A copper(Ⅱ) complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-(4-fluorophenyl)iminomethyl-8-quinolinoxy]butane(L). X-ray crystal structure shows that it is ...A copper(Ⅱ) complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-(4-fluorophenyl)iminomethyl-8-quinolinoxy]butane(L). X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387(2), b = 9.968(2), c = 10.291(2) ?, α = 87.532(3), β = 63.762(2), γ = 86.628(3)o, V = 862.1(3) ?^3, Z = 1, Dc = 1.640 Mg/m^3, F(000) = 428, R = 0.0416 and wR = 0.1141. Each Cu(Ⅱ) metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper(Ⅱ) complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.展开更多
Three polymeric copper(Ⅰ) halide complexes beating phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy = bipyridine), [(PPh3)2Cu2(μ-Br)2(μ- bpe)]∞ 2 (bpe = trans-...Three polymeric copper(Ⅰ) halide complexes beating phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy = bipyridine), [(PPh3)2Cu2(μ-Br)2(μ- bpe)]∞ 2 (bpe = trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122(3), b = 9.322(3), c = 13.201(4) A, α = 106.440(4), β= 105.965(5), γ= 94.167(5)°, V = 1021.3(6) A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F(000) = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections (I 〉 2σ(I)). Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420(3), b = 10.209(4), c = 12.407(4) A, α = 104.136(6), β = 108.132(5), γ= 95.338(6)°, V = 1081.0(7) A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F(000) = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections (I 〉 2σ(I)). Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32(1), b = 11.53(2), c = 13.94(3) A, α = 109.57(3), β= 93.85(3), γ= 97.28(3)°, V= 1242(4) A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F(000) = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections (I 〉 2σ(I)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.展开更多
The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crys...The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).展开更多
The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemen...The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemental analyses, thermogravimetric analyses, IR and UV-visible spectroscopy. The crystal belongs to the monoclinic system, space group P21/c with a = 9.4564(10), b = 18.2679(19), c = 15.7284(12) A,β= 126.045(4)°, V= 2196.9(4)A^3, Z= 4, Dc = 1.618 g/cm^3, Mr = 535.02,μ = 1.141 mm^-1, F(000) = 1100, 2(MoKα) = 0.71073 A, the final R = 0.0429 and wR = 0.1044 for all observed reflections. In the structure, every two Cu(II) atoms are bridged by a bivalent 5-sulfosalicylic anion to form a 1D chain-like coordination polymer. Lattice waters between chains link them to form 2D layers which are further linked by C-H…O hydrogen bonds to form a three-dimensional supramolecular network.展开更多
The title compound [Cu (ADC) (2, 2'-bipy)]n (ADC = C2 (COO)2^2.) was prepared and characterized by elemental analysis, IR spectroscopy, X-ray analysis, respectively. The analysis of the crystal structure reve...The title compound [Cu (ADC) (2, 2'-bipy)]n (ADC = C2 (COO)2^2.) was prepared and characterized by elemental analysis, IR spectroscopy, X-ray analysis, respectively. The analysis of the crystal structure reveals that the copper atom is five-coordinated with two nitrogen atoms of 2, 2'-bipy and three oxygen atoms of different acetylenedicarboxylate dianions. ADC as bridging ligands link the Cu (Ⅱ) ions, forming coordination polymer structure.展开更多
