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1.
The binuclear copper(II) complexes with acyldihydrazones formed by 1,4-cyclohexanedicarboxylic acid and salicylaldehyde or 2-hydroxyacetophenone were synthesized and studied. The structure of the complex with 1,4-cyclohexanedicarboxylic acid bis(salicylidene)hydrazone (H4L1) [Cu2L1(Py)2] was studied by X-ray diffraction. The crystals are triclinic: a = 8.1852(4) Å, b = 8.5157(5) Å, c = 11.6553(7) Å, α = 80.678(3)°, β = 70.041(4)°, γ = 74.803(3)°. Space group \(P\bar 1\), Z = 1. The number of symmetrically independent reflections with I > 2(σ(I)) is 2245, R = 0.0395; R w = 0.0917. The complex contains two equivalent copper atoms located at a 10.772 Å distance from each other. The coordination polyhedra have a square geometry and are involved in the intermolecular π/π-stacking. The EPR spectra of solutions of the binuclear complexes show an isotropic signal of seven HFS lines (g = 2.113–2.118, A Cu ≈ 38 G), indicating interaction between the unpaired electrons and the two equivalent copper nuclei. The possible exchange interaction channels were analyzed.  相似文献   

2.
A new complex of copper (II) with 3-(2-hydroxy-3-sulfo-5-nitrophenylazo)-pentadione-2,4 (HL) is synthesized and analyzed by single crystal XRD. The crystals are monoclinic: a = 7.7563(4) Å, b = 24.0157(12) Å, c = 24.6353(13) Å, β = 91.9490(10)°, V = 4586.2(4) Å3, space group P21/c, Z = 2, ρcalc = 1.713 g/cm3, R = 0.0695. The environment of the copper atom is formed by three oxygen atoms, the nitrogen atom of tetradentate ligand, and the oxygen atom of a water molecule.  相似文献   

3.
The adducts of binuclear copper(II) complexes with acyldihydrazones formed by 1,3- or 1,4-benzenedicarboxylic acid and some nitrogen-containing Lewis bases (pyrrolidine, piperidine) were synthesized and studied. The structure of copper(II) complex with bis(salicylidene)hydrazone of terephthalic acid (H4L), [Cu2L(Pirr)4] · CH3OH, was determined by X-ray diffraction data. The crystals are monoclinic: a = 15.5142(7) Å, b = 13.8784(6) Å, c = 17.8873(8) Å; β = 91.990(2)°, space group C2/c, Z = 4. The number of symmetrically independent reflections was 4269, R = 0.0303, R w = 0.0827. The complex contains two equivalent copper atoms located at a 11.021 Å is a tetragonal pyramid. EPR spectral features of the adducts were studied.  相似文献   

4.
The structure and the EPR spectra of copper(II) coordination compounds with acyldihydrazones of N-benzenesulfonyl-L-aspartic acid and salicylaldehyde (2-hydroxyacetophenone) were described. The compounds were studied by chemical and thermal analyses, IR spectroscopy, and EPR. The molecular and crystal structures of copper(II) complexes with N-benzenesulfonyl-L-aspartic acid bis(salicylidene)hydrazone (H4L1) [Cu2L1 · 2Py] · 1.5 H2O was determined by X-ray diffraction. The crystals are triclinic: a = 10.4714(4) Å, b = 12.9702(5) Å, c = 14.6187(9) Å, α = 104.763(2)°, β = 93.082(2)°, γ = 111.4240(10)°, space group P \(\bar 1\), Z = 2. The binuclear complexes containing copper cations whose coordination polyhedra are connected by an aliphatic spacer (Cu...Cu, 8.669 Å) are additionally linked by phenoxy bridges (Cu...Cu, 3.398 Å). The EPR spectra of these compounds in solutions exhibit an isotropic signal of seven HFS lines due to two equivalent copper ions with the spin Hamiltonian parameters g = 2.115?2.120, a Cu = (35.5?38.0) × 10?4 cm?1, which is indicative of weak exchange interactions between the paramagnetic sites.  相似文献   

