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1.
The crystal structures of copper(II) nitrate complexes with 2-(2-hydroxybenzylideneamino)-2-hydroxymethylpropane-1,3-diol (HL) and 2-hydroxymethyl-2-(2-hydroxy-5-nitrobenzylideneamino)propane-1,3-diol (HL1) were determined. The resulting complexes were formulated as [Cu3OL3(H2O2]NO3 · 3H2O (I) and [Cu(H2O)L1]NO3 (II). The crystals of I are monoclinic, a = 17.809(4) Å, b = 30.549(6) Å, c = 18.962(4) Å, β = 115.36(3)°, space group Cc, Z = 8, R = 0.0482. Complex I is composed of two independent three-dimensional µ3-oxo complexes; the coordination polyhedron of the copper atoms in both compounds is an elongated tetragonal bipyramid. The coordination polyhedron of the third Cu atom is a tetragonal pyramid. The bases of the pyramids are composed of the oxygen atoms of the phenol and alcohol OH groups, the imine N atom of ligand L, and µ 3-oxo atoms. The phenol and water O atoms serve as the apices in both the tetragonal bipyramids. The crystals of II are triclinic, a = 6.062(1) Å, b = 7.701(2) Å, c = 16.162(3) Å, α = 88.15(3)°, β = 84.94(3)°, γ = 78.13(3)°, space group P1¯, Z = 2, R = 0.0272. Complex II is composed of polymer chains formed by coordination bonds between the copper atom and two O atoms of the amino alcohol in the azomethine of the neighboring complex connected to the initial one by translation along the x axis. These chains are linked through hydrogen bonds involving the oxygen atoms of the NO2 groups. The benzene rings of the azomethine ligands of the adjoining complexes from different chains are antiparallel to each other. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Its equatorial plane is formed by the phenol O atom, one of the alcohol O atoms, the N atom of ligand L1, and the O atom of the amino alcohol in the neighboring complex. The apices are the O atom of the water molecule and the O atom of the amino alcohol in the neighboring azomethine molecule. In complexes I and II, the outer-sphere nitrato group mainly serves to unite trimers and polymers in the crystal by means of hydrogen bonds.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 8, 2005, pp. 621–629.Original Russian Text Copyright © 2005 by Chumakov, Tsapkov, Simonov, Antosyak, Bocelli, Perrin, Starikova, Samus, Gulea.  相似文献   

2.
Summary Some copper(II) complexes of the type Cu(HL)X·nH2O (where H2L = benzoin thiosemicarbazone; X=NO3; Cl, Br, SCN, ClO4 or 1/2SO4; n=O–2) have been prepared and characterized. All complexes have tetragonally distorted octahedral stereochemistry except the sulphatocomplex which is square pyramidal. The i.r. spectra reveal that HL acts as a monobasic tridentate ligand coordinating through the azine group nitrogen atom, thiocarbonyl sulphur atom and hydroxylic oxygen atom while NO3, Cl, Br and ClO4 act as terminal monodentate ligands and SCN and SO4 act as bidentate bridging ligands. The polycrystalline e.s.r. spectra suggest tetragonal symmetry for the copper(II) ion, involving a dx 2–y2 ground state.  相似文献   

3.
Benzoylhydrazine, isonitrosoacetone react in ethanol with cobalt, nickel, copper halides andacetates to give the coordination compounds MX2(HL) · nH2O, MX2(HL)2 · nH2O, and ML2 · nH2O [M = Co,Ni, Cu; X = Cl, Br; HL = C6H5C(O)NHNC(CH3)CHNOH; n = 1-4]. The same reactions performed in the presence of sodium acetate and pyridine (pH 7-8) yield the complexes MLCl · nH2O and MPy2LCl ·nH2O (n = 1-4). All the complexes have a pseudooctahedral coordination geometry. The hydrazone HL behaves as a tridentate O,N,N-donor ligand. Thermolysis of the substances involves dehydration (70-90°C), deaquation (155-170°C) or deamination (175-195°C), and complete thermal decomposition (285-360°C).  相似文献   