Reaction of bis(4,6-dimethyl-2-pyrimidinethiolato)methane(bpytm) with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2(μ-bpytm)]n which was charac...Reaction of bis(4,6-dimethyl-2-pyrimidinethiolato)methane(bpytm) with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2(μ-bpytm)]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433(5),b=13.6986(4),c=7.8434(2),β=100.371(2)°,V=1790.71(9)3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ(MoKα)=1.751mm-1,F(000)=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ(I) and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025(2) and 2.234(1) A, respectively.展开更多
One new polymer, [Na(NPHSNPAB)(CH3OH)]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and sin...One new polymer, [Na(NPHSNPAB)(CH3OH)]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex: C(17)H(17)N4NaO9S, Mr = 476.39, triclinic system, space group P1, a = 8.8741(18), b = 10.942(2), c = 12.039(2) A, α = 65.74(3), β = 77.49(3), γ = 84.30(3)o, V = 1040.3(4) A3, Z = 2, Dc = 1.521 g/cm^3, λ = 0.71073 A, F(000) = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 〉 2(I). X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium(I) center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units(3.768 A) indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.展开更多
The title compound, C24H28ClCuN4O6 (Mr = 567.49), has been prepared and its crystal structure has been determined by X-ray diffraction method. The crystal belongs to monoclinic, space group C2/c with a = 23.1905(14...The title compound, C24H28ClCuN4O6 (Mr = 567.49), has been prepared and its crystal structure has been determined by X-ray diffraction method. The crystal belongs to monoclinic, space group C2/c with a = 23.1905(14), b = 30.1877(12), c = 7.4881 (3) A, β = 97.631 (2)°, V = 5195.8(4) A^3, Z = 8, Dc = 1.451 g/cm^3,μ = 0.989 mm^-1, F(000) = 2352, S = 1.030, R = 0.0694, wR = 0.2120 (I 〉 2σ(I)), R = 0.0950 and wR = 0.2322 (all data). The crystal consists of the Cu(Ⅰ) complex and lattice water molecules. The Cu(Ⅰ) atom is coordinated by two phenanthroline (phen) molecules and one chlorine anion with a distortetl trigonal dipyramidal coordination geometry. By the aid of aromatic π-π stacking, the Cu(Ⅰ) complex molecules form two-dimensional supramolecular layers. Lattice water molecules locate between the adjacent layers to form a three-dimensional sandwich-like supramolecular structure.展开更多
A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoc...A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I>2σ (Ⅰ)].展开更多
Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic ...Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic Pbca,a = 18.5858(12),b = 8.1821(5),c = 20.6066(13) ,V = 3133.7(3) 3,Z = 8,Dc = 1.843 g/cm3,F(000) = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2:Orthorhombic Pbca,a = 18.7883(16),b = 8.3249(7),c = 19.0294(17) ,V = 2976.4(4) 3,Z = 8,Dc = 1.731 g/cm3,F(000) = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3:monoclinic P21/c,a = 13.812(10),b = 9.910(7),c = 23.444(17) ,β = 104.3350(10)°,V = 3090(4) 3,Z = 4,Dc = 1.476 g/cm3,F(000) = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2(1) and C14H16BrCuN2O2(2) are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional(3D) supramolecular network in 1 and a two-dimensional(2D) sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4(3) is ionic.In 3,the [Cu(dmbp)2]+ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional(1D) chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.展开更多
A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type l...A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.展开更多
Reaction of Cu powder with 2-thenoyltrifluoroacetone and 2, 2-bipygave a complex [Cu(C8H4SO2F3) (2, 2' -bipy)]. The title compound is monoclinic sys-tem, sapce grop C2/c, a= 17. 892(5), b= 18. 495(4), c= 16. 242(6...Reaction of Cu powder with 2-thenoyltrifluoroacetone and 2, 2-bipygave a complex [Cu(C8H4SO2F3) (2, 2' -bipy)]. The title compound is monoclinic sys-tem, sapce grop C2/c, a= 17. 892(5), b= 18. 495(4), c= 16. 242(6) A, β=121. 02(2)°, Z=8, V=4606. 2 A3, Dc= 1. 512 g/cm3, μ= 12. 724 cm-1, F(000) = 1766,Mr = 440. 6, Final R = 0. 061 and R. = 0. 071. X-ray crystal structure analysis revealedthat copper(I) is coordinated by two O and two N atoms. The Cu(I) atom displays anearly square planar coordination geometry.展开更多
