Synthesis,Crystal Structure and Magnetic Property of a New Cd（Ⅱ） Complex with Four Nitronyl Nitroxide Radicals

A new Cd(Ⅱ) complex with four nitronyl nitroxide radicals [Cd(NIT4Py)4Cl2](NIT4Py = 2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441(4),b = 13.6964(8),c = 13.7354(8) ,α = 89.8610(10),β = 77.9180(10),γ = 87.2250(10)°,V = 1331.01(13) 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ(MoKα) = 0.573 mm-1,F(000) = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections(I > 2σ(I)).The title complex exists in the mononuclear-metal structures,in which each Cd(Ⅱ) ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.     

氮氧自由基-锌配合物[Zn(NIT3Py)2Cl2]的合成、结构和磁行为

A Zn(Ⅱ) complex with nitronyl nitroxide radicals [Zn(NIT3Py)₂Cl₂] (1) (NIT3Py=2-(3′-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction crystal structure determination method. The complex has a mononuclear-metal structure in which each Zn(Ⅱ) ion adopts a distorted tetrahedral geometry and is coordinated by two Cl^- anions and two pyridyl-N atoms from two NIT3Py radical ligands. The magnetic measurements show the weak antiferromagnetic interaction between the nitroxide radicals through the diamagnetic Zn(Ⅱ) ion. CCDC: 292363.     

A Cu(Ⅱ) Complex with IM-MeImz-к2 N,O Mode in [Cu(IM-MeImz)2]·(SCN)2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.     

A Cu(Ⅱ) Complex with IM-MeImz-к2 N,O Mode in [Cu(IM-MeImz)2]·(SCN)2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.     

二维网状Pd(Ⅱ)配合物的合成、晶体结构及电化学性质(英文)

A novel palladium(Ⅱ) complex [Pd(H2bpdc)Ala]Cl·3H2O (where H2bpdc is 2,2′-bipyridine-3,3′-dicar- boxylic acid and Ala is L-alanine) has been synthesized and characterized by IR spectra and elemental analysis. The crystal structure of the complex has been determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic system, space group P1 with a=0.685 5(2) nm, b=0.988 4(4) nm, c=1.349 6(4) nm, α=98.375(8)°, β= 97.900(15)°, γ=90.118(15)°, V=0.895 9(5) nm3, Z=2. In the molecule, Pd(Ⅱ) atom is four-coordinated and located at the centre of a planar quadrangle. The complex is assembled via intramolecular π-π stacking interactions and hydrogen bonds, which forms 2D network. The cyclic voltammetric behavior of the complex was also investigated.     

四(4-乙烯基吡啶)硝酸铜(Ⅰ)配合物的结构、电化学和热稳定性能研究(英文)

The title complex Cu(Vpy)NO3 (Vpy=4-vinylpyridine) has been synthesized and structurally characterized by X-ray single crystal diffractometry. The complex crystallizes in triclinic system, P1 space group with the cell parameters of a=1.004 2(2) nm, b=1.631 7(3) nm, c=1.887 7(4) nm, α=81.54(2)°, β=77.44(2)°, γ=79.39(2)°, V= 2.948 9(11) nm3, Z=4, and Dc=1.230 g·cm-3, the final R1=0.075 2, wR2=0.139 1. The complex crystallizes with two molecules in the asymmetric unit. Each Cu(Ⅰ) ion is coordinated by four N atom from the Vpy ligands and one O atoms from the nitrate anion, resulted in a square pyramidal geometry. The electrochemical studies reveal that redox of Cu2+/Cu+ in the complex is a quasi-reversible process. CCDC: 736638.     

配合物[Tb(p-ClBA)_3(phen)]_2的结构和性能(英文)

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb( p-ClBA)_3phen]_2 (1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(Ⅲ) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(Ⅲ) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)_3phen]_2 is quite stable to heat. CCDC: 221921.     

A Novel Binuclear Cu（Ⅱ） Complex with Nitroxide Radicals Exhibiting Ferromagnetic Interactions

A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I > 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.     

