A common chemical extractant for estimating plant-available zinc in different soil types (peaty,red and alluvial)

Summary Relative efficiency of five chemical extractants for the extraction of available Zn in four different soils and its uptake by rice seedlings was studied in a pot culture experiment. The Zn extracted by dithizone-ammonium acetate showed a significant relationship with plant uptake whereas the values for other extractants except NH₄OAc (pH4.8) did not approach the level of significance. Among the soil properties studied, pH and CaCO₃ correlated negatively and organic matter and CEC positively with Zn uptake by rice plants.Contribution from the Soil Science and Agricultural Chemistry Dept., Banaras Hindu University, Varanasi-221005, India.Lecturer and Research Scholar of the Soil Science and Agricultural Chemistry Department, respectively.Lecturer and Research Scholar of the Soil Science and Agricultural Chemistry Department, respectively.     

Chemical speciation of Zn in acidic soils: suitable soil extractant for assessing Zn availability to maize (Zea mays L.)

Abstract

Chemical fractions of soil Zn namely: water soluble (WS), exchangeable (EX), Pb displaceable (Pb-disp.), acid soluble (AS), Mn oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline Fe oxide occluded (CFeOX), residual (RES) were determined in 20 surface (0–15 cm) samples of acidic soils from the provinces of Uttarakhand and Uttar Pradesh, India. The chemical fractions of soil Zn in acidic soils were found to be in the following descending order of Zn concentration: RES > CFeOX > Pb-Disp. > AFeOX > MnOX > AS > OB > EX > WS. These soil samples were also extracted by: DTPA (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich 3 (pH 2.0), Modified Olsen, 0.01 N CaCl₂, 1 M MgCl ₂ and ion exchange resins. Chemical fractions and the soil extractable content of Zn estimated by different soil extractants were significantly correlated with some general soil properties. Maize (cv. Pragati) plants were grown in these soils for 35 days after emergence and Zn uptake by plants was compared with the amount of Zn extracted by different soil extractants and chemical fractions of Zn. Among chemical fractions of soil Zn, Pb-displaceable and acid soluble chemical fractions of soil Zn showed a significant and positive correlation with Zn uptake by maize. Path coefficient analysis also revealed that the acid soluble Zn fraction showed the highest positive and direct effect on Zn uptake (P=0.960). Among different multinutrient soil extractants evaluated for their suitability to assess Zn availability in acidic soils, DTPA (pH=5.3) was most suitable soil extractant, as the quantity of soil Zn extracted by this extractant showed a significant and positive correlation with the dry matter yield, Zn concentration and uptake by maize plants.     

Dilute hydrochloric acid as an extractant for available zinc,copper and boron in rice soils

Summary Because zinc deficiency is a widespread disorder of wetland rice and copper deficiency may occur with it, 0.05M HCl was compared with 0.1M HCl, EDTA and DTPA as an extractant for available zinc and copper. It was also compared with the reflux method for boron assay.Thirty-three wetland rice soils were analyzed for zinc and copper by the four methods. Rice was grown on the flooded soils, scored visually for zinc deficiency, and the plants analyzed for zinc and copper content. In the boron study, 53 soils were extracted by the reflux method and the 0.05M HCl procedure. Rice was grown on the flooded soils, scored visually for boron toxicity, and the plants analyzed for boron content.Fourteen of the 16 soils on which rice showed zinc deficiency gave <1.0 mg/kg Zn by the 0.05M HCl method but values far in excess of the critical limits by the other methods. The r values for available and plant zinc were: 0.05M HCl (0.88^**); 0.1M HCl (0.55^**); EDTA (0.43^**); and DTPA (0.31^ns).Twelve of the zinc-deficient soils gave<0.1 mg/kg Cu by the 0.05M HCl method but values exceeding the critical limits by the EDTA and DTPA methods. The r values for available and plant copper were: 0.05M HCl (0.74^**), 0.1M HCl (0.64^**), EDTA (0.28^ns), and DTPA (0.20^ns).The critical limit of 1.0 mg/kg by the 0.05M HCl extraction was confirmed for zinc deficiency and a tentative value of 0.1 mg/kg for copper deficiency proposed.The 0.05M HCl method separated boron-toxic soils from non-toxic soils and gave a better correlation (r=0.91^**) between available and plant boron than the reflux extraction (r=0.84^**). The toxic limit by the 0.05M HCl method was provisionally set at 4 mg/kg.     