4.
A new series of hexacoordinate cobalt(II), nickel(II) and copper(II) complexes of 5-(2-carboxyphenylazo)-2-thiohydantoin HL having formulae [LM(OAc)(H2O)2] · nH2O (M = CoII, CuII and NiII), [LMCl(H2O)2] · nH2O (M = CoII and NiII), [LCuCl(H2O)]2 · 2H2O, [LCu(H2O)3](ClO4) and [LCu(HSO4)(H2O)2] were isolated and characterized by elemental analyses, molar conductivities and magnetic susceptibilities, and by i.r., electronic and e.s.r. spectral measurements, as well as by thermal (t.g. and d.t.g.) analyses. The i.r. spectra indicate that the ligand HL behaves as a monobasic tridentate towards the three divalent metal ions via an azo-N, carboxylate-O and thiohydantoin-O atom. The magnetic moments and electronic spectral data suggest an octahedral geometry for CoII complexes, distorted octahedral geometry for both NiII and CuII complexes with a dimeric structure for [LCuCl(H2O)]2 · 2H2O through bridged chloro ligands. The X-band e.s.r. spectra reveal an axial symmetry for the copper(II) complexes with unsymmetrical Ms = ± 1 signal and G-parameter less than four for the dimeric [LCuCl(H2O)]2 · 2H2O. The thermogravimetry (t.g. and d.t.g.) of some complexes were studied; the order and kinetic parameters of their thermal degradation were determined by applying Coats–Redfern method and discussed.  相似文献   

5.
Copper(II) complexes with (1R*,4S*)-1-N-morpholino-n-menth-8-en-4-one (HL), namely, [Cu2(HL)2Cl4] (I) and [Cu2(HL)LCl3] · CH3CN (II), were synthesized and characterized by X-ray diffraction analysis, magnetic susceptibility, and EPR methods. The complexes have binuclear structures. In compound I, the coordination polyhedron of CuCl3N2 is a square pyramid in planar Cu2Cl2 metal cycle; the exchange couplings of unpaired electrons of Cu(II) ions are weak. Complex II incorporates polyhedra of CuCl2N2 (flattened tetrahedron) and of CuCl2N2O (trigonal bipyramid). The Cu2ClNO metal cycle is nonplanar with antiferromagnetic exchange coupling and exchange parameter –2J = 182 cm–1. The EPR spectrum of compound I are analyzed.  相似文献   

6.
A dinuclear copper(II) [(LCu)(MeOH)Cu(phen)(MeOH)]ClO4·NO3 macrocyclic complex (where H2L = 2,3-dioxo-5,6:15,16-dibenzo-1,4,8,13-tetraazacyclo-pentadeca-7,13-diene; phen = 1,10-phenanthroline) has been synthesized and characterized by means of elemental analysis and its i.r. spectrum. Its crystal structure has been determined by single-crystal X-ray diffraction. In the complex, both the copper ions are penta-coordinated and have a distorted square pyramid configuration. Magnetic susceptibility measurements show antiferromagnetic exchange interactions (J = –207.64 cm–1) between the copper(II) ions.  相似文献   

7.
Complete structural characterization of dibenzo-18-crown-6·2 CH3NO2 and dibenzo-18-crown-6·2 CH3CN have been carried out, including location and refinement of the methyl hydrogen atoms. Dibenzo-18-crown-6·2 CH3NO2 is monoclinic,P21/c, with (at –150°C)a=9.573(2),b=14.636(2),c=33.471(7) Å, =93.77(2)°, andD calc=1.37 g cm–3 forZ=8. Interactions between the solvent methyl groups and the crown ethers and other solvent nitro groups associate the 1 : 2 complexes into polymeric chains alongb. The acetonitrile adduct exists as discreet 1 : 2 complexes in the solid state with C–H...O interactions exlusively to the ether. This complex is triclinic,P 1, with (at –150°C)a=9.458(6),b=9.570(5),c=14.404(5) Å, =73.18(4), =79.85(5), =66.82(6)°, andD calc=1.28 g cm–3 forZ=2. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82070 (22 pages).For part 4, see reference [1].  相似文献   