2-(1H-1,2,4-三氮唑)乙酸Cu(Ⅱ)配合物的水热合成、晶体结构及性质

A copper(Ⅱ) complex [CuL2] [L=2-(1H-1,2,4-triazol-1-yl)acetic acid] has been synthesized by means of hydrothermal method, and characterized by elemental analysis, IR spectra and X-ray diffraction. Crystal data for this complex: monoclinic, space group P21/n, a=0.481 3(2) nm, b=1.151 1(6) nm, c=0.993 9(5) nm, β=100.528(8)°, V=0.541 4(5) nm3, Z=2, F(000)=318, Dc=1.937 g·cm-3, Final GooF=1.109, R1=0.027 6, wR2=0.075 6. The crystal structure shows the copper(Ⅱ) atom is six-coordinated by two triazole nitrogen atom and four carboxylate group oxygen atom from four distinct L- ligand, thereby forming a 2D network structure. The cyclic voltammetric behavior of the complex was described.     

氮氧自由基配合物[Cu(NIT4Py)(IDA)]_n的合成与晶体结构(英文)

A novel one-dimensional (1D) Cu(Ⅱ) nitronyl nitroxide complex bridged by iminodiacetate dianion [Cu(NIT4Py)(IDA)]n,where NIT4Py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and IDA= iminodiacetate dianion,was synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a=0.921 09(10) nm,b=0.780 09(9) nm,c=2.486 3(3) nm,β=96.826(2)°. The Cu(Ⅱ) ion is five-coordinated with a distorted square-pyramidal geometry. Each iminodiacetate dianion bridges two Cu(Ⅱ) ions via a monodentate-tridentate mode into a 1D chain,and these 1D chains are further linked into a 2D network via hydrogen-bonding interactions.     

A Cu(II) Complex with IM-MeImz-κ~2 N,O Mode in [Cu(IM-MeImz)_2]·(SCN)_2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(II) compound with imino nitroxide radicals [Cu(IM-MeImz)2]?(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) , β = 105.0290(10)o, V = 1552.25(19) 3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) = 650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(II) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(II) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(II) ion and radicals.     

配合物[Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O的合成、晶体结构及热稳定性

One novel manganese(Ⅱ) complex [Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O with α-furacrylic acid radical and 1,10-phenanthroline has been synthesized and characterized. Crystal data for this complex:monoclinic,space group C2/c,a=1.082 34(16)nm,b=2.445 8(4) nm,c=1.857 4(3) nm,β=104.353(2)°,V=4.763 5(12) nm3,Dc=1.471 g·cm-3,Z=4,F(000)=2 168. Final GooF=1.004,R1=0.039 7,wR2=0.108 7. The crystal structure shows that two neighboring manganese(Ⅱ) ions are linked together by two bridging α-furacrylic acid radicals and one bridging water molecule,forming a cage structure. The Mn(1)…Mn(1A) bond distance is 0.357 6 nm. Each manganese(Ⅱ) ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline molecule and four oxygen atoms from three α-furacrylic acid radicals and one water molecule,forming distorted octahedral coordination geometry. Thermal stability of the complex was also discussed.     

铜配合物[CuL_2Cl_2]·4H_2O的合成和晶体结构(L=3-乙基-4-对甲氧苯基-5-(2-吡啶基)-1,2,4-三氮唑)

A new copper(Ⅱ)complex,[CuL_2Cl_2]·4H_2O,[L=3-ethyl-4-(p-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole],was synthesized and characterized by X-ray crystallography and infrared spectroscopy.The complex crystallizes in triclinic system with space group P(1),α=0.843 9(7)nm,b=0.965 5(8)nm,c=1.093 6(8)nm,α=84.026(19)°,β=82.33(2)°,γ=89.167(19)°,V=0.878 3(12)nm~3,Z=1 with final R=0.033 8.The copper atom lies in a distorted octahedral environment with two bidentate chelating ligands(L)in the equatorial plane and two Cl~- ions in the axial positions.The ligand L coordinates via one triazole nitrogen and one pyridine nitrogen atom.The molecules are stabilized by intermolecular hydrogen bonds in the crystal lattice.CCDC:705817.     

