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Low-dimensional compounds containing cyano groups. IV. Bis(2,2'-bipyridine-kappa(2)N,N1)(dicyanamido-kappaN')copper(II) perchlorate and mu-dicyanamido-kappa(2)N1:N5-bis[bis(2,2'-bipyridine-kappa(2)N,N')copper(II)] triperchlorate ethanol hemisolvate, complexes with unusual dicyanamide coordination.

From reaction mixtures containing the same reagents, the two novel title complexes, with unusual coordination modes of the dicyanamide (dca) ligand, have been prepared. The first compound, [Cu(C(2)N(3))(C(10)H(8)N(2))(2)]ClO(4), represents a relatively rare class of compounds, with the dca ligand coordinated in a monodentate manner. Its structure is formed by the [Cu(bpy)(2)N(CN)(2)](+) complex cation (bpy is 2,2'-bipyridine) and a ClO(4)(-) anion, which does not enter the inner coordination sphere. The Cu centre is five-coordinate within a strongly distorted trigonal bipyramid to two bpy molecules and one dca ligand, which is coordinated through one nitrile N atom in the equatorial plane. The second compound, [Cu(2)(C(2)N(3))(C(10)H(8)N(2))(4)](ClO(4))(3).0.5C(2)H(6)O, contains dca coordinated in the more common bidentate manner, but instead of a chain structure, a unique binuclear complex is formed. The asymmetric unit consists of the [Cu(bpy)(2)N(CN)(2)(bpy)(2)Cu](3+) binuclear complex cation, the charge of which is neutralized by three uncoordinated perchlorate anions, and a half-molecule of ethanol. Both Cu centres in the cation are five-coordinate, adopting a slightly distorted trigonal-bipyramidal environment.

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Bis(dicyanamido)(diethylenetriamine-kappa(3)N)copper(II) and (dicyanamido)(triethylenetetramine-kappa(4)N)copper(II) dicyanamide.

Two new complexes, [Cu(C(2)N(3))(2)(dien)] (dien is diethylenetriamine, C(4)H(13)N(3)), (I), and [Cu(C(2)N(3))(trien)](C(2)N(3)) (trien is triethylenetetramine, C(6)H(18)N(4)), (II), have been characterized by single-crystal X-ray diffraction. Both complexes display a distorted tetragonal-pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethylenetriamine N atoms [Cu-N = 2.000 (2), 2.004 (2) and 2.025 (2) A] and one terminal N atom [Cu-N = 1.974 (2) A] from one monodentate dicyanamide group, and in the apical position by one terminal N atom [Cu-N = 2.280 (2) A] from the other monodentate dicyanamide group. In (II), the Cu atom is surrounded by four triethylenetetramine N atoms [Cu-N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) A in the basal plane] and a terminal N atom [Cu-N = 2.130 (2) A in the apical site] from one monodentate dicyanamide group. The other dicyanamide anion is not directly coordinated to the metal atom. In both (I) and (II), hydrogen-bond interactions between the uncoordinated terminal N atoms of two dicyanamide ions and the amine H atoms lead to the formation of three-dimensional networks.

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Di-mu-cyanato-bis[(cyanato-kappaN)(tetramethylethylenediamine-kappa2N,N')copper(II)] and catena-poly[[mu3-cyanato-kappa3O:N:N-bis[(cyanato-kappaN)(1,3-diaminopropane-kappa2N,N')copper(II)]]-mu3-cyanato-kappa3N:N:O].