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO₄)₂·6H₂O in methanol in 3:1 M ratio at room temperature yields light green [CuL₃](ClO₄)₂·H₂O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL₃](ClO₄)₂·0.5CH₃CN has been determined which shows Jahn-Teller distortion in the CuN₆ core present in the cation [CuL₃]²⁺. Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g_|| = 2.262 (A_|| = 169 × 10⁻⁴ cm⁻¹) and g_⊥ = 2.069. The Cu(II/I) potential in 1 in CH₂Cl₂ at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL₃]⁺ in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL₃]⁺ are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 Å while the ideal Cu(I)-N bond length in a symmetric Cu(I)N₆ moiety is estimated as 2.25 Å. Reaction of L with Cu(CH₃CN)₄ClO₄ in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL₂]ClO₄ (2). Its ¹H NMR spectrum indicates that the metal in [CuL₂]⁺ is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH₂Cl₂ at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From ¹H NMR titration, the free energy of binding of L to [CuL₂]⁺ to produce [CuL₃]⁺ in CD₂Cl₂ at 298 K is estimated as −11.7 (±0.2) kJ mol⁻¹.     

Evaluation of A resin-bag procedure for determining plant-available P in organic,volcanic soils

Summary An anion-exchange procedure in which soil samples are shaken with polyester-netting bags containing a strongly basic resin has proved to be the only method too date which yields reproducible plantavailable P estimates on Marion Island soils. Available P determinations using chemical extractants are hampered by high iron, aluminium and organic matter contents in these soils. Resin-extractable soil P levels correlated strongly with plant leaf P contents at a wide variety of sites.     

Phosphatase production and activity in copper (II) accumulating Rhizopus delemar

The fungus Rhizopus delemar produced extracellular and cellular acid phosphatase during the growth in starch-supplemented medium in the presence or absence of copper ions. The levels of both AP-ase activities were maximal at the end of exponential growth phase and were dependent on copper concentrations. Copper ions in the medium provoked slight decrease of specific AP-ase activities and significant increase of the values of secreted enzyme per gram dry cells. On the other hand, an increase of copper ions in the reaction mixture leads to considerable increase of the values of cellular enzyme activity. Total uptake of copper (II) was highest at the highest copper (II) concentration, when resting cells were used. Between 27 and 30% copper (II) was not removed by acid washing, suggested that this copper was bound intracellularly by mycelium. Determination of the Michaelis constant for the cellular AP-ase gave value of 0.325 mM. The pH optimum of the enzyme was determined to be in the range of 3.5–4.5 using p-nitrophenyl phosphate (pNPP) as a substrate. The data obtained indicated a possible participation of AP-ases in the processes of heavy metal resistance and heavy metal uptake of this fungus.     

Copper in plant species in a copper gradient in Catalonia (North East Spain) and their potential for phytoremediation

The accumulation of Cu in roots and shoots of 32 plant species growing on soils with a wide range of Cu concentrations (30–18 500 g g^–1 total soil Cu) located in Collserola Mountain (Barcelona, Spain) was analysed. High Cu availability decreased the species diversity in the Hyparrhenietum hirto-pubescentis, the natural plant association at the study sites. Shoot and root Cu concentrations in relation to extractable soil Cu concentrations were used for the evaluation of the Cu resistance strategy in the different species. Saturation of Cu accumulation in roots was observed in most species. Hyparrhenia hirta was the most efficient shoot excluder, while the linear increase of shoot Cu with the Cu soil concentration exhibited the highest slope in Hirschfeldia incana. Most species accumulated more Cu in roots than in shoots. High shoot/root Cu ratios were only found in the highly Cu-resistant Hirschfeldia incana, in the resistant or moderately resistant Spartium junceum and Reseda sp. (R. lutea and R. phyteuma), and in the much less resistant Ononis natrix. Only two species, Hirschfeldia incana and Sedum sediforme were able to support the extreme Cu-toxicity conditions on soils with 5000–16 800 g g^–1 extractable Cu. Among the grass species tested Hyparrhenia hirta was the most Cu-resistant species (up to 1950 g g^–1 extractable soil Cu). The potential usefulness of these pseudometallophytes for phytoremediation of Cu-contaminated soils is discussed.     

