 1 and 2 were investigated in the solid state at room temperature.     

Synthesis and Crystal Structure of Diaqua(1,10-Phenanthroline-N,N')(Thiosulfato-O,S)Manganese(II). Biological Properties

The synthesis of diaqua(1,10-phenanthroline-N,N')(thiosulfato-O,S)manganese(ll) [Mn(phen)(S(2)O(3))(H(2)O)(2)] was investigated. Its structure was determined by single crystal X-ray diffraction from 2418 reflections (I > 3 sigma(I)) to a final value of R = 0.047 and Rw = 0.054. Crystal data are as follows : space group P(2) (1); a = 10.356(3), b = 7.097(3), c = 20.316(2) A, beta = 94.29(2) degrees , V = 1489.1(8) , A(3), Z = 2. There are two independent title compounds in the asymetric unit. Each manganese atom has a distorted octahedral Mn(SO)N(2)O(2) geometry with the S and O atoms (from two neighbouring thiosulfate ligands) mutually trans, two N atoms from the 1,10-phenanthroline ligand and two water oxygen. The thiosulfate group behaves as a bridging ligand, connecting, through sulfur and oxygen, Mn atoms related by the binary b translation, thus forming infinite chains running parallel to this axis. Infrared and electronic spectra are reported.     

Syntheses and Crystal Structures of Zinc(II) and Nickel(II) Coordination Polymers Based on Diphenic Acid and 1,2-Bis(4-pyridyl)ethane Coligands

Two new metal coordination polymers [Zn₂(dpa)₂(bpa)] (1) and [Ni₄(dpa)₄(bpa)₃] (2) [H₂dpa = 2,4′-biphenyldicarboxylic acid and bpa = 1,2-bis(4-pyridyl)ethane] have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that complex 1 shows a 2D (4,4) topological net and complex 2 features a 3D network with (4.6²)₂(4².6¹⁰.8³) topology. Fluorescent study of complex 1 shows that it has an emission at 414 nm in the solid state at room temperature.     

Synthesis, Crystal Structure and Magnetic Properties of a Nickel(II) Coordination Polymer Based the V-Shaped Ligands

Abstract  

A new nickel(II) coordination polymer, Ni₂(DBA)₂(BIDPE)₂(H₂O) (1) (H₂DBA = 4,4′-methylenedibenzoic acid and BIDPE = 4,4′-bis(imidazole-l-yl)diphenyl ether), has been prepared by hydrothermal synthesis and structurally characterized by IR, elemental analysis, TGA and single crystal X-ray diffraction. Complex 1 features a one-dimensional chain structure based on triply bridged binuclear units, which is further interlinked into a higher-dimensional supramolecular framework by intermolecular weak interactions. Variable-temperature magnetic data shows weak antiferromagnetic behavior in 1.     

Tris-Alkoxylphenylterpyridine Cobalt(II) Complexes: Synthesis, Structure, and Magnetic and Mesomorphic Behaviors

Two novel cobalt(II) complexes [Co(L1)₂](BF₄)₂·CH₃CN·0.5H₂O (1) and [Co(L2)₂](BF₄)₂ (2) (L1 = 4′-(3,4,5-trimethoxy-phenyl)-[2,2′:6′,2″]terpyridine, L2 = 4′-(3,4,5-tris-hexadecyloxy-phenyl)-[2,2′:6′,2″]terpyridine) have been synthesized, and their structural, magnetic and mesomorphic properties were characterized by single crystal X-ray diffraction (XRD) analysis, temperature-dependent magnetic susceptibility, POM, DSC, and powder XRD analysis. The molecular structure of the complex 1 with short alkyl substituents exhibited that the metal ion has an N₆ coordination sphere of distorted octahedral geometry and various intermolecular π–π interactions are important factors influencing the crystalline array. The magnetic behaviour of 1 displayed a typical of gradual spin transition for cobalt(II) terpyridine complexes. On the other hand, the complex 2 possessing linear long alkyl chains showed a gradual spin transition between low-spin and high-spin with a thermal hysteresis loop (T _1/2↑ = 338 and T _1/2↓ = 327 K) triggered by the crystal-to-mesophase transition. The powder XRD and POM analyses were indicative of the liquid crystalline lamellar phase of 2.     

