A novel Cu(II)-2,2'-bipy-supported (bipy = bipyridine) mixed valence decatungstate, [Cu(2,2'-bipy)2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crys...A novel Cu(II)-2,2'-bipy-supported (bipy = bipyridine) mixed valence decatungstate, [Cu(2,2'-bipy)2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1^- with a= 10.9393(10), b = 12.0492(2), c = 12.3783(2)A, a = 80.631(10), β= 70.226(10), γ= 72.329(9)^o, V = 1459.64(4)A^3, Z = 1, Dc = 3.582 g/cm^3, F(000) = 1404, R = 0.0553 and wR = 0.1242 for 4607 observed reflections (I 〉 2σ(I)). The EPR spectrum of 1 indicates that its unpaired electrons are placed in the dx2-y2 orbital of the ground state of Cun. Furthermore, compound 1 shows an antiferromagnetic interaction.展开更多
Reaction of hydrated ytterbium nitrate and copper nitrate with diglycolic acid at pH= 7 produced a new Yb-Cu mixed metal complex, Yb2Cu3L6. 6H2O(L= O(CH2COO)2). Complex Yb2Cu3O36C2H36 (Mr= 1437. 23) crystallized in he...Reaction of hydrated ytterbium nitrate and copper nitrate with diglycolic acid at pH= 7 produced a new Yb-Cu mixed metal complex, Yb2Cu3L6. 6H2O(L= O(CH2COO)2). Complex Yb2Cu3O36C2H36 (Mr= 1437. 23) crystallized in hexagonalP6/mcc (No. 192) with cell parameters of a= 14. 344 (3), c= 15. 470(7) A,V= 2757(2) A 3; Z= 2; F(000) = 1390; Dcalc.= 1- 731 g/cm3 μ(MoKa) =45. 8 cm-1. The final agreernent factors are R= 0. 077 and Rw = 0.089 for 867 observed reflections with I>3δ(I). It has been characterized by elemental analysis, IR spectrum, magnetic measurement and X-ray crystallography. In the complex, the Yb3+ ion is 9-coordinated tothree ether oxygen and six carboxylate oxygen atoms from three ligands, the copper ionis coordinated to four oxygen atoms from four carboxylate groups of four ligands andtwo water molecules. The Yb3+ ions and the Cu2+ ions are connected by the carboxylate groups of the ligands, thus resulting in the formation of the complicated networkstructure.展开更多
The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP = 5-sulfoisophthalic acid), has been synthesized by the hydrothermal reaction of CuCI2 with NaH2SIP at 160 ℃, and characterized by single-cry...The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP = 5-sulfoisophthalic acid), has been synthesized by the hydrothermal reaction of CuCI2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum. The crystal of the complex crystallizes in a triclinic system, space group P^-1, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13)A^°, α = 78.8540(10), β = 85.1710(10), γ = 83.6080(10)°, V = 1553.24(19)A^°^3 Z = 1, C32H60O51S4Cu5, Mr= 1706.74, Dc= 1.825 g/cm^3,μ = 1.937 mm^-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I 〉 2σ(I). The five Cu^2+ ions are connected by two symmetry-related tddentate SIP^3- ligands and charge-balanced by two monodentate HSIP^2- ligands, giving a discrete pentanuclear structure. The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu^2+ ions.展开更多
A new ternary neodymium zirconium sulfide Nd_2ZrS_5 was synthesized by high-temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic spac...A new ternary neodymium zirconium sulfide Nd_2ZrS_5 was synthesized by high-temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic space group Pnma(No. 62) belonging to the Y_2HfS_5 structure-type with a = 11.461(4), b = 8.009(3), c = 7.315(3) A, Z = 2 and V = 671.5(4)A3. Its structure features NdS_8 and ZrS_7 polyhedra-constructed a 3-D network. The data of magnetic susceptibility indicate its antiferromagnetic-like behavior without magnetic order down to 2 K.展开更多