Synthesis, crystal structure, spectroscopic and magnetic properties of copper(II) complexes with 2-(2-pyridyl)imino-N-(2-thiazolin-2-yl)thiazolidine (PyTT)

The copper(II) complexes [Cu(PyTT)₂(H₂O)](NO₃)₂ (A) and [CuCl₂(μ-PyTT)₂CuCl(H₂O)]Cl · 3H₂O (B) were synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, UV-Vis-NIR diffuse reflectance and magnetic susceptibility measurements. In the mononuclear compound A the copper ion is in a distorted square pyramidal geometry, with the equatorial plane formed by two thiazoline nitrogen atoms, one imino nitrogen atom and one water molecule, whereas the axial site is occupied by one imino nitrogen atom. The compound B is dinuclear and both Cu(II) centres present environments that can be described as slightly distorted square pyramidal geometries. The observed molar magnetic susceptibility for A (μ=2.13 BM) allows to exclude metal-metal interactions, supporting a monomeric structural formulation for this compound. In compound B, magnetic susceptibility measurements in the temperature range 6.2-288 K show an intradimer antiferromagnetic interaction (J=−11.8 cm⁻¹).     

Influence of sulphur on the yield and concentration of copper,manganese, iron and molybdenum in berseem (Trifolium alexandrinum) grown on two different soils

A screen-house experiment with 0, 25, 50 and 75 ppm S was conducted to study the effect of S on the yield and, Mn, Cu, Fe and Mo concentrations of berseem (Trifolium alexandrinum) at three stages of growth in a normal and reclaimed soil. Higher levels of S decreased the yield in both the soils. Yield in normal soil was much higher than in reclaimed soil. Application of S increased Cu, Mn, and Fe concentrations in all cuts in both soils. Molybdenum concentration was lowered following S application in both the soils in all the cuts. Molybdenum content increased with the stage of plant growth.     

Radical production by hydrogen peroxide/bicarbonate and copper uptake in mammalian cells: modulation by Cu(II) complexes

The presence of the bicarbonate/carbon dioxide pair is known to accelerate the transition metal ion-catalysed oxidation of various biotargets. It has been shown that stable Cu(II) complexes formed with imine ligands that allow redox cycling between Cu(I) and Cu(II) display diverse apoptotic effects on cell cultures. It is also reported that Cu(II)-tetraglycine can form a stable Cu(III) complex. In the present study, radical generation from H₂O₂ and H₂O₂/HCO₃⁻ in the presence of these two different classes of Cu(II) complexes was evaluated by monitoring the oxidation of dihydrorhodamine 123 and NADH and by the quantitative determination of thiobarbituric acid reactive substances (TBARs method). Cu(II)-imine complexes produced low levels of reactive species whereas Cu(II)-Gly-derived complexes, as well as the free Cu(II) ion, produced oxygen-derived radicals in significantly larger amounts. The effects of these two classes of complexes on mammalian tumour cell viability were equally distinct, in that Cu(II)-imine complexes caused apoptosis, entered in cell and remained almost unaffected in high levels whilst, at the same concentrations, Cu(II)-Gly peptide complexes and Cu(II) sulphate stimulated cell proliferation, with the cell managing copper efficiently. Taken together, these results highlight the different biological effects of Cu(II) complexes, some of which have been recently studied as anti-tumour drugs and radical system generators, and also update the effects of reactive oxygen species generation on cell cycle control.     

Investigations of different carbohydrate anomers in copper(II) complexes with D-glucose, D-fructose, and D-galactose by Raman and EPR spectroscopy