Syntheses and Structural Analytical Studies of Two Co(II) Complexes Based on 1,4-Di(benzimidazole-1-yl)benzene

Two new Co(II) complexes of 1,4-di(benzimidazole-1-yl)benzene ligand (L) with the formulas [(CoLCl₂)(CHCl₃)(DMF)]_∞ (1) and [CoL(NO₃)₂]_∞ (2) have been synthesized by anion-directed self-assembly. Both complexes have been characterized by elemental analyses, IR, and X-ray single crystal diffraction. Complexes 1 and 2 exhibit 1D chain structures. In 1, Co(II) ions possess a distorted tetrahedral coordination environment composed of N₂Cl₂ donors from two L ligands and two chloride ions, while the Co(II) ions in 2 reveal a distorted octahedral structure defined by the N₂O₄ donors from two L ligands and two nitrate anions. These results illustrate that the anions play an important role in the self-assembly of metal–organic materials.     

Hydrothermal Synthesis, Crystal Structures and Fluorescent Properties of Two Complexes Based on 1,2-Phenylenedioxydiacetic Acid and Polypyridyl Ligands

Hydrothermal reactions of flexible 1,2-phenylenedioxydiacetic acid (H₂pda) with zinc nitrate or cadmium nitrate in the presence of auxiliary 4,4′-bypyridine (bpy) or 1,3-bis(4-pyridyl)propane (bpp) ligands gave rise to two coordination polymers, {[Cd₂(pda)₂(bpy)(H₂O)₂]·4H₂O} _n (1) and [Zn(pda)(bpp)] _n (2). The polymers were characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction methods. Compound 1 shows 1D ribbon structure and compound 2 displays twofold parallel interpenetrated 2D?→?2D architecture. The different conformations of pda anions in these two compounds are mainly induced by different metal coordination configurations in compound 1 and 2. In addition, the photoluminescence emission of 1 and 2 has been investigated in the solid state at room temperature.     

Facile Routes to Manganese(II) Triflate Complexes

Manganese(II) chloride reacts with trimethylsilyl triflate (TMS(OTf) where OTf = (-)OSO(2)CF(3)) in a 1:1 mixture of acetonitrile and tetrahydrofuran, and after recrystallization affords the linear coordination polymer [Mn(II)(CH(3)CN)(2)(OTf)(2)](n). Each distorted octahedral manganese(II) center in the polymeric chain has trans-acetonitriles and the remaining equatorial coordination positions are occupied by the bridging triflate anions. Dissolving [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) in equal volumes of acetonitrile and pyridine followed by recrystallization with diethyl ether yields trans-[Mn(II)(C(5)H(5)N)(4)(OTf)(2)]. The distorted octahedral geometry of the manganese center features monodentate trans-triflate anions and four equatorial pyridines. Exposure of either [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) or [Mn(II)(C(5)H(5)N)(4)(OTf)(2)] to water readily gives [Mn(II)(H(2)O)(6)](OTf)(2). XRD reveals hydrogen-bonding interactions between the [Mn(II)(H(2)O)(6)](2+) cation and the triflate anion. All three of these species are easily crystallized and provide convenient sources of manganese(II) for further synthetic elaboration.     