A novel compound, (IBzQI)(TCNQ)2 2 (IBzQ1=1-(4-iodobenzyl)quinolinium and TCNQ = 7,7,8,8-tetracyanoquinodimethane) has been fabricated and X-ray single-crystal structurally analyzed. This compound crystallizes...A novel compound, (IBzQI)(TCNQ)2 2 (IBzQ1=1-(4-iodobenzyl)quinolinium and TCNQ = 7,7,8,8-tetracyanoquinodimethane) has been fabricated and X-ray single-crystal structurally analyzed. This compound crystallizes in the triclinic system, space group P1 with a = 8.3540(17), b = 13.284(3), c = 16.185(3) А, α= 82.12(3), β= 75.19(3), γ= 72.34°, V = 1651.2(6) А^3, Z= 2, C_40H_21IN_9, Mr = 754.56, Dc = 1.518 g/cm^3,μ= 1.015 mm^-1, S = 1.010, F(000) = 754, R = 0.0387 and wR = 0.0948. The structure analysis shows that the anions are stacked into column with tetrads, and there are two types of TCNQ entries (TCNQ-1 and TCNQ^0) in agreement with the IR spectra analysis of the compound. The temperature dependence of the magnetic susceptibility (2-300 K) for 2 exhibits spin gap of singlet-triplet feature, and the best fit gave △/kB = 1523.4 K. In order to understand both magnetic behavior and local charge distribution of [(TCNQ)2]-unit, the molecular orbital calculations and analysis based on extended Hückel method were performed, and the results support the analyses of both crystal structure and IR spectra.展开更多
One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxyli...One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(Hbtc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.展开更多
A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18....A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)A, V = 2074.42(7)A^3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm^3, μ = 0.670 mm^-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ〉 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.展开更多
A new complex [Co(4,4'-bpy)2(H2O)2(4-FBA)2]·(4,4'-bpy)(1) has been hydro-thermally synthesized using cobalt,4,4'-bipyridyl(4,4'-bpy) and 4-fluorobenzoic acid(4-HFBA),and characterized by thermal...A new complex [Co(4,4'-bpy)2(H2O)2(4-FBA)2]·(4,4'-bpy)(1) has been hydro-thermally synthesized using cobalt,4,4'-bipyridyl(4,4'-bpy) and 4-fluorobenzoic acid(4-HFBA),and characterized by thermal analysis,single-crystal X-ray diffraction and magnetic property.The complex crystallizes in the triclinic system,space group P,Z = 1.Crystal data:C54H44CoF2N8O6,Mr = 997.90,a = 9.134(2),b = 11.555(2),c = 12.867(3) ,α = 66.02(3),β = 77.96(3),= 73.11(3)°,V = 1180.9(4) 3,Dc = 1.403 g/cm3,μ(MoKα) = 0.433 mm-1,F(000) = 517,the final R = 0.0633 and wR = 0.1171 for 2152 observed reflections(I 〉 2σ(I)).The title complex is assembled into 1D supramolecular chains parallel to [001] based on the adjacent molecular ··· stacking interactions and hydrogen bonds.The variable temperature magnetic measurements show a weak ferromagnetic behavior over 300-160 K followed by antiferromagnetic behavior below 160 K for the title complex.展开更多