With the aim of verifying different carbohydrate anomers coordinated to copper(II) ions, some copper(II) complexes with D-glucose (Glc), D-fructose (Fru), and D-galactose (Gal) were prepared and investigated by spectroscopic techniques. Their compositions were verified by elemental, ICP-AES and thermal analyses, in addition to conductivity measurements. The compounds isolated were consistent with the formula Na2[Cu2(carbohydrate)3].8H2O and Na[Cu2(carbohydrate)3].6H2O for the aldoses Glc and Gal, respectively, and Na2[Cu3(carbohydrate)4].8H2O in the case of the ketose, Fru. EPR spectra of these solids showed a rhombic environment around the metal center and suggested the presence of different anomers of the carbohydrates in each case. By Raman spectroscopy, it was possible to verify the predominance of the beta anomer of d-glucose in the corresponding copper complex, while in the free ligand the alpha anomer is predominant. In the case of the analogous complex with d-galactose, the spectrum of the complex shows bands of both anomers (alpha and beta) in approximately the same relative intensities as those observed in the isolated free ligand spectrum. On the other hand, for the complex with d-fructose a mixture of both furanose (five-membered ring) and pyranose (six-membered ring) structures was detected with prevalence of the furanose structure. Based on variations in the relative intensities of characteristic Raman bands, the binding site for copper in the fructose ligand was identified as most likely the 1-CH2OH and the anomeric 1-OH, while in beta-D-glucose it is presumably the anomeric 1-OH and the O-5 atom. These results indicated that EPR and Raman spectroscopy are suitable supporting techniques for the characterization of carbohydrate anomers coordinated to paramagnetic ions.     

铜陵狮子山铜尾矿场植被调查与土壤酶活性研究

对安徽铜陵狮子山铜尾矿废弃地进行植被调查,发现当地现今自然定居植物共42种,隶属于13科36属,主要包括禾本科10种,豆科6种,菊科6种,十字花科5种。全部植物中,1～2年生草本植物21种,多年生草本植物20种,形成6种相对稳定的演替群落和单种斑块。尾矿场土壤的5种土壤酶（蔗糖酶、过氧化氢酶、脲酶、磷酸酶、多。酚氧化酶）活性的高低与植被丰富度和群落分布有一定的对应关系。结合本实验室前期工作,证实某些植物如白茅、狗牙根、白车轴草等已在尾矿场上成功定居且综合优势比较高,可作为铜尾矿治理中优先选用的物种。     

Distribution of fungicide-derived copper in soils,litter and vegetation of different aged stands of coffee (Coffea arabica L.) in Kenya

Summary Samples of soils, litter and vegetation, collected from 24, 14 and 4 years old stands of coffee (Coffea arabica L.), which had been routinely treated with copper fungicides, were analysed for copper content. Total soil copper content was found to be a function of (a) stand age and (b) soil depth. Highest levels were encountered in the 0–20 cm zone of the 24 year old stand; soil collected beneath these bushes showed significant contamination to a depth of 80 cm. Soils from the younger stands showed proportionally less copper contamination. Copper levels in litter samples showed increases relative to stand age; litter from the oldest stand was heavily contaminated and leaf litter showed a higher copper content than that of the woody fraction. Tissues from coffee bushes could be divided into 2 groups on the basis of their copper content; those tissues which demonstrated a progressive age-dependent increase (bark, lateral stems and fine roots) and those tissues where copper levels did not reflect the cumulative exposure of the plant to this element (wood, different age classes of foliage).     

Orally active antioxidative copper(II) aspirinate: synthesis, structure characterization, superoxide scavenging activity, and in vitro and in vivo antioxidative evaluations

Ever since it was proposed that reactive oxygen species (ROS) are involved in the pathogeneses of various diseases, superoxide dismutase (SOD)-mimetic complexes have been intensively studied. We prepared copper(II) aspirinate [Cu₂(asp)₄] from Cu(II) and aspirin, which has been in use for many years as an antipyretic, an analgesic, and an anti-inflammatory agent. However, Cu₂(asp)₄ has been found to have additional activities, including anti-inflammatory, antiulcer, anti-ischemic/reperfusion agent, anticancer, antimutagenic, and antimicrobial activities. The activity of copper salicylate [Cu(sal)₂] was also compared with that of Cu₂(asp)₄. The structure of the Cu₂(asp)₄ was determined using X-ray structure analysis. Its SOD-mimetic activity was determined using cytochrome c, electron spin resonance (ESR) spectroscopy, and ESR spin trap methods. The activity of Cu₂(asp)₄ was slightly greater than CuSO₄ and copper acetate [Cu(ace)₂] and slightly less than that of Cu(sal)₂. The in vitro antioxidant activity, evaluated in human epithelial or transformed neoplastic keratinocyte cells, HaCaT, and normal dermal fibroblasts in terms of cell survival following ultraviolet B (UVB) irradiation, was significantly increased in the presence of Cu₂(asp)₄, Cu(sal)₂, and CuSO₄. Further, ROS generation following UVA irradiation in the skin of hairless mice following oral treatment with Cu₂(asp)₄ for three consecutive days was significantly suppressed compared to the vehicle- or Cu(ace)₂-treated mice. On the basis of these results, Cu₂(asp)₄ was observed to be a potent antioxidative compound possessing antioxidative activity in biological systems. In conclusion, Cu₂(asp)₄ is a potent antioxidative agent that may be useful for future treatment of diseases resulting from ROS.     