A novel copper(I) coordination polymer [C30 H18 Cu3 Cl3 N4]n was solvethermally synthesized with 1-(prop-2-en-1-yl)-2-{4-[1-(prop-2-en-1-yl)-1 H-1,3-benzodiazol-2-yl]phenyl}-1 H-1,3-benzodiazole as the flexible ligand...A novel copper(I) coordination polymer [C30 H18 Cu3 Cl3 N4]n was solvethermally synthesized with 1-(prop-2-en-1-yl)-2-{4-[1-(prop-2-en-1-yl)-1 H-1,3-benzodiazol-2-yl]phenyl}-1 H-1,3-benzodiazole as the flexible ligand. It crystalizes in orthorhombic system, space group Pbcn with a = 22.0890(7), b = 6.3626(2), c = 18.2480(6) ?, V = 2564.64(14) ?3 and Mr = 365.73. The compound characterized by elemental analysis, infrared spectroscopy and powder X-ray diffraction analysis displays a 2 D structure. The complex shows strong green luminescence at 506 nm and better property of electrochemical oxygen evolution.展开更多
Two copper complexes [Cu(TTA)(2)(4, 4'-azpy)] (1) and [ Cu- (TTA)(2)(3,3'-azpy)] (2) (HTTA = 1,1,1-trifluoro-3-(2-thenoyl)-acetone, 4,4'-azpy = 4,4'-azobispyridine, 3,3'-azpy = 3,3'-azobispyrid...Two copper complexes [Cu(TTA)(2)(4, 4'-azpy)] (1) and [ Cu- (TTA)(2)(3,3'-azpy)] (2) (HTTA = 1,1,1-trifluoro-3-(2-thenoyl)-acetone, 4,4'-azpy = 4,4'-azobispyridine, 3,3'-azpy = 3,3'-azobispyridine) were synthesized and characterized. The crystal structures were determined by X-ray diffraction analysis. The crystal I belongs to triclinic with space group P1, a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, alpha = 66.126(9)degrees, beta = 79.667(9)degrees, gamma = 90.13(1)degrees, Z = 1, V = 0.6692(2) nm, D-c = 3.425 g/cm(3), mu = 2.113 mm(-1), F(000) = 694, R-1 = 0.0594, wR(2) = 0.1499. The crystal 2 belongs to monoclinic with space group P2(1)/c, a = 1.0661(2) nm, b = 1.4296(3) nm, c = 1.0041(3) nm, beta = 114.50(3)degrees, V = 1.3926(5) nm(3), Z = 2, D-c = 1.646 g/ cm(3), mu = 1.015 mm(-1), F (000) = 694, R-1 = 0.0535, wR(2) = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one-dimensional linear chains linked through the rod- like 4,4'-azpy ligands or 3,3'-azpy ligands.展开更多
The copper(Ⅱ) complex [Cu_3(nta)_2(azpy)_2(H_2O)_2]·6H_2O (nta =nitrilotriacetate, azpy = 4,4′-azobispyridine) has been synthesized and characterized. The X-rayanalysis reveals that there are two kinds of copp...The copper(Ⅱ) complex [Cu_3(nta)_2(azpy)_2(H_2O)_2]·6H_2O (nta =nitrilotriacetate, azpy = 4,4′-azobispyridine) has been synthesized and characterized. The X-rayanalysis reveals that there are two kinds of copper(Ⅱ) coordination environments. Cu(1) has adistorted square plane symmetry and Cu(2) has a distorted octahedral symmetry. Cu(1) is linked toCu(2) through nta and bound to Cu(1C) by azpy, and Cu(2) is linked to Cu(2A) through azpy, whichextends to two-dimensional network with large rhombus 1.2 nm x 1.7 nm.展开更多
In an attempt to synthesize supra-molecular complex of copper(II) with mixed ligands in a solution reaction of Cu(ClO 4) 2·6H 2O with 4,5-diazafluorene-9-one (dafo) and o-phthalic acid, the bright blue col...In an attempt to synthesize supra-molecular complex of copper(II) with mixed ligands in a solution reaction of Cu(ClO 4) 2·6H 2O with 4,5-diazafluorene-9-one (dafo) and o-phthalic acid, the bright blue column-like crystal [Cu(dafo) 2(H 2O) 2]-(ClO 4) 2 was obtained. Its structure was determined by single-crystal X-ray diffraction study. The crystal belongs to monoclinic system, space group P2(1)/n with cell dimensions: a=0.7947(3) nm, b=1.2021(5) nm, c=1.3190(5) nm, α=90.000(5)°, β=90.000(5)°, γ= 90.000(5)°, V=1.2600(9) nm 3, Z=2, F(000)=670, M r=662.83, D c=1.747 g/cm 3, μ (Mo Kα)=1.154 mm -1, R 1=0.0455, wR 2=0.1041. The analysis of the crystal structure indicates that the complex has a two-dimensional network structure which is formed by hydrogen bonds.展开更多