The title compound, Na 2Co(CO 3) 2·4H 2O, was synthesized by dropwise addition of 1.0 mL of 1 mol/L Co(CH 3COO) 2 to 50 mL of aqueous solution containing 7.0 g(66.0 mmol) of Na 2CO 3 and 2.5 g(29.8 mmol)...The title compound, Na 2Co(CO 3) 2·4H 2O, was synthesized by dropwise addition of 1.0 mL of 1 mol/L Co(CH 3COO) 2 to 50 mL of aqueous solution containing 7.0 g(66.0 mmol) of Na 2CO 3 and 2.5 g(29.8 mmol) of NaHCO 3 under stirring. A rose colored rhombohedral crystal grew by the slow evaporation of the solution of the title compoud at room temperature. The crystal structure was established on the basis of the single crystal X ray diffraction data. Na 2Co(CO 3) 2·4H 2O crystallizes in the monoclinic space group C2/c with a =0.856 6(1) nm, b =0.714 6(1) nm, c = 1 438 7(2) nm, β =97.59(1)° , V =0.873 0(2) nm 3 , D x=2.260 g/cm 3, F (000)=596, M r=296 99, μ (Mo K α)=21.06 cm -1 , Z =4 and the final R(F) =0.032 and wR(F 2) =0.068 on the basis of 947 reflections ( F 2 ≥ 2σ(F 0 2)). The crystal consists of H 2O molecules, Na + ions and 2D 2 ∞[Co(CO 3) 2] 2- layers extending parallel to (001). H 2O molecules and Na + cations are located between the 2D layers. Each Co atom is tetrahedrally coordinated by four O atoms from four CO 2- 3 groups with d (Co\_O)=0.206 5(2) nm, 0.207 6(2) nm and the angle of O\_Co\_O is in the range of 97.7(1)°—128.5(1)°. The CO 2- 3 group bridging two Co atoms via two O atoms deviates from D 3h symmetry with d (C\_O)=0.127 2(3)\_0.129 9(3) nm and the angle of O\_C\_O is in the range of 119.5(2)°\_123.4(2)°. Each Na atom, with two close Na neighbours at 0.338 4(2) nm and 0 346 7(2) nm, respectively, is octahedrally coordinated by six O atoms from four H 2O molecules and two carbonate groups belonging to two layers with d (Na\_O)=0.232 7(2)\_0.241 1(2) nm. Of two crystallographically different H 2O molecules, one forms hydrogen bonds to two CO 3 2- groups of one 2D layer, and the other to those from two different 2D layers. Na 2Co(CO 3) 2·4H 2O is antiferromagnetic below 16 K, and between 30\_300 K its magnetic behaviour obeys Curie Weiss law χ m(cm 3·mol -1 )=2.625/( T -12.1) with μ eff =4.5 B.M. at 298 K.展开更多
A new mixed metal iodate, namely Ag Cu(IO3)3, has been prepared using hydrothermal method. Ag Cu(IO3)3 crystallizes in the triclinic group P1 with a = 7.3063(6), b = 7.8050(6), c = 8.2447(6) A, α = 67.212(...A new mixed metal iodate, namely Ag Cu(IO3)3, has been prepared using hydrothermal method. Ag Cu(IO3)3 crystallizes in the triclinic group P1 with a = 7.3063(6), b = 7.8050(6), c = 8.2447(6) A, α = 67.212(7), β = 74.978(7), γ = 80.972(7)°, V = 417.80(6) A^3 and Z = 2. The structure features one-dimensional [Cu(IO3)3]n^n- anionic chains that are separated by Ag~+ cations. Such [Cu(IO3)3]n^n- chain is composed of [Cu2O(11)]n chain decorated by unidentate hanging and bidentate bridging iodate groups. Thermal study implies that Ag Cu(IO3)3 is thermally stable up to 460 oC and the optical measurement determined the optical band gap of 3.11 eV with a broad absorption band centered at 765 nm. Magnetic investigations show that Ag Cu(IO3)3 is a soft ferromagnet.展开更多
A new dinuclear iron(Ill) complex has been synthesized and structurally charac- terized by X-ray crystallography: [Fem2(L)(C6HsCOO)(SO4)(CH3OH)2]·CH3CN'CH3OH (1, H3L = N,N'-bis(salicylidene)q,3-di...A new dinuclear iron(Ill) complex has been synthesized and structurally charac- terized by X-ray crystallography: [Fem2(L)(C6HsCOO)(SO4)(CH3OH)2]·CH3CN'CH3OH (1, H3L = N,N'-bis(salicylidene)q,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400(8), b = 22.9705(2), c = 12.5712(9)A, V= 3303.5(4)A3, Z= 4, F(000) = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.展开更多
A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffr...A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13)A, β = 103.904(2)°, V = 1919.6(5)A^3, Dc = 1.528 g/cm^3, μ(MoKα) = 1.579 mm^-1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I〉 2σ(I). X-ray analysis reveals that the Zn(Ⅱ) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.展开更多