Synthesis, Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1'-MeBzIm-κ2 N, O Mode

A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals [Cu2(NO3)2(IM-1'-MeBzlm)2(dca)2] (IM-1'-MeBzlm = 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimi-dazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinie, space group P1, with a =9.440(5), b = 10.124(6), c = 11.603(7)(A°), α= 102.904(7),β = 94.033(6), γ= 104.299(7)°,C34H40Cu2N16O8, Mr= 927.90, V= 1038.2(10) (A°)3, Z = 1, Dc=1.484 g/cm3,μ(MoKα) = 1.093 mm-1,F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with I > 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1'-MeBzlm ligand coordinates to the metal ion with the κ2 N(1'-MeBzlm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1'-MeBzlm are ferromagnetic with J = 12.46 cm-1, where the spin Hamitonian is defined as H= -2JS1S2 within the complex.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

A Chain Cadmium(Ⅱ) Coordination Polymer with Diacylhydrazide: Synthesis,Crystal Structure and Luminescent Property

A novel Cd(Ⅱ) coordination polymer with diacylhydrazide ligand N,N?-bis(3-methoxysalicyl)-2,6-pyridinedicarbohydrazide(H_6msphz),[Cd_2(H_2msphz)(Py)_4]_n(1,Py = pyridine) has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230(11),b = 11.7264(15),c = 17.3395(14) ?,α = 70.520(9),β = 84.806(7),γ = 81.965(9)°,V = 2089.9(4) ?~3,Dc = 1.638 gcm~(–3),μ = 1.083 mm~(-1),F(000) = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd(Ⅱ) ion,but also its two terminal groups to chelate other two Cd(Ⅱ) ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π* transitions.     

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5-Benzenetetracarboxylato Trivalent Anion

The title complex [(phen)2Cu(Htcb)Cu(phen)2]H3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.     

Hydrothermal Synthesis,Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd(H2biim)2(H2O)2]·(ino)2·4H2O (H2biim = 2,2'-biimidazole, ino = isonicotinate-N-oxide) has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380(6), b = 8.0402(7), c = 13.5094(11) , α = 104.269(1), β = 93.604(1), γ = 98.349(1)°, V = 780.93(11) 3, Mr = 765.00, Dc = 1.627 g/cm3, F(000) = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ(I) and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.     

一维链状锰配位聚合物[Mn(1,5-nds)(Him)_4]_n的合成、晶体结构及热稳定性研究(英文)

The synthesis,structural characterization and thermal behavior of a novel one-dimensional manganese (Ⅱ) complex of formula [Mn(1,5-nds)(Him)4]n [1,5-nds=naphthalene-1,5-disulfonate,Him=imidazole] is reported.The complex crystallizes in the triclinic system,space group P1,with a=0.835 42(13) nm,b=0.983 45(18) nm,c= 0.987 42(19) nm,α=60.523 0(10)°,β=97.748(2)°,γ=87.189(2)° and Z=2.The 1,5-nds ligand assumes the μ2 coordination mode and interlinks Mn(Ⅱ) ions into infinite one-dimensional chain structure along [111] direction,with the adjacent Mn…Mn distance being 1.144 99(12) nm.The chains are assembled into a three-dimensional supramolecular architecture via hydrogen bonds and C-H…π interactions.IR spectra and thermal analysis data are in agreement with the crystal structure.     

Syntheses, Structural Characterization of Fe and Ni Complexes with Polypyrazolyl Borate Ligand ： Fe [ HB （pz） 3 ] 2 and Ni [ HB （pz） 3 ] 2

Fe(Ⅱ) complex Fe[HB(pz)3]2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)3]2(compound 2) have been obtained by the reaction of MCI2(M=Fe and Ni) with NaHB(pz)3 in MeOH. The two complexes(compounds 1 and 2) were characterized by IR, NMR, elemental analysis and X-ray diffraction. Compound 1 crystallizes in space group P21/c with a=1.224(3) nm, b=1.161(2) nm, c=1.648(3) nm, β=107.62(15)°, V=2.233(8) nm3, Z=2. Compound 2 crystallizes in space group P21/c with a=0.97926(18) nm, b=1.7423(3) nm, c=1.3156(2) nm, β=97.055(16)°, V=2.2277(7) nm3, Z=4. The results of X-ray structural analyses show that both compounds 1 and 2 are monomeric neutral, possessing a similar coordination mode and a similar structure around the metal centers. The related spectral characterizations, steric effects and binding properties are discussed.