5.
The structure and EPR spectra of copper(II) complexes with bis(salicylidene)hydrozones of N-benzoyl-L-aspartic and N-benzoyl-L-glutamic acids have been described. The compounds have been studied by chemical and thermal analyses, IR spectroscopy, and EPR spectroscopy. The molecular and crystal structure of the copper(II) complex with bis(salicylidene)hydrozone of N-benzoyl-L-aspartic acid (H4L) of composition [Cu2L · 2Py] · 2CH3OH · H2O has been determined by X-ray single-crystal diffraction. The crystals are monoclinic: a = 10.3316(7) Å, b = 16.7552(9) Å,c = 11.0137(6) Å, β = 105.758(3)°, space group P21, Z = 2. The complex has a polymeric structure composed of alternating copper-containing binuclear fragments bound to each other either via phenoxy bridges or via an aliphatic spacer (the Cu…Cu distances are 3.471 Å and 8.939 Å, respectively). The EPR spectra of the solutions of the complexes under study shows an isotropic signal comprising seven HFS lines due to two equivalent copper nuclei with the spin Hamiltonian parameters g = 2.115–2.122 and a Cu = (36.1–36.9) × 10?4 cm?1, which indicates the reaization of weak exchange coupling of the paramagnetic centers.  相似文献   

6.
Binuclear copper(II) complexes with acyldihydrazones of benzenedicarboxylic acid and trifluoroacetylacetone have been synthesized and studied. The structure of the copper(II) complex with diacylhydrazone of 1,3-benzenedicarboxylic acid (H4L) of composition [Cu2L · 2LPy] has been studied by X-ray diffraction. The crystals are triclinic: a = 9.2298(4) Å, b = 11.8510(6) Å, c = 13.8314(7) Å, α = 90.780(3)°, β = 96.124(3)°, γ = 99.264(3)°, space group \(P\bar 1\), Z = 2. The number of symmetry-unrelated reflections with I > 2σ(I) 5941; R = 0.0357, R w = 0.0589. The complex contains two equivalent copper atoms at a distance of 9.56 Å from each other in the square-planar coordination environment. The high-temperature EPR spectra of the complexes show a signal of seven HFS lines indicating the coupling of unpaired electrons to two equivalent copper nuclei (g = 2.113?2.116, a Cu = 37.0?37.2 × 10?4 cm?1).  相似文献   

7.
A copper(II) complex with salicylaldehyde N-(2-salicylideneiminoglutaryl)hydrazone (H4L) of the formula [Cu2L · 2Py]2 · 8H2O (I) was obtained and characterized by X-ray diffraction. The crystals are monoclinic, space group P21, a = 13.0663 Å, b = 16.5553 Å, c = 17.7650 Å, β = 97.9420°; Z = 4. The complex is tetranuclear with a “dimer-of-dimers” structure in which the copper cations of two binuclear subunits are linked by phenoxy bridges. The EPR spectra of solutions of complex I show a superposition of two signals of four HFS lines (g 1 = 2.111, a 1 = 56.8 × 10?4 cm?1 and g 2 = 2.183, a 2 = 71.0 × 10?4 cm?1).  相似文献   

8.
Crystals of the π copper(I) cyanide complex with N,N′-diallyl thiocarbamide, 2CuCN · (C3H5NH)2CS (I), are synthesized from an aqueous-methanol solution of potassium nitroprusside, diallyl thiocarbamide on a copper electrode using the method of alternating-current electrochemical synthesis. The crystals are monoclinic: space group P21/n, a = 6.9440(5) Å, b = 13.760(1)) Å, c = 12.733(1) Å, β = 97.280(9)°, V = 1206.8(2) Å3, Z = 4, R = 0.0361, R w = 0.0362 for 2836 independent reflections with F ≥ 4σ(F). A unique polymeric structure is built due to the Cu(I)-(C=C) π bond and the bridging function of the thioamide S atom of the ligand molecule and one of the two independent cyano groups.  相似文献   

9.
The centrosymmetric binuclear manganese(II) nitrate complex with a bicyclic bis-carbamide, namely, 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo(3.3.0)octane-3,7-dione, or mebicar (Mk) [Mn(C8H14N4O2)(H2O)(NO3)2]2 · H2O (I), has been synthesized for the first time. The structure of complex I has been solved (CCDC no. 1435139). Crystals of complex I are monoclinic, space group P21/c, a = 12.8108(11) Å, b = 10.0662(2) Å, c = 18.6367(17) Å, β = 136.512(16)°, V = 1654.0(4) Å3, ρcalcd = 1.659 g/cm3, Z = 2. Each manganese atom is coordinated to the two oxygen atoms of two Mk molecules related by the symmetry codes (1–x, 2–y, 1–z) and to two bidentate nitrate anions and one water molecule. The coordination polyhedron of the manganese atom is a strongly distorted pentagonal bipyramid. The Mn···Mn distance in the complex is 8.7261(9) Å.  相似文献   