我国红壤区土壤钼、硼、硒元素特征及其对牧草生长影响研究进展

实行肥料科学配施与红壤培肥管理是山区草业发展的重要技术环节．我国南方红壤区土壤普遍存在着硼、钼、硒元素缺乏现象,合理施用钼、硼、硒微量元素肥料对豆科与禾本科牧草的植株生长以及提高产草量和种子产量有明显的促进作用．文中概述了我国红壤区土壤中钼、硼、硒元素的存在形态、化学特征、内在变化、可给性及含量状况,探讨了施用3种微量元素肥料对牧草生长过程有效养分吸收与累积的影响及其相应生理功能,综述了牧草植物缺乏钼、硼、硒元素的特征症状、诊断方法及其矫治措施．     

Assessment of the feasibility of using CCA (copper,chromium and arsenic)-treated and boric acid-treated sawdust as soil amendments

A pot trial was conducted to determine the effects, on plant growth and element uptake, of soil amendment with Cu- Cr- and As-(CCA) treated, or boric-treated sawdust. Three indicator plants (beetroot, white clover, lettuce) were chosen and the trial was carried out at both soil pH 5 and pH 7. Comparisons were made with an untreated sawdust amendment and with a non-sawdust control. Amendment with 10% treated-sawdust (v/v) increased soil concentrations of Cu, Cr, As and B, by 45, 136, 63 and 32 mg kg^-1, respectively. Much of the Cu and B was extractable using standard soil extractants, but extract concentrations of Cr and As were below detection limits. Seeds germinated in all pots, but the boric treatment subsequently proved unsatisfactory as a growth medium for all plants except beetroot grown at pH 7. The CCA treatment had no negative effect on any of the plants at either pH, but yield depression occurred with untreated sawdust. This was attributed to nutrient immobilization by the decomposing untreated sawdust. Plant roots, especially beetroot fibrous roots, in the CCA treatment, concentrated Cu, Cr and As to high levels. Uptake of these elements was generally higher at pH 5 than at pH 7. However, the above-ground parts of the plants, and the beetroot bulbs, i.e. the normal edible parts, had very much lower concentrations. Although Cu was concentrated to some extent in beetroot and clover, the concentrations were below animal toxicity levels, especially at the higher soil pH. B, in contrast, was concentrated in the above-ground portions of the plants, in preference to the roots. These treatments had no important effects on the uptake of major and minor nutrient elements by the plants. Clover nitrogen-fixation was not adversely affected by the CCA treatment, but was totally absent in the boric treatment. These rerults are discussed, and the need to conduct tests on a wider range of edible plants before concluding that amendment with CCA-treated sawdust may be acceptable, is stressed.     

Comparison of different osmolalities and egg-yolk composition in processing media for the cryopreservation of red wolf (Canis rufus) sperm

Successful cryopreservation of sperm and the maintenance of a sperm-based genome resource bank have been identified as priorities for the recovery of the endangered red wolf (Canis rufus). The objectives were to improve sperm processing and to determine the relative timing of damage to red wolf sperm during freezing and thawing. Fresh ejaculates (n=37) from adult red wolves (n=15, aged 2-13 y) were collected via electroejaculation and subjected to cooling, freezing and thawing in four TRIS-egg-yolk extender treatments varying in osmolality ( approximately 305 mOsm versus approximately 350 mOsm) and egg-yolk composition (0.8 microm-filtered versus unfiltered). Ejaculates were evaluated for sperm percentage motility, forward progressive motion, and morphological characteristics immediately upon collection and following extension, cooling (prior to freezing) and thawing. Although no single treatment consistently produced superior results, sperm suspended in approximately 305 mOsm extenders exhibited slight losses in motility post-thawing (13 and 7%). Also, sperm suspended in approximately 350 mOsm extenders tended to have slower rates of decline in motility in vitro post-thawing than those stored in approximately 305 mOsm extenders (P=0.55). Finally, extenders incorporating unfiltered egg yolk exhibited a slightly larger ratio of absent to partial acrosomes than did sperm frozen in extenders prepared with clarified egg yolk. For approximately 350 mOsm extenders, most motility loss occurred during the cooling rather than freezing and thawing. In conclusion, these data contribute to knowledge regarding cryopreservation of red wolf sperm.     