Two metal-dithiolene compounds with a formula of[4-ClBz-l-APy][Ni(dmit)2](1)and[4-NO2Bz-l-APy][Ni(dmit)2](2,4-ClBz-1-APy = 1-N-(4'-chlorobenzyl)pyridinium,4-NO2Bz-1-APy = l-N-(4'-nitrobenzyl)pyridinium,dm...Two metal-dithiolene compounds with a formula of[4-ClBz-l-APy][Ni(dmit)2](1)and[4-NO2Bz-l-APy][Ni(dmit)2](2,4-ClBz-1-APy = 1-N-(4'-chlorobenzyl)pyridinium,4-NO2Bz-1-APy = l-N-(4'-nitrobenzyl)pyridinium,dmit^(2-)= 1,3-dithiole-2-thione-4,5-dithiolate) were synthesized and characterized.Two compounds crystallize in triclinic space group P1 and P1,respectively,but with different cell parameters and packing structures.The[Ni(dmit)2]^- anions and cations of 1 form mixed column stacks along the a axis and alternately layered alignments in the crystal of 2,which are parallel to the crystallographic(110) plane.Two compounds show a similar magnetic behavior,the magnetic exchange natures are mainly antiferromagnetic,and the magnetic susceptibility data can be fitted to the simple Curie-Weiss law.For 1 and 2,the fitted Curie constants are much less than the spin-only value expected for an S =1/2 system,and the fitted Weiss constants marking magnetic interaction are also very smaller.This fact implies that the weak CurrieWeiss-type paramagnetism is not the intrinsic characteristics of two compounds.展开更多
A 2D coordination polymer, [Co(NPA)(H_2 O)_2]_n(1, H_2 NPA = 3-nitrophthalic acid), has been synthesized by solvothermal method and characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy,...A 2D coordination polymer, [Co(NPA)(H_2 O)_2]_n(1, H_2 NPA = 3-nitrophthalic acid), has been synthesized by solvothermal method and characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. Complex 1 crystallizes in orthorhombic space group Pbca with a = 7.2261(2), b = 14.6450(5), c = 19.6671(7) ?, V = 2081.31(11) ?~3, Z = 8, C_8 H_7 CoNO_8, M_r = 304.08, D_c = 1.941 mg/m^3, μ = 1.686 mm^(-1), S = 1.054, F(000) = 1224, the final R = 0.0248 and wR = 0.0603 for 1834 observed reflections(I 〉 2σ(I)). The crystal structural analysis demonstrates that the Co(Ⅱ) ions in 1 are linked by single and double μ_2-1,3-bridging carboxylate bridges, forming a 2D layer structure. Moreover, magnetic property of 1 was also discussed.展开更多
An iron(Ⅱ) coordination polymer, [Fe(Haip)2(H2O)2]n (1, Haip = 5-ammoniumiso- phthalato), has been hydro/solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, i...An iron(Ⅱ) coordination polymer, [Fe(Haip)2(H2O)2]n (1, Haip = 5-ammoniumiso- phthalato), has been hydro/solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectrum and magnetic measurement. Compound 1 crystalizes in monoclinic, space group P2/c with a = 6.9874(14), b = 9.960(2), c = 12.894(4) A, β = 117.47(2)°, Fe(C8H6NO4)2(H2O)2, Mr = 452.16, V= 796.2(3) A3, Z = 2, Dc = 1.886 g.cm-3, p = 1.017 mm-1, F(000) = 464.0, 2.71〈0〈28.42°, R = 0.0307, wR = 0.0840 and S = 1.005. Single-crystal X-ray diffraction analysis reveals that 1 features an infinite one-dimensional loop-like chain structure and Haip ligand in 1 is of zwitterionic form. Magnetic measurement results show the dominated ferromagnetic interactions among Fe11 atoms.展开更多