10.
Crystals of [Cu(Eddp)·(HgCl2)3]n (monoclinic, a = 9.7547(7) Å, b = 18.3716(12) Å, c = 11.7811(9) Å, β = 94.828(9)°, Z = 4, space group P21/n) are made of infinite sheets involving dimeric complexes [Cu2(Eddp)2] interacting with quasi-molecules of HgCl2 (Hg-Cl 2.29-2.36 Å). In the dimers, copper atoms are squarely surrounded by two N atoms and two O atoms of the ethylendiamine-N,N′-di(3-propionate) anion, and atom from a neighboring Eddp ion in the apical position; the second apical position is occupied by a Cl atom of one of HgCl2 molecules. Weak Hg-Cl interactions (2.98-3.07 Å) join the molecules of HgCl2 in almost planar centrosymmetrical Hg6Cl12 hexamers, and further (Hg-Cl 3.168(3) Å, 3.250(2) Å) in infinite chains of the hexamers. Finally, the dimeric copper complexes are linked to six Hg atoms of four adjacent hexamers by virtue of their oxygen atoms (Hg-O 2.322(8), 2.609(6) Å, 2.730(5) Å).  相似文献   

11.
A copper(II) complex with 2-(diphenylacetyl)indanedione-1,3 (HL) was synthesized. CuL2·0.5C4H8O2 crystals prepared from chloroform + 1,4-dioxane are triclinic, space group P \(\bar 1\), a = 15.0206(9) Å, b = 16.0132(9) Å, c = 16.8323(10) Å, α = 109.6850(10)°, β = 96.4390(10)°, γ = 97.7120(10)°, Z = 4. A unit cell contains two crystallographically independent centrosymmetric dinuclear complexes of the same structure. Each copper(II) atom is coordinated by bidentate cis-oriented deprotonated ligands L at the corners of the square. Bridging 1,4-dioxane molecules make the CN of each metal atom five.  相似文献   

12.
The binuclear Ni(II) 1-(2-carboxyphenyl)-3-isopropyl-5-(benzimidazole-2-yl)formazanate (Ni2L2 · 2H2O) (I) was synthesized and its crystal and molecule structures were determined by X-ray diffraction. Crystals I are triclinic: space group P \(\bar 1\), a = 7.4811(11), b = 10.8821(15), c = 11.4168(13) Å, α = 105.690(11) Å, β = 90.537(11) Å, γ = 93.166(11) Å, V = 893.2(2) Å3, ρ(calcd.) = 1.581 g/cm3, Z = 1.  相似文献   

13.
The structure of the hexanuclear copper(II) β-diketonate complex with gfa (hexafluoroacetylacetone) and dpm (dipivalylmethanate) ligands was studied by low-temperature (T = 100 K) X-ray diffraction. Crystal data for Cu6(gfa)4(dpm)4(OH)4 [C64H84Cu6F24O20]: a = 28.2364(7) Å, b = 12.8072(3) Å, c = 24.7199(7) Å, β= 115.900(1)°, V = 8041.5(4) Å3, space group C2/m, Z = 4, d calc 1.661 g/cm3. The coordination polyhedra of the copper atoms — squares and octahedra — are formed by the oxygen atoms of the gfa and dpm ligands and groups. In all cases, the Cu-O distances vary from 1.89 Å to 2.13 Å. The complexes follow the sites of the rhombohedral sublattice with the parameters a c ≈ 14.4 Å and a c ≈ 61.5°.  相似文献   

14.
Single crystal X-ray diffraction is used to investigate two synthesized β-diketonate complexes of copper(II) with aminopyridine: Cu(4-NH2Py)(aa)2 (I) and Cu(4-NH2Py)(hfa)2 (II). The crystals of I and II have a monoclinic system; the unit cell parameters of I are: P21/n space group, a = 8.2921(3) Å, b = 14.7243(5) Å, c = 13.4970(4) Å, β = 102.426(1)°, V = 1609.32(9) Å3, Z = 4; for II: C2/c space group, a = 23.5704(5) Å, b = 11.4977(2) Å, c = 16.0285(3) Å, β = 109.265(1)°, V = 4100.6(1) Å3, Z = 8. The structures of I and II are molecular; they are composed of isolated molecules. The coordination polyhedron of the copper atom is formed by the O atoms of two acetylacetonate ligands (Cu-O 1.940(2)–2.171(2) I and the O atoms of two hexafluoroacetylacetonate ligands (Cu-O 1.940(2)–2.215(3) Å) in II. The molecules of 4-NH2Py are bonded to the copper atom via the nitrogen atom of the aromatic ring (Cu-N 2.008(2) Å in I and Cu-N 1.978(3) Å in II). Noncoordinated amino groups join the molecules of the complexes together by means of N-H…O hydrogen bonds.  相似文献   

