The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction....The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.展开更多
The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126...The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126(4)nm; β =113.89(2)° ; Mr=587.52 (C16H28Cu2N8O8); V=1.1299(5)nm3. The copper atom lies in a distorted square pyramidal environment. The four equatorial donors are four nitrogen atoms from bidentate chelate dimethylglyoxime anion ligands. The oxygen atom from the dimethylglyoxime ligand acts as a bridging atom occupying the apical position of the symmetry related copper atom in the dimer structure. The two dimethylglyoximes bridge two copper atoms to form a six member Cu2O2N2 ring, respectively. The thermal gravity (TG) data indicate that the compound [Cu2(Hdmg)4] undergoes two exothermic reactions with loss of the organic ligand to give residue CuO. CCDC: 208729.展开更多
The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and ...The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to triclinic, space group P with a = 0.74485(14), b = 1.6094(3), c = 1.7472(3) nm, a = 114.662(4), b = 99.997(4), g = 93.218(4), V = 1.8551(6) nm3, Mr = 882.31, Z = 2, Dc = 1.580 g/cm3, m = 1.395 mm-1 and F(000) = 906. The complex is a binuclear copper compound, and the two copper ions nearly have the same coordination environment. There exists MM bond in the complex. The distance of Cu(1)Cu(2) is 0.29747(7) nm. The two ions form two distorted octahedral geometries.展开更多
Four cyanide-bridged heterometallic complexes { [CuPb（L1）][FenI（bpb）（CN）2] }2-（C104）2.2H20.2CH3CN （1）, { [CuPb（LI）]2[FeII （CN）6]（HzO）z}＇10H20 （2）, {[Cu2（L2）][Fent（bpb）（CN）2]2}＇2H20＇2CH3OH （...Four cyanide-bridged heterometallic complexes { [CuPb（L1）][FenI（bpb）（CN）2] }2-（C104）2.2H20.2CH3CN （1）, { [CuPb（LI）]2[FeII （CN）6]（HzO）z}＇10H20 （2）, {[Cu2（L2）][Fent（bpb）（CN）2]2}＇2H20＇2CH3OH （3） and {[Cu2（L2）]3[FeIII（CN）6]z（H20）2}-10H20 （4） have been synthesized by treating K[Fem（bpb）（CN）2] [bpb2-=l,2-bis（pyridine-2-carboxamido）benzenate] and K3[Feln（CN）]6 with dinuc[ear compartmental macrocyclic Schiff-base complexes [CuPh（LI）].（C104）2 or [Cu2（L2）]-（CIO4）2, in which H2LJ was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2：1：1 and H2L2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1：1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [Fem（bpb）（CN）2]- and [CuPb（L＋）]2＋ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe（CN）6]4- anion sandwiched in two [CuPu（L1）]2＋ cations, and the pentanuclear moieties are further connected by the hydro- gen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cuz（L2）]2＋ segment and two terminal cyanide-containing blocks [Fetn（bpb）（CN）2]-. Octanuclear compound 4 is built from two [Fe（CN）6]3- anions sandwiched in the three [Cu2L2]2＋ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.展开更多
文摘The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.
文摘The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126(4)nm; β =113.89(2)° ; Mr=587.52 (C16H28Cu2N8O8); V=1.1299(5)nm3. The copper atom lies in a distorted square pyramidal environment. The four equatorial donors are four nitrogen atoms from bidentate chelate dimethylglyoxime anion ligands. The oxygen atom from the dimethylglyoxime ligand acts as a bridging atom occupying the apical position of the symmetry related copper atom in the dimer structure. The two dimethylglyoximes bridge two copper atoms to form a six member Cu2O2N2 ring, respectively. The thermal gravity (TG) data indicate that the compound [Cu2(Hdmg)4] undergoes two exothermic reactions with loss of the organic ligand to give residue CuO. CCDC: 208729.
基金This work was supported by the NSF of Guangxi Province (0339034) and the Science Research Foundation of Guangxi Universities
文摘The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to triclinic, space group P with a = 0.74485(14), b = 1.6094(3), c = 1.7472(3) nm, a = 114.662(4), b = 99.997(4), g = 93.218(4), V = 1.8551(6) nm3, Mr = 882.31, Z = 2, Dc = 1.580 g/cm3, m = 1.395 mm-1 and F(000) = 906. The complex is a binuclear copper compound, and the two copper ions nearly have the same coordination environment. There exists MM bond in the complex. The distance of Cu(1)Cu(2) is 0.29747(7) nm. The two ions form two distorted octahedral geometries.
基金financially supported by the National Natural Science Foundation of ChinaMinistry of Education of China+1 种基金Beijing Municipal Commission of EducationFundamental Research Funds for the Central Universities
文摘Four cyanide-bridged heterometallic complexes { [CuPb（L1）][FenI（bpb）（CN）2] }2-（C104）2.2H20.2CH3CN （1）, { [CuPb（LI）]2[FeII （CN）6]（HzO）z}＇10H20 （2）, {[Cu2（L2）][Fent（bpb）（CN）2]2}＇2H20＇2CH3OH （3） and {[Cu2（L2）]3[FeIII（CN）6]z（H20）2}-10H20 （4） have been synthesized by treating K[Fem（bpb）（CN）2] [bpb2-=l,2-bis（pyridine-2-carboxamido）benzenate] and K3[Feln（CN）]6 with dinuc[ear compartmental macrocyclic Schiff-base complexes [CuPh（LI）].（C104）2 or [Cu2（L2）]-（CIO4）2, in which H2LJ was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2：1：1 and H2L2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1：1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [Fem（bpb）（CN）2]- and [CuPb（L＋）]2＋ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe（CN）6]4- anion sandwiched in two [CuPu（L1）]2＋ cations, and the pentanuclear moieties are further connected by the hydro- gen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cuz（L2）]2＋ segment and two terminal cyanide-containing blocks [Fetn（bpb）（CN）2]-. Octanuclear compound 4 is built from two [Fe（CN）6]3- anions sandwiched in the three [Cu2L2]2＋ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.