A new 2D compound,{[Mn6 L3(H2O)8]·0.69(C3 H7 NO)·3.31H2O}n(1,H4 L=1,1’-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylic acid)),was synthesized and characterized by IR,TGA and X-ray single-crys...A new 2D compound,{[Mn6 L3(H2O)8]·0.69(C3 H7 NO)·3.31H2O}n(1,H4 L=1,1’-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylic acid)),was synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group C2/c with a=26.468(5),b=19.750(4),c=13.660(3)A,β=92.73(3)°,V=7132(2)A^3,Z=4,Mr=1824.12,Dc=1.699 g/cm3,F(000)=3705,R=0.042 and w R=0.117 for 8965 observed reflections(I>2σ(I)).In compound 1,all of the Mn(II)atoms are six-coordinated and take the octahedral geometry of[MnNO5].The 2D compound consists of secondary building unit[Mn3(μ2-O)(R-COO)3](SBU),in which two of the Mn^2+ions exhibit the same coordinated environments while another Mn^2+ion has a different one.The SBUs further connect with each other to form a 1 D inorganic chain which is connected with L^4-ligands to construct a 2D layer.Finally,strong O–H···O hydrogen bonds among the rich carboxyl molecules and O atoms from free DMF and guest water molecules connect the two-dimensional coordination network into a three-dimensional framework.Variable temperature magnetic measurements indicate the antiferromagnetic behavior in the Mn3 core in compound 1.展开更多
A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurall...A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurally as well as magnetically in detail. The crystal belongs to the monoclinic system, space group P2_1/c with a = 9.6896(1), b = 20.539(4), c = 12.147(2) ?, β = 93.84(3)°, M_r = 997.65, V = 2412.1(8) ?~3, Z = 2, Dc = 1.374 g/cm, F(000) = 1038, m = 0.635 mm^(-1), the final R = 0.0539 and w R = 0.1289 for 5998 observed reflections(I 〉 2σ(I)). The Co(Ⅱ) ion is coordinated by two nitrogen atoms of quinoxaline rings from two NITQs and four oxygen atoms from two acac ions to complete a distorted octahedral coordination environment. Compound 1 is further linked into a three-dimensional(3D) supramolecular network by hydrogen-bonding, Cl×××O weak contact and π···π stacking interactions. The magnetic measurements show compound 1 exhibits weak ferromagnetic interactions.展开更多
A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhom...A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.展开更多
One new mixed-valence heptanuclear manganese complex, [Mn^ⅡMn^Ⅲ6O2L6-(NaCH3COO)2(CH3COO)4](1)(L = 3-ethoxy-6-((2-hydroxyethyl)imino)methyl) phenol, was synthesized by treating the Schiff-base ligand with Mn(acac)3...One new mixed-valence heptanuclear manganese complex, [Mn^ⅡMn^Ⅲ6O2L6-(NaCH3COO)2(CH3COO)4](1)(L = 3-ethoxy-6-((2-hydroxyethyl)imino)methyl) phenol, was synthesized by treating the Schiff-base ligand with Mn(acac)3·4H2O and characterized by elemental analysis, IR spectra, thermogravimetric analyses and X-ray single-crystal diffraction. 1 has a similar new mixed-valence heptanuclear structure. The magnetic measurements indicate that 1 exhibits the antiferromagnetic interactions.展开更多
基金Supported by the NNSFC (90206040)NSF of Fujian Province (2006F3134, 2005J058)
文摘A novel Cu(II)-2,2'-bipy-supported (bipy = bipyridine) mixed valence decatungstate, [Cu(2,2'-bipy)2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1^- with a= 10.9393(10), b = 12.0492(2), c = 12.3783(2)A, a = 80.631(10), β= 70.226(10), γ= 72.329(9)^o, V = 1459.64(4)A^3, Z = 1, Dc = 3.582 g/cm^3, F(000) = 1404, R = 0.0553 and wR = 0.1242 for 4607 observed reflections (I 〉 2σ(I)). The EPR spectrum of 1 indicates that its unpaired electrons are placed in the dx2-y2 orbital of the ground state of Cun. Furthermore, compound 1 shows an antiferromagnetic interaction.