15.
A centrosymmetric mononuclear copper(II) complex, [Cu(L1)2] (I), and a phenolate oxygen-bridged dinuclear copper(II) complex, [Cu2(L2)4] (II) (HL1 = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol, HL2 = 4-chloro-2-(cyclohexylimino-methyl)phenol), were synthesized and characterized by elemental analyses, IR, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group {ITP}21/n, a = 13.396(3), b = 5.339(1), c = 19.740(4) Å, β = 108.64(3), V = 1337.8(5) Å3, {ITZ} = 2. The crystal of II is monoclinic: space group P21, a = 9.157(2), b = 22.715(4), c = 12.169(2) Å, = 95.28(3), {ITV} = 2520.4(8) Å3, {ITZ}= 2. The Cu atom in I, lying on the inversion center, is four-coordinate in a square planar geometry with two phenolate oxygen and two imine nitrogen atoms. Each Cu atom in II is five-coordinate in a square pyramidal geometry with two phenolate oxygen and two imine nitrogen atoms from two L2 ligands defining the basal plane and with one phenolate oxygen atom of another L2 ligand occupying the apical position.  相似文献   

16.
A novel Cu(II) complex Cu2(Endc)2(Bipy)2 has been synthesized by the reaction of Cu(NO3)2 · 3H2O, Endc (endo-norbornene-cis-5,6-dicarboxylic acid), and Bipy (2,2-bipyridine) at room temperature. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: triclinic, P \(\bar 1\) with a = 9.0373(10), b = 10.1637(11), c = 10.5574(12) Å, α = 65.78(1)°, β = 72.32(2)°, β = 73.23(2)°, Z = 1, V = 827.46(16) Å3, ρ c = 2.160 g/cm3, F(000) = 410.0, R = 0.0483 and wR = 0.0958 independent reflections for 4468 observed ones (I > 2 σ(I)).The Cu2+ ion is coordinated by two nitrogen atoms from the Bipy molecule and three oxygen atoms from two Endc, giving a distorted squarepyramidal coordination geometry. Two neighboring Cu2+ ions are bridged by a pair of bimonodentate carboxyl groups of different Endc acids, giving a centrosymmetrical binuclear structure which a Cu…Cu distance of 3.2946 Å. The photoluminescence properties of the complex were studied at room temperature. The complex displays an obvious photoluminescent emission upon excitation at 390 nm in the solid state.  相似文献   

17.
The heteronuclear germanium(IV) and neodymium(III) complex with 1,3-diamino-2-propanoltetraacetic acid (H5Hpdta) [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H2O)3] · H2O has been synthesized for the first time and characterized by physicochemical methods (elemental analysis, X-ray powder diffraction, thermogravimetry, IR spectroscopy, X-ray crystallography). The crystals are monoclinic: a = 9.331(3) Å, b= 10.279(4) Å, c = 21.474(7) Å, β = 94.59(3)°, V = 2053.0(12) Å3, Z = 4, space group P21/n, R1 = 0.0245 for 4060 reflections with I > 2σ(I). The compound is built of complex binuclear molecules [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H2O)3] and water molecules of crystallization. The germanium and neodymium atoms are bridged by the oxygen atom of the hydroxo group (Ge-O, 1.798(2) Å; Nd-O, 2.539(2) Å) and the deprotonated oxygen atom of the isopropanol group of the HHpdta4? ligand (Fe-O, 1.858(2)Å; Nd-O, 2.420(2) Å) to form a dimeric molecule. Each coordination sphere (of the Ge atom and of the Nd atom) contains one nitrogen atom (Ge-N, 2.096(3) Å; Nd-N, 2.807(2) Å) and two carboxylic oxygen atoms from four acetate branches of the octadentate HHpdta4? ligand (av. Ge-O, 1.928(2) Å; Nd-O, 2.391(2) Å). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group (Ge-O 1.811(2) Å), and the polyhedron of the Nd atom is completed to a nine-vertex polyhedron by the oxygen atoms of the terminal hydroxo group (Nd-O 2.494(3) Å) and three water molecules (Nd-O, 2.512(3), 2.520(3), and 2.723(3) Å). In the crystal structure, the complex molecules and the water molecules of crystallization are joined by a hydrogen bond system.  相似文献   