Metal(II) Nicotinamide Complexes Containing Succinato,Succinate and Succinic Acid: Synthesis,Crystal Structures,Magnetic, Thermal,Antimicrobial and Fluorescent Properties

Four novel divalent transitional metal succinates (suc) with nicotinamide (nia), {[M(μ-suc)(H₂O)₂(nia)₂]·2H₂O} _n [M = Mn (1), Ni (2)], [Cu(suc)(nia)₂] (3) and [Ni(H₂O)₄(nia)₂](suc)·(H₂suc) (4), have been synthesized and characterized by elemental analyses, IR and TG-DTA. X-ray analyses of 2 and 4 reveal that they crystallize in a triclinic space group P[`1]. P\bar{1}. Complex 2 is a 1-D coordination polymer, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centres through the carboxylate groups. 4 contains the [Ni(H₂O)₄(nia)₂]²⁺ complex cations, uncoordinated suc and H₂suc species, which are connected into a two-dimensional layered structure by the combination of N–H⋯O and OW–H⋯O hydrogen bonds. This is one of the scarce examples encountered in coordination chemistry, which contains uncoordinated suc and H₂suc at the same time. The spectroscopic and structural analysis, luminescent and magnetic properties and the antimicrobial activities of the synthesized complexes were investigated.     

两个铜簇配合物的合成和晶体结构

在溶剂热条件下合成了标题配合物1和2,经X射线衍射测定了两个配合物的晶体结构,配合物1属单斜晶系,空间群为C2/c,晶胞参数a=26.1533(15),b=16.1993(6),c=18.3077(8),β=110.305(6)o,V=7274.3(6)3,Z=8,Mr=905.42,Dc=1.653 g/cm3,F(000)=3520,R1=0.0453,wR2=0.1122配合物2属三斜晶系,空间群为P-1,晶胞参数a=11.0606(13),b=13.7697(16),c=20.7506(17),α=94.809(8),β=90.608(8),γ=108.464(11)o,V=2984.8(6)3,Z=2,Mr=1293.92,Dc=1.440 g/cm3,F(000)=1300,R1=0.0400,wR2=0.0779配合物1具有梯子状四核铜簇结构,配合物2具有菱形双核铜簇结构。     

Antimicrobial, Antifertility and Antiinflammatory Approach to Tetradentate Macrocyclic Complexes of Iron(II) and Manganese(II)

Some antifertility inhibitors of 18 to 24-membered tetraazamacrocyclic complexes of iron(II) and manganese(II) have been synthesised by the template condensation using 1,3-phenylenediamine with malonic acid, succinic acid, glutaric acid and adipic acid. The reaction proceed smoothly to completion. The complexes were characterized by elemental analyses, molecular weight determinations, infrared, electronic, magnetic moment, mössbaur and mass spectral studies. The elemental analyses are consistent with the formation of the complexes [M(N₄L_n)Cl₂] (M = Fe(lI) or Mn(II)). All these complexes are stable and monomeric in nature as indicated by the molecular weight determinations. The spectral studies confirm the octahedral geometry around the central metal atom. The complexes have been screened in vitro against a number of fungi and bacteria to assess their growth inhibiting potential. The testicular sperm density and testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trials and biochemical parameters of reproductive organs have been examined and discussed.     

Synthesis, Crystal Structure, Fluorescence and Thermostability of Ni(II), Zn(II), Cd(II) Complexes with Schiff Base 2-Acetylpyridine-d-tryptophan

Three novel transition metal coordination polymers, [Ni(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (1), [Zn(C₁₈H₁₆N₃O₂)₂·4CH₃OH] _n (2) and [Cd(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (3) (C₁₈H₁₆N₃O₂=2-acetylpyridine-d-tryptophan) were synthesized and characterized by elemental analysis, IR, UV, ¹H NMR and X-ray diffraction single crystal analysis. The analyses of the structures indicate that all three materials crystallize in the tetragonal crystal system, space group P4₁2₁2. They have similar structures; i.e., the Schiff base coordinates in its deprotonated form and behaves as a hexadentate (4N+2O) coordinated ligand to form a distorted octahedron geometry. On the other hand, as a result of the alternate arrangement of chains through N–H···O intermolecular hydrogen bonds interactions, 2-D layers are formed for the three complexes. Furthermore, the luminescent properties and thermal stabilities of the three complexes were investigated.     