The two title Cu(II) complexes, [Cu(2)(NCO)(4)(tmeda)(2)] (tmeda is tetramethylethylenediamine, C(6)H(16)N(2)), (I), and [Cu(NCO)(2)(pn)](n) (pn is 1,3-diaminopropane, C(3)H(10)N(2)), (II), have been synthesized and their crystal structures determined. In (I), which lies about an inversion centre, each Cu centre possesses a distorted tetragonal-pyramidal geometry with four basal N atoms from two cyanate anions [Cu-N = 1.945 (2) and 1.948 (3) A] and one tmeda molecule [Cu-N = 2.053 (2) and 2.071 (2) A], and one axial O atom [Cu-O = 2.737 (3) A] from another cyanate anion. The two neighbouring Cu atoms in (I) are joined by a pair of cyanates in an end-to-end fashion, forming a dimer. In (II), each Cu centre adopts a distorted square-bipyramidal geometry, with four equatorial N atoms from two cyanates [Cu-N = 1.988 (2) and 2.007 (3) A] and a pn ligand [Cu-N = 1.996 (3) and 2.011 (3) A], and one apical N atom [Cu-N = 2.437 (3) A] and an apical O atom [Cu-O = 2.900 (3) A] from two cyanates. In contrast with (I), the two neighbouring Cu atoms in (II) are bridged by two cyanates in an end-on fashion, to form a centrosymmetric dimeric unit. These units are further crosslinked, forming a two-dimensional network structure, via weak interactions between the bridging cyanate O atom and a neighbouring Cu atom, plus interactions of the amine H atoms with the cyanate O atoms and the terminal cyanate N atom.

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Bis[(R)-3,5-dichloro-N-(1-phenylethyl)salicylideneaminato-kappa2N,O]copper(II) and bis[(R)-3-ethoxy-N-(1-phenylethyl)salicylideneaminato-kappa2N,O]copper(II).

The title compounds, [Cu(C(15)H(12)Cl(2)NO)(2)], (I), and [Cu(C(17)H(18)NO(2))(2)], (II), both adopt a compressed tetrahedral trans-[CuN(2)O(2)] coordination geometry, the molecules having an umbrella conformation overall. These complexes differ from one another with respect to the 1-phenylethylamine moieties, the direction of the benzene rings being either inside [in (I)] or inside and outside [in (II)] of the molecules. The crystals of (I) and (II) have Delta(R,R) and Lambda(R,R) absolute configurations, respectively.

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A mixed-valence CuII/CuI anion-cation complex: bis[mu-5-sulfosalicylato(3-)]bis[(di-2-pyridylamine)copper(II)] bis[bis(di-2-pyridylamine)copper(I)] dihydrate.

The title compound, [CuII(2)(C7H3O6S)2(C10H9N3)2][CuI(C10H9N3)2]2.2H2O, consists of anionic CuII moieties, cationic CuI species and uncoordinated water molecules. The anionic dimeric unit consists of one crystallographically independent fully deprotonated 5-sulfosalicylate (2-oxido-5-sulfonatobenzoate) anion, a di-2-pyridylamine group and a CuII atom. Each CuII atom is five-coordinate within a square-pyramidal geometry. The anion lies on a special position of -1 site symmetry. In the cationic monomer, the CuI atom adopts tetrahedral geometry. The cations and anions are connected by O-H...O and N-H...O hydrogen bonds.

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Bis{1-n-hexyl-3-methyl-4-[1-(phenylimino)propyl]-1H-pyrazol-5-olato}copper(II): a new copper(II) complex with a chelating alkylpyrazolone-based enamine.

The title compound, [Cu(C19H26N3O)2], is the first reported complex of the alkylpyrazolone-derived ligand 1-n-hexyl-3-methyl-4-[1-(phenylimino)propyl]-1H-pyrazol-5(4H)-one. The most notable feature is the imine-enol character presented by the ligand due to coordination, in spite of its enamine-ketone structure in the free state. The ligand chelates through N and O atoms, resulting in a square-planar coordination around the CuII atom, which lies on an inversion centre.

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Bis[bis(methoxycarbimido)amine-kappa2N,N']bis(perchlorato-kappaO)copper(II) bis[bis(methoxycarbimido)amine-kappa2N,N']bis(methanol-kappaO)copper(II) bis(perchlorate) methanol disolvate.

The title compound, [Cu(ClO4)2(C4H9N3O2)2][Cu(C4H9N3O2)2(CH4O)2](ClO4)2.2CH3OH, comprises two independent Cu(II) species lying on different inversion sites. In the Cu complexes, a distorted octahedral geometry arises (from basic square-planar N4 coordination) from the weak coordination of two perchlorate ions (as Cu-O) in one species and two methanol molecules in the other (also as Cu-O). Interactions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive intermolecular hydrogen-bonding network.