A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structur...A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structure of which was characterized by elemental analysis, IR spectrum and X-ray diffraction. Single crystal X-ray analysis indicates that this compound crystallizes in triclinic system, space group P1 with parameters: a=1.180 7(2) nm, b=1.330 0(3) nm, c=1.568 6(2) nm. 1.332 g穋m-3, F(000)=1 032, 腎=0.804+23.770C, r=0.995). CCDC: 231388.展开更多
文摘A copper(Ⅱ) complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-(4-fluorophenyl)iminomethyl-8-quinolinoxy]butane(L). X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387(2), b = 9.968(2), c = 10.291(2) ?, α = 87.532(3), β = 63.762(2), γ = 86.628(3)o, V = 862.1(3) ?^3, Z = 1, Dc = 1.640 Mg/m^3, F(000) = 428, R = 0.0416 and wR = 0.1141. Each Cu(Ⅱ) metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper(Ⅱ) complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.
基金the State Key Project (No. 2005CCA06800)the NSFC/RGC Joint Research Foundation (50418010)
文摘Three polymeric copper(Ⅰ) halide complexes beating phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy = bipyridine), [(PPh3)2Cu2(μ-Br)2(μ- bpe)]∞ 2 (bpe = trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122(3), b = 9.322(3), c = 13.201(4) A, α = 106.440(4), β= 105.965(5), γ= 94.167(5)°, V = 1021.3(6) A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F(000) = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections (I 〉 2σ(I)). Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420(3), b = 10.209(4), c = 12.407(4) A, α = 104.136(6), β = 108.132(5), γ= 95.338(6)°, V = 1081.0(7) A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F(000) = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections (I 〉 2σ(I)). Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32(1), b = 11.53(2), c = 13.94(3) A, α = 109.57(3), β= 93.85(3), γ= 97.28(3)°, V= 1242(4) A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F(000) = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections (I 〉 2σ(I)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.
文摘The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).
基金supported by the Project for Innovation Team of Liaoning Province (No. 2007T052)Liaoning Provincial Key Laboratory (No. 2008S104)Startup Project of Doctor of Liaoning University
文摘The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemental analyses, thermogravimetric analyses, IR and UV-visible spectroscopy. The crystal belongs to the monoclinic system, space group P21/c with a = 9.4564(10), b = 18.2679(19), c = 15.7284(12) A,β= 126.045(4)°, V= 2196.9(4)A^3, Z= 4, Dc = 1.618 g/cm^3, Mr = 535.02,μ = 1.141 mm^-1, F(000) = 1100, 2(MoKα) = 0.71073 A, the final R = 0.0429 and wR = 0.1044 for all observed reflections. In the structure, every two Cu(II) atoms are bridged by a bivalent 5-sulfosalicylic anion to form a 1D chain-like coordination polymer. Lattice waters between chains link them to form 2D layers which are further linked by C-H…O hydrogen bonds to form a three-dimensional supramolecular network.
文摘The title compound [Cu (ADC) (2, 2'-bipy)]n (ADC = C2 (COO)2^2.) was prepared and characterized by elemental analysis, IR spectroscopy, X-ray analysis, respectively. The analysis of the crystal structure reveals that the copper atom is five-coordinated with two nitrogen atoms of 2, 2'-bipy and three oxygen atoms of different acetylenedicarboxylate dianions. ADC as bridging ligands link the Cu (Ⅱ) ions, forming coordination polymer structure.