8.
The cobalt(III) complexes with tridentate ethylenediamine-N,N"-diacetate ions (Edda2–) and additional ligands, namely, diethylenetriamine (Dien) or ethylenediamine (En) and cyanide ions, were synthesized. As follows from X-ray diffraction analysis of [Co(Edda)(Dien)]ClO4· H2O (monoclinic crystals with a = 9.243 (2) Å, b = 14.167 (4) Å, c = 13.046 (3) Å, = 91.19 (2)°, Z = 4, space group P21/c), the secondary N atom of the Dien ligand occupies the trans-position relative to the N atom of the Edda2– ligand, which contains a free acetate group. Two fac-isomers of [Co(Edda)(En)(CN)] with the CN ion in the cis- and trans-positions relative to the oxygen atom of the carboxyl group were isolated, and the structure of the trans-(O,CN)-[Co(Edda)(En)(CN)]· 2H2O was determined: monoclinic crystals with a = 9.136 (3) Å, b = 15.484 (3) Å, c = 10.564 (3) Å, = 110.67 (5)°, Z = 4, space group P21/c.  相似文献   

9.
Summary By a kinetic study of the indicator reaction of quinalizarin with hydrogen peroxide, catalysed by Co2+ ions, the optimum conditions necessary for determining traces of the catalyst have been found. These conditions are: pH=12.0 (sodium tetraborate-sodium hydroxide buffer), wavelength of measurement 565 nm,c (H2O2)/c(R)=200, temperature=25° C, Co2+ concentration range 1×10–8-2×10–7 M. A mechanism similar to that for enzymatic reactions, involving the occurrence of two intermediate complexes, gives a good explanation for the optimal conditions found.
Analytisch-kinetische Untersuchung der Indikator-Reaktion von Chinalizarin mit Wasserstoffperoxid zur Co(II)-Bestimmung
Zusammenfassung Durch eine kinetische Untersuchung der Indikator-Reaktion von Chinalizarin mit Wasserstoffperoxid, die durch Co(II)ionen katalysiert wird, wurden die optimalen Bedingungen für die Bestimmung von Spuren des Katalysators ermittelt: pH=12,0 (Natriumtetraborat-Natriumhydroxid); Wellenlänge: 565 nm;c (H2O2)/c(R)=200; Temperatur=25° C; Konzentrationsbereich von Co(II): l·10–8 bis 2·10–8 M. Ein Reaktionsmechanismus ähnlich wie für enzymatische Reaktionen einschließlich zwei Zwischenprodukt-Komplexe bieten eine gute Erklärung für die gefundenen Optimalbedingungen.
  相似文献   

10.
Yi  Long  Zhu  Li-Na  Ding  Bin  Cheng  Peng  Liao  Dai-Zheng  Zhai  Yu-Ping  Yan  Shi-Ping  Jiang  Zong-Hui 《Transition Metal Chemistry》2004,29(2):200-204
Two novel complexes, [Cu(HL)2(H2O)]2(OH)2(ClO4)2·1.5H2O (1) and [Cu(HL)2]Cl2·4H2O (2), have been prepared by reacting copper salts with the 4-amino-3-ethyl-1,2,4-triazole-5-thione (HL) ligand in neutral solution and in HCl (6 mol L–1) medium, respectively. They were characterized by FT-IR and u.v.–vis. spectra, and the structures were determined by single crystal X-ray diffraction techniques. In both complexes, the triazole ligand chelated the metal ions through the amine and thione substituents on the five-membered ring. Complex (1) has a square-pyramidal copper(II) ion coordinated by two triazole ligands and one water molecule. Unlike (1), the Cu2+ ion in (2) displays its characteristic Jahn–Teller distortion with the distance of the Cl anions to metal ion further away than that of the triazole ligands. The most intriguing structural features of the title complexes are that the HL ligands chelate copper(II) ions through the N(1) and S(1) atoms, in a cis mode in (1) and a trans mode in (2). In both cases, self-assembled crystals, by supramolecular contacts simultaneously, form two multi-dimensional frameworks.  相似文献   

11.
Complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with potassium thiocyanate, [K2(NCS)2L2] (I) was synthesized and studied using X-ray diffraction analysis: space group P , a = 7.771 Å, b = 11.711 Å, c = 11.965 Å, = 72.22°, = 79.21°, = 89.07°, Z = 1. Structure I was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.040 for all 4370 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains [K(NCS)L] monomers of the host–guest type united into centrosymmetrical [K2(NCS)2L2] dimers via two bridging OH groups (one group from two L podands). In the monomer, the L podand appears as though to envelope the octacoordinated K+ cation, whose the coordination polyhedron is a strongly distorted hexagonal bipyramid with all six oxygen atoms of the L podand in its base and the N atom of the SCN ligand and the O atom of one of OH group of the neighboring (in dimer) L podand at its axial vertices. Molecules of I in crystal are joined through the O–H···N hydrogen bonds to form broad infinite chains along the x-axis.  相似文献   