18.
Copper(II) binuclear complexes with acyldihydrazones of saturated carboxylic acids and pyruvic acid in which the coordination polyhedra are connected by polymethylene chains of different length (1 to 5 units) were synthesized and studied by chemical and thermogravimetric analysis, IR spectroscopy, and EPR. The structure of binuclear copper(II) complex with succinic acid acyldihydrazone [Cu2L · 4Py] · 2Py was determined by X-ray diffraction. The crystals are monoclinic: a = 14.3795(6), b = 8.8736(4), c = 15.9147(7) Å, β = 101.062(3)°, space group P21/c, Z = 2. The number of independent reflections with I > 2σ(I) = 2804, R = 0.042, R w = 0.087. The copper atoms are spaced by a chain of seven σ bonds at 8.922 Å. The coordination polyhedron can be described as a tetragonal pyramid highly distorted toward a trigonal bipyramid. The EPR spectra of solutions of complexes based on malonic, succinic, glutaric, and adipinic acids exhibit a poorly resolved signal of seven HFS lines with a constant of (26.3–27.0) × 10?4 cm?1, which attests to the presence of weak exchange interactions between paramagnetic centers. An increase in the length of the polymethylene spaur suppresses exchange interactions, and the EPR spectrum of the complex based on pimelic acid acyldihydrazone shows a signal of four HFS lines with a constant of 43.8 × 10?4 cm?1 typical of monomeric copper(II) complexes.  相似文献   

19.
The synthesis of copper(II) binuclear complexes with acyldihydrazones of saturated carboxylic acids and 4-formyl-5-hydroxy-3-methyl-1-phenylpyrazoles in which the coordination polyhedra are connected by polymethylene chains of different length (two to five units) is described. The complexes were studied by chemical and thermal analysis, IR spectroscopy, and EPR. The molecular and crystal structure of the copper(II) complex with glutaric acid and 1-(4′-chlorophenyl)-4-formyl-5-hydroxy-3-methylpyrazole acyldihydrazone (H4L) described as [Cu2L·2Py] · Py · 4H2O was determined by X-ray diffraction. The crystals are orthorhombic: a = 24.789(7) Å, b = 39.319(9) Å, c = 4.6336(14) Å, space group Pnma, Z = 4. The number of symmetrically unrelated reflections is 4716, R = 0.0606, R w = 0.1307. The central atoms are separated by a chain of eight σ bonds and are located at a distance of 8.939 Å. The copper coordination polyhedron is a square. A specific feature of the crystal structure is the stacking interaction involving chelate rings and the pyrazole ring, resulting in stacks of molecular complexes. The EPR spectrum of a solution of the complex based on the acyldihydrazone of succinic acid and 4-formyl-5-hydroxy-3-methyl-1-phenylpyrazole recorded at room temperature exhibits seven HFS lines with an intensity ratio of 1: 2: 3: 4: 3: 2: 1 and a constant of 33.3 G as a result of exchange coupling of the unpaired electrons to the two equivalent copper nuclei. An increase in the length of the polymethylene chain to 3–5 units or introduction of the para-chlorine atom into the benzene ring hampers the exchange interactions, and the EPR spectrum shows a signal of four HFS lines with a constant of 55–70 G typical of monomeric copper(II) complexes.  相似文献   

20.
trans-Bis-(4-phenyliminopentan-2-onato)Cu(II) (5), which is a phenyl-substituted ketoimine, was synthesized, and an X-ray study was performed for this compound. Crystal data for CuN2O2C22H24: a = 11.4557(3) Å, b = 26.6845(9) Å, c = 14.2976(5) Å, β = 113.2270(10)°; space group P21/n, Z = 8, d calc = 1.363 g/cm3, R = 0.033. The structure is molecular and built of isolated trans complexes. The central copper atom is surrounded by four atoms (2O+2N) with the average distances Cu-O 1.904(3) Å and Cu-N 1.962(3) Å. The polyhedron around the copper atom is a distorted tetrahedron; the average values of the O-Cu-O and N-Cu-N trans bond angles are 147(2)° and 150(2)°, respectively. The average value of the O-Cu-N angles is 94(1)°.  相似文献   

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