基金supported by the Natural Science Foundation of the Education Bureau of Anhui Provincethe Program for New Century Excellent Talents in University (2006kj035a and NCET-06-0556)
文摘Reaction of bis(4,6-dimethyl-2-pyrimidinethiolato)methane(bpytm) with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2(μ-bpytm)]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433(5),b=13.6986(4),c=7.8434(2),β=100.371(2)°,V=1790.71(9)3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ(MoKα)=1.751mm-1,F(000)=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ(I) and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025(2) and 2.234(1) A, respectively.
基金supported by the Soft Science project of Shanxi Province(No.2013041020-03)the National Natural Science Foundation of China(No.51174275)
文摘One new polymer, [Na(NPHSNPAB)(CH3OH)]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex: C(17)H(17)N4NaO9S, Mr = 476.39, triclinic system, space group P1, a = 8.8741(18), b = 10.942(2), c = 12.039(2) A, α = 65.74(3), β = 77.49(3), γ = 84.30(3)o, V = 1040.3(4) A3, Z = 2, Dc = 1.521 g/cm^3, λ = 0.71073 A, F(000) = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 〉 2(I). X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium(I) center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units(3.768 A) indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.
文摘The title compound, C24H28ClCuN4O6 (Mr = 567.49), has been prepared and its crystal structure has been determined by X-ray diffraction method. The crystal belongs to monoclinic, space group C2/c with a = 23.1905(14), b = 30.1877(12), c = 7.4881 (3) A, β = 97.631 (2)°, V = 5195.8(4) A^3, Z = 8, Dc = 1.451 g/cm^3,μ = 0.989 mm^-1, F(000) = 2352, S = 1.030, R = 0.0694, wR = 0.2120 (I 〉 2σ(I)), R = 0.0950 and wR = 0.2322 (all data). The crystal consists of the Cu(Ⅰ) complex and lattice water molecules. The Cu(Ⅰ) atom is coordinated by two phenanthroline (phen) molecules and one chlorine anion with a distortetl trigonal dipyramidal coordination geometry. By the aid of aromatic π-π stacking, the Cu(Ⅰ) complex molecules form two-dimensional supramolecular layers. Lattice water molecules locate between the adjacent layers to form a three-dimensional sandwich-like supramolecular structure.
文摘A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I>2σ (Ⅰ)].
基金supported by the National Natural Science Foundation of China (No.20872057)
文摘Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic Pbca,a = 18.5858(12),b = 8.1821(5),c = 20.6066(13) ,V = 3133.7(3) 3,Z = 8,Dc = 1.843 g/cm3,F(000) = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2:Orthorhombic Pbca,a = 18.7883(16),b = 8.3249(7),c = 19.0294(17) ,V = 2976.4(4) 3,Z = 8,Dc = 1.731 g/cm3,F(000) = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3:monoclinic P21/c,a = 13.812(10),b = 9.910(7),c = 23.444(17) ,β = 104.3350(10)°,V = 3090(4) 3,Z = 4,Dc = 1.476 g/cm3,F(000) = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2(1) and C14H16BrCuN2O2(2) are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional(3D) supramolecular network in 1 and a two-dimensional(2D) sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4(3) is ionic.In 3,the [Cu(dmbp)2]+ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional(1D) chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.
文摘A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.
文摘Reaction of Cu powder with 2-thenoyltrifluoroacetone and 2, 2-bipygave a complex [Cu(C8H4SO2F3) (2, 2' -bipy)]. The title compound is monoclinic sys-tem, sapce grop C2/c, a= 17. 892(5), b= 18. 495(4), c= 16. 242(6) A, β=121. 02(2)°, Z=8, V=4606. 2 A3, Dc= 1. 512 g/cm3, μ= 12. 724 cm-1, F(000) = 1766,Mr = 440. 6, Final R = 0. 061 and R. = 0. 071. X-ray crystal structure analysis revealedthat copper(I) is coordinated by two O and two N atoms. The Cu(I) atom displays anearly square planar coordination geometry.