12.
Summary The following copper(I) complexes of 4,6-dimethylpyrimidine-2(1H)-thione (HL), its protonated cation (H2L+) and deprotonated anion (L) have been prepared: CuL, Cu(HL)X (X = Cl, Br or I), Cu(HL)2X (X = C1 or Br), Cu2(HL)3Br2, Cu(H2L)X2 (X = Cl or Br), Cu3(HL)2LA2 (A = ClO4 or BF4 ). The i.r. spectra show that in all the HL and L complexes and in the Cu(H2L)Br2 complex, the ligands are S, N coordinated to the metal ion, while in Cu(H2L)Cl2 only the thiocarbonylic sulphur is coordinated, probably bridging two copper(I) atoms. Thev(CuN) (288–317 cm–1 ) andv(CuS) (191–225 cm–1 ) have uniform frequency values in all the complexes. The halide ions are, in all their complexes, wholly or in part coordinated giving twov(CuX) bands which may indicate an asymmetrical Cu-X Cu halide bridging bond.Author to whom all correspondence should be directed.  相似文献   

13.
The [M(HL)2(H2O)2]X2 complexes were synthesized (M = Mn(II), Co(II), Ni(II), Cu(II), Zn; X = CH3COO, Cl, BF4 ) that incorporate bidentately coordinated molecules of N,N-dimethylhydrazide of 4-nitrobenzoic acid (HL). The latter molecules chelate the metal atom through the carbonyl O atom and the N atom of dimethylamino group. The square-planar complexes of Cu and Ni with deprotonated form of a ligand with composition ML2 were also isolated. The synthesized complexes were studied by IR, electronic and EPR spectroscopies, and by cyclic voltammetry.  相似文献   

14.
Zusammenfassung Die Kristallstruktur des Adduktes Tetrachloräthylencarbonat—Antimon(V)-chlorid, C2Cl4O2CO·SbCl5 wurde mit Hilfe der Schweratom-Methode aus dreidimensionalen Röntgendaten bestimmt und nach der Methode der kleinsten Quadrate bis zu einemR-Wert von 13,1% verfeinert (Raumgruppe P21/n — Nr. 14;a=10,13,b=12,15 undc=12,55 Å, =108°40). Die Elementarzelle enthält 4 Moleküle C2Cl4O2CO· SbCl5. Das Antimonatom ist oktaedrisch von 5 Chloratomen und dem Carbonylsauerstoffatom des Tetrachloräthylencarbonats umgeben (Sb–Cl 2,28–2,33 und Sb–O 2,40 Å).
The crystal structure of tetrachloroethylene carbonate antimony(V) chloride, C2Cl4O2CO·SbCl5
The crystal structure of the adduct tetrachloroethylene carbonate antimony(V)-chloride, C2Cl4O2CO·SbCl5, has been determined by the heavy-atom method from three-dimensional X-ray data. The refinement of the parameters was carried out by least-squares resulting anR-value of 13.1% (space group P21/n — No. 14;a=10.13,b=12.15 andc=12.55 Å, =108°40). The unit cell contains 4 discrete molecules C2Cl4O2CO·SbCl5. The antimony atom is coordinated octahedrally by 5 chlorine atoms and the carbonyl oxygen atom of tetrachloroethylene carbonate (Sb–Cl 2.28–2.33 and Sb–O 2.40 Å).


Mit 2 Abbildungen  相似文献   

15.
The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium perchlorate of the composition [Sr(ClO4)L(H2O)2]+ · ClO4 · H2O (I) was synthesized and studied using X-ray diffraction analysis: space group P21/c, a = 16.195 Å, b = 11.382 Å, c = 16.646 Å, = 117.01°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.069 for 4278 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(ClO4)L(H2O)2]+ of the host–guest type. The Sr2+ cation (coordination number 9) is coordinated to all six O atoms of the L podand, O atom of a disordered ClO4 ligand, and two O atoms of two water molecules. The coordination polyhedron of Sr2+ is irregular; in a rough approximation, it can be described as a face-centered cube. The crystal structure of I contains an infinite three-dimensional network of the O–H···O hydrogen bonds joining the complex cations, ClO4 anions, and molecules of crystallization water.  相似文献   