Lewis-base copper(I) formates: Synthesis, reaction chemistry, structural characterization and their use as spin-coating precursors for copper deposition

Consecutive synthesis methodologies for the preparation of a series of copper(I) formates [L_mCuO₂CH] (L = ⁿBu₃P: 4a, m = 1; 4b, m = 2; 5, L = [Ti](CCSiMe₃)₂, m = 1, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) and [L_mCuO₂CH·HO₂CR] (L = ⁿBu₃P: 7a, m = 1, R = H; 7b, m = 2, R = H; 7c, m = 2, R = Me; 7d, m = 2, R = CF₃; 7e, m = 2, R = Ph. L = (^cC₆H₁₁)₃P, R = H: 8a, m = 2; 8b, m = 3. L = (CF₃CH₂O)₃P, R = H: 9a, m = 2; 9b, m = 3. L = (CH₃CH₂O)₃P, R = H: 10a, m = 2; 10b, m = 3. L = [Ti](CCSiMe₃)₂; m = 1: 11a, R = H; 11b, R = Ph) is reported using [CuO₂CH] (1) and L (2a, L = ⁿBu₃P; 2b, L (^cC₆H₁₁)₃P; 2c, L = (CF₃CH₂O)₃P; 2d, L = (CH₃CH₂O)₃P; 3, L = [Ti](CCSiMe₃)₂) as key starting materials. Addition of formic acid (6a) or carboxylic acid HO₂CR (6b, R = Me; 6c, R = CF₃; 6d, R = Ph) to the afore itemized copper(I) formates 4 and 5 gave metal-organic or organometallic 7-11. The molecular structures of 8a and 11a in the solid state are reported showing a threefold coordinated copper(I) ion, setup by either two coordinatively-bonded phosphorus atoms and one formate oxygen atom (8a) or two π-bonded alkyne ligands and one oxygen atom (11a). A formic acid molecule is additionally hydrogen-bonded to the CuO₂CH moiety. The use of 7b as suitable precursor for the deposition of copper onto TiN-coated oxidized silicon wafers by the spin-coating process below 300 °C is described. Complex 7b offers an appropriate transformation behavior into metal phase by an elimination-decarboxylation mechanism. The morphology of the copper films strongly depends on the annealing conditions. A closed grain network densified by a post-treatment is obtained (8 °C min⁻¹, N₂/H₂ carrier gas). Hydrogen post-anneal to 420 °C after film deposition gave a copper film showing resistivities from 2.5 to 3.7 μΩ cm. This precursor was also used for gap-filling processes.     

The use of trans-4-cotininecarboxylate to construct a polymeric copper(II) azido complex: Hydro(solvo)thermal synthesis, structure and magnetic properties

A new pyridyl-carboxylate ligand, the anion of trans-4-cotininecarboxylic acid, HL, 1, has been used to prepare a new polymeric copper(II) complex, [CuLN₃]_2n, 2, based on a [CuLN₃]₂ dimeric building block. The single crystal structures of both 1 and 2 have been determined and 1 has been found to be in its zwitterionic configuration. The structure of 2 is a one-dimensional tape-like polymeric structure based on an end-on azido-bridged binuclear [Cu₂N₃]₂ backbone moiety. Magnetic studies reveal that 2 is close to paramagnetic from 2 to 300 K with a Curie constant of 1.094 emu K/mol, a Weiss temperature of 0.73 K and a corresponding μ_eff of 2.09 μ_B. A fit of χ_MT for 2 with S₁ = S₂ = ½, yields g = 2.441(6), J = −0.49(3) cm⁻¹, zJ = −0.38(2) cm⁻¹ and N(α) = 0.00053(12) emu/mol, a fit that indicates the presence of both very weak intramolecular intrachain antiferromagnetic exchange coupling within the one-dimensional tape-like chains and very weak interchain antiferromagnetic exchange coupling between these chains.