基金Supported by the National Natural Science Foundation of China (NSFC21671084)。
文摘A novel copper(I) coordination polymer [C30 H18 Cu3 Cl3 N4]n was solvethermally synthesized with 1-(prop-2-en-1-yl)-2-{4-[1-(prop-2-en-1-yl)-1 H-1,3-benzodiazol-2-yl]phenyl}-1 H-1,3-benzodiazole as the flexible ligand. It crystalizes in orthorhombic system, space group Pbcn with a = 22.0890(7), b = 6.3626(2), c = 18.2480(6) ?, V = 2564.64(14) ?3 and Mr = 365.73. The compound characterized by elemental analysis, infrared spectroscopy and powder X-ray diffraction analysis displays a 2 D structure. The complex shows strong green luminescence at 506 nm and better property of electrochemical oxygen evolution.
基金ProjectsupportedbytheFoundationofOrganicSynthesisKeyLaboratoryofJiangsuProvince (No .KJS0 10 18)
文摘Two copper complexes [Cu(TTA)(2)(4, 4'-azpy)] (1) and [ Cu- (TTA)(2)(3,3'-azpy)] (2) (HTTA = 1,1,1-trifluoro-3-(2-thenoyl)-acetone, 4,4'-azpy = 4,4'-azobispyridine, 3,3'-azpy = 3,3'-azobispyridine) were synthesized and characterized. The crystal structures were determined by X-ray diffraction analysis. The crystal I belongs to triclinic with space group P1, a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, alpha = 66.126(9)degrees, beta = 79.667(9)degrees, gamma = 90.13(1)degrees, Z = 1, V = 0.6692(2) nm, D-c = 3.425 g/cm(3), mu = 2.113 mm(-1), F(000) = 694, R-1 = 0.0594, wR(2) = 0.1499. The crystal 2 belongs to monoclinic with space group P2(1)/c, a = 1.0661(2) nm, b = 1.4296(3) nm, c = 1.0041(3) nm, beta = 114.50(3)degrees, V = 1.3926(5) nm(3), Z = 2, D-c = 1.646 g/ cm(3), mu = 1.015 mm(-1), F (000) = 694, R-1 = 0.0535, wR(2) = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one-dimensional linear chains linked through the rod- like 4,4'-azpy ligands or 3,3'-azpy ligands.
文摘The copper(Ⅱ) complex [Cu_3(nta)_2(azpy)_2(H_2O)_2]·6H_2O (nta =nitrilotriacetate, azpy = 4,4′-azobispyridine) has been synthesized and characterized. The X-rayanalysis reveals that there are two kinds of copper(Ⅱ) coordination environments. Cu(1) has adistorted square plane symmetry and Cu(2) has a distorted octahedral symmetry. Cu(1) is linked toCu(2) through nta and bound to Cu(1C) by azpy, and Cu(2) is linked to Cu(2A) through azpy, whichextends to two-dimensional network with large rhombus 1.2 nm x 1.7 nm.
文摘In an attempt to synthesize supra-molecular complex of copper(II) with mixed ligands in a solution reaction of Cu(ClO 4) 2·6H 2O with 4,5-diazafluorene-9-one (dafo) and o-phthalic acid, the bright blue column-like crystal [Cu(dafo) 2(H 2O) 2]-(ClO 4) 2 was obtained. Its structure was determined by single-crystal X-ray diffraction study. The crystal belongs to monoclinic system, space group P2(1)/n with cell dimensions: a=0.7947(3) nm, b=1.2021(5) nm, c=1.3190(5) nm, α=90.000(5)°, β=90.000(5)°, γ= 90.000(5)°, V=1.2600(9) nm 3, Z=2, F(000)=670, M r=662.83, D c=1.747 g/cm 3, μ (Mo Kα)=1.154 mm -1, R 1=0.0455, wR 2=0.1041. The analysis of the crystal structure indicates that the complex has a two-dimensional network structure which is formed by hydrogen bonds.
文摘A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structure of which was characterized by elemental analysis, IR spectrum and X-ray diffraction. Single crystal X-ray analysis indicates that this compound crystallizes in triclinic system, space group P1 with parameters: a=1.180 7(2) nm, b=1.330 0(3) nm, c=1.568 6(2) nm. 1.332 g穋m-3, F(000)=1 032, 腎=0.804+23.770C, r=0.995). CCDC: 231388.