16.
Sodium acetylacetonate reacts with S-metliylisothiosemicarbazidium nitrate and Fe(NO3)3 · 9H2O in ethanol to make [Fe(HL)NO]NO3, in which H3L is bis(S-methyl-isothiosemicarbazone)-2,4-puntandione. The [Fe(HL)NO]+ cation has a square pyramidal structure with the HL2- arranged around the central ion in the basal plane and the nitrogen atom of the NO group in the apical position, with the iron atom diverging from the plane of the base of the pyramid by 0.477 Å. The FeN0 moiety has a linear structure (FeNO = l72.7°). XRD, IR, and Mössbauer spectroscopy have been combined with calculations on the electronic structure to demonstrate that the Fe-NO bond is covalent.Chemical Institute, Academy of Sciences of Moldavian SSR. Applied Physics Institute, Academy of Sciences of the Moldavian SSR. Kishinev. Institute of Crystallography, Academy of Sciences of the USSR. Kurnakov Institute for General and Inorganic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No, 3, pp. 376–381, May–June, 1991. Original article submitted February 18, 1991.  相似文献   

17.
The complex salt [Cu4(SCN2H4)7(NO3)](NO3)(SO4) · 3.3H2O was synthesized via reaction of aqueous solutions of thiourea with copper nitrate at 80°C and studied using X-ray diffraction analysis. The conditions and reasons for the partial oxidation of thiourea to sulfate ions were established. The crystals are monoclinic: a = 12.6072(7) Å, b = 15.4265(8) Å, c = 22.108(1) Å, = 120.133(6)°, space group P21/c, Z = 4. The crystal structure consists of [Cu4(SCN2H4)7(NO3)]3+ complex cations, SO4 2–, and NO3 anions, and molecules of the water of crystallization. Three types of coordination of the Cu atom were distinguished in the structure: trigonal (Cu–S 2.213–2.279 Å), tetrahedral (Cu–S 2.315–2.459 Å), and trigonal–pyramidal (3+1) (Cu–S 2.26–2.288, Cu–O 2.68 Å). The NO3 ligand was found to be orientationally disordered.  相似文献   

18.
Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl2(I), Cu(HL)(SO4) · 2H2O (II), and Cu(HL)(NO3)2(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C6H14Cl2CuN2O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) Å3, space group P21/c, calcd = 1.679 g/cm3, Z = 4 for R 1 = 0.0250; for II(C6H18CuN2O7S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) Å3, space group P21/c, calcd = 1.753 g/cm3, Z = 4 for R 1 = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H2O) + 2O(SO4)). Complexes IIIIare characterized by IR and EPR spectroscopy.  相似文献   

19.
For the first time the adducts of 2-amino-I-methylbenzimidazole (L) with cobalt, copper, and zinc chelates based on 2-tosylamino-N-salicylideneaniline were electrochemically synthesized, and the properties and structures of these adducts were studied. According to the IR and1H NMR spectral data on the adducts obtained and X-ray structural analysis of the copper complex, the adducts of composition mL · ML' · nH2O (m = 1 or 2; n = 0, 1, or 2) contain the L moiety bonded to the metal atom through the pyridine-type N atom of the imidazole ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2093–2097, August, 1996.  相似文献   

20.
A new coordination compound [Co(Pht)(2-MeIm)2] (I), where Pht2–is the deprotonated radical of o-phthalic acid (H2Pht) and 2-MeIm is 2-methylimidazole, was synthesized. Its structure was established using X-ray diffraction analysis. The crystal is orthorhombic: space group Pca21, a= 15.350(3), b= 7.957(2), c= 13.997(3) Å, (calcd.) = 1.505 g/cm3, and Z= 4. The tetrahedral coordination of the Co(II) atom includes two N atoms of two 2-methylimidazole molecules and two oxygen atoms of two carboxyl groups from different acid radicals. The Co–N distances are equal to 2.022(2) and 2.031(2) Å, while the Co–O distances are 1.972(2) and 2.000(2) Å. The carboxyl groups of the Pht2–radical and the aromatic nucleus form angles of 47.2° and 35.9°, whereas the angle formed by the carboxyl groups themselves is 50.3°. Compound Iis a polymer, which is confirmed by the 1,6-bridging function of the o-phthalic acid radical. The Co···Co distance in a chain is equal to 7.367 Å. Separate chains are united in the crystal into a framework via N–H···O hydrogen bonds.  相似文献   

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