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Structures of chloro(glycinato)(1,10-phenanthroline)copper(II) monohydrate (I) and aqua(1,10-phenanthroline)(L-phenylalaninato)copper(II) nitrate monohydrate (II).

(I) [CuCl(C2H4NO2)(C12H8N2)].H2O, Mr = 371.28, orthorhombic, P2(1)2(1)2(1), a = 6.795 (3), b = 12.496 (4), c = 17.273 (5) A, V = 1467 (1) A3, Dx = 1.680 Mg m-3, Z = 4, F(000) = 756, lambda(Mo K alpha) = 0.71069 A, mu(Mo K alpha) = 1.742mm-1. Room temperature. Final R = 0.046 for 1302 unique observed reflections. (II) [Cu(C9H10NO2)(C12H8N2)(H2O)]NO3.-H2O, Mr = 505.98, monoclinic, P2(1), a = 5.782 (2), b = 20.700 (6), c = 9.355 (3) A, beta = 97.58 (2)degrees, V = 1110 (1) A3, Dx = 1.514 Mg m-3, Z = 2, F(000) = 522, lambda(Mo K alpha) = 0.71069 A, mu(Mo K alpha) = 1.076 mm-1. Room temperature. Final R = 0.069 for 1929 unique observed reflections. The Cu ion displays distorted square-pyramidal coordination in both (I) and (II), with the chlorine atom (I) or the water molecule (II) in the apical position. The Cu-N bond lengths alter according to the electronegative character of the trans atom. The conformations of the five-membered chelate rings appear to depend on H bonding and van der Waals interactions.

Hydrogen Bonding↗

Structure of a thiolate-bridged polymeric copper(I) compound, catena-(2,9-dimethyl-1,10-phenanthroline)-mu-(thiophenolato)-copper(I).

[Cu(C6H5S)(C14H12N2)], Mr = 380.97, monoclinic, P2(1), a = 10.047 (1), b = 15.797 (2), c = 10.581 (1) A, beta = 90.78 (1) degrees, V = 1679.2 A3, Z = 4, Dm (CCl4/C5H12) = 1.50, D chi = 1.51 g cm-3, lambda(Mo K alpha) = 0.7107 A, mu = 14.2 cm-1, F(000) = 784, T = 293 (1) K, R = 0.026, wR = 0.026 for 2709 observed reflections. The title compound, [Cu(Me2-phen)(C6H5S)]n, exists as chains of [Cu(Me1phen)]+ units linked by thiophenolate S atoms. Large bridging angles at thiolate S atoms [Cu(1)--S--Cu(2)(av.) = 134 (1) degrees] preclude any Cu--Cu bonding [Cu ... Cu = 4.246 (1), 4.284 (1) A] along the chain. The CuI atoms exhibit highly distorted tetrahedral coordination, with the largest deviations from tetrahedral stereochemistry involving the N--Cu--N and S--Cu--S angles [N--Cu--N(av.) = 78.0(2), S--Cu--S(av.) = 126 (3) degrees].

Chemical Phenomena↗

Copper(I) Complexes with a Proximal Aromatic Ring: Novel Copper-Indole Bonding.

A unique bonding of indole to a metal ion has been established. Two new tridentate N ligands with a pendent indole ring gave Cu(I) complexes 1 and 2, the latter of which exhibits the new form of bonding between the Cu(I) ion in a distorted tetrahedral geometry and the indole C(2)-C(3) moiety. The bond is dependent upon the length of the side chain and therefore the accessibility of the ring to the metal center.

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Distribution and fractionation of copper in soils of apple orchards.

BACKGROUND: Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. MATERIALS AND METHODS: Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L(-1) HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L(-1) HCI and then copper and other elements were measured with ICP-MS. RESULTS AND DISCUSSION: Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg(-1). The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0-10 cm layer, all the copper fractions in the 0-5 cm layer, and some fractions in the deeper layers. CONCLUSION: Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66 mg kg(-1) Cu). RECOMMENDATION AND PERSPECTIVE: Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.

Agriculture↗