4，5-二甲基-2-（2-吡啶基）咪唑的合成、晶体结构及表征

2-取代咪唑是-种用途广泛的精细化学品,不仅可以作为医药中间体、杀虫剂及杀菌剂,还可以作为催化剂、环氧树脂固化剂、交联剂等。2-取代咪唑与过度金属离子形成的配合物在光学材料、磁性材料及超导材料等诸多方面有极好的应用前景。为了制备研究2-取代咪唑配合物,设计合成了4,5-二甲基-2-（2-吡啶基）咪唑,用IR、MS、1H—NMR对其结构进行了确证,并对其晶体结构进行了分析。     

Synthesis of (N,N'-Bis(2-Hydroxyethyl)Ethane-1,2-Diamine)Malonatoplatinum(II) and X-Ray Crystal Structure of the Cis-R,S-Isomer

Hydroxyethyl substituted amineplatinum(II) and (IV) complexes are an interesting class of platinum based antitumour compounds due to their uncoordinated hydroxy groups. These hydroxy groups could play an important role in the mode of action of such complexes with respect to their ability to act as donor or acceptor for hydrogen bonds. Moreover, their chemistry in solution is of interest because it was found that there is the possibility of an intramolecular attack to form ethanolatoamine chelated species which are responsible for very stable monoadducts with 5'-GMP. Furthermore, there is the possibility of derivatisation at the OH site to form a new series of platinum compounds which may be used for a carrier mediated transport to tumour tissues. In this context a series of (N,N'-bis(2-hydroxyethyl)ethane-l,2-diamine)-platinum(II) complexes has been synthesised. During purification of one of the platinum based compounds, it was possible to isolate (SP-4-3)-R,S-(N,N'-bis(2-hydroxyethyl)ethane-l,2-diamine)malonatoplatinum(ll) and to resolve the structure by single crystal structure analysis. Intra- and intermolecular hydrogen bonds have been found which may explain the spontaneous crystallisation of the cis-R,S isomer and the stabilisation of the boat conformation of the malonatoplatinum(II) six-membered ring.     

Nematicidal, Fungicidal and Bactericidal Activities of Manganese (II) Complexes with Heterocyclic Sulphonamide Imines

Some manganese(II) complexes derived from different sulphadrugs and heterocyclic ketones have been prepared. These complexes have been characterized on the basis of elemental analyses, molecular weight determinations, conductivity measurements, infrared, ESR and magnetic measurements. The spectral data suggest that the ligands act in a monobasic, bidentate manner coordinating through nitrogen atom. A high spin tetrahedral geometry around this metal has been proposed on the basis of magnetic and spectral studies. The isolated products are coloured solids, soluble in DMSO, DMF and MeOH. All the complexes are monomeric in nature as indicated by their molecular weight determinations and conductivity measurements in dry DMF show them to be non-electrolytes. All the ligands and their corresponding complexes have been screened for their fungicidal, bactericidal and nematicidal activities.     

Preparation,Crystal Structure and Explosive Properties of Copper(II) Perchlorate Complex with 4‐Amino‐1,2,4‐Triazole and Water

A complex from copper(II) perchlorate with 4‐amino‐1,2,4‐triazole (4‐AT, C₂H₄N₄) was synthesized, and elemental composition, molecular structure, and explosive properties were determined. To this end, elemental and X‐ray analyses were carried out, sensitivity to mechanical and thermal stimuli was measured, mechanism of thermal decomposition was investigated, and kinetic parameters of decomposition were determined. In the next step measurements of heat of combustion and detonation velocity were performed. Detonation parameters were also calculated. It was stated that the complex has slightly distorted square bipyramidal (4+2) coordination. The four basal bonds are formed by nitrogen atoms of four 4‐AT molecules. The coordination of the metal is completed by two axial oxygen atoms, one of the perchlorate ion, and one of the water molecule. With respect to explosive properties, tetrakis(4‐AT)copper(II) perchlorate monohydrate belongs to the group of sensitive secondary explosives.     

1,2—二（五溴苯基）乙烷的合成及阻燃性能研究

合成了新型含溴有机阻燃剂１,２－二（五溴苯基）乙烷,并研究了其阻燃性能。