文摘Reaction of hydrated ytterbium nitrate and copper nitrate with diglycolic acid at pH= 7 produced a new Yb-Cu mixed metal complex, Yb2Cu3L6. 6H2O(L= O(CH2COO)2). Complex Yb2Cu3O36C2H36 (Mr= 1437. 23) crystallized in hexagonalP6/mcc (No. 192) with cell parameters of a= 14. 344 (3), c= 15. 470(7) A,V= 2757(2) A 3; Z= 2; F(000) = 1390; Dcalc.= 1- 731 g/cm3 μ(MoKa) =45. 8 cm-1. The final agreernent factors are R= 0. 077 and Rw = 0.089 for 867 observed reflections with I>3δ(I). It has been characterized by elemental analysis, IR spectrum, magnetic measurement and X-ray crystallography. In the complex, the Yb3+ ion is 9-coordinated tothree ether oxygen and six carboxylate oxygen atoms from three ligands, the copper ionis coordinated to four oxygen atoms from four carboxylate groups of four ligands andtwo water molecules. The Yb3+ ions and the Cu2+ ions are connected by the carboxylate groups of the ligands, thus resulting in the formation of the complicated networkstructure.
基金Supported by the Education Department of Jiangxi Province (No. 2007-125)Jiangxi Normal University
文摘The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP = 5-sulfoisophthalic acid), has been synthesized by the hydrothermal reaction of CuCI2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum. The crystal of the complex crystallizes in a triclinic system, space group P^-1, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13)A^°, α = 78.8540(10), β = 85.1710(10), γ = 83.6080(10)°, V = 1553.24(19)A^°^3 Z = 1, C32H60O51S4Cu5, Mr= 1706.74, Dc= 1.825 g/cm^3,μ = 1.937 mm^-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I 〉 2σ(I). The five Cu^2+ ions are connected by two symmetry-related tddentate SIP^3- ligands and charge-balanced by two monodentate HSIP^2- ligands, giving a discrete pentanuclear structure. The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu^2+ ions.
基金Supported by Higher Education Science Foundation of Jiangsu Province(No.15KJB150031)State Key Laboratory of Structural Chemistry Fund(No.20150009)+1 种基金Yangzhou University for the start-up grantthe Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘A new ternary neodymium zirconium sulfide Nd_2ZrS_5 was synthesized by high-temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic space group Pnma(No. 62) belonging to the Y_2HfS_5 structure-type with a = 11.461(4), b = 8.009(3), c = 7.315(3) A, Z = 2 and V = 671.5(4)A3. Its structure features NdS_8 and ZrS_7 polyhedra-constructed a 3-D network. The data of magnetic susceptibility indicate its antiferromagnetic-like behavior without magnetic order down to 2 K.
基金supported by the National Natural Science Foundation of China (No. 20731004)Natural Science Foundation of Anhui Provincial Education Commission (No. KJ2008B004)
文摘A novel compound, (IBzQI)(TCNQ)2 2 (IBzQ1=1-(4-iodobenzyl)quinolinium and TCNQ = 7,7,8,8-tetracyanoquinodimethane) has been fabricated and X-ray single-crystal structurally analyzed. This compound crystallizes in the triclinic system, space group P1 with a = 8.3540(17), b = 13.284(3), c = 16.185(3) А, α= 82.12(3), β= 75.19(3), γ= 72.34°, V = 1651.2(6) А^3, Z= 2, C_40H_21IN_9, Mr = 754.56, Dc = 1.518 g/cm^3,μ= 1.015 mm^-1, S = 1.010, F(000) = 754, R = 0.0387 and wR = 0.0948. The structure analysis shows that the anions are stacked into column with tetrads, and there are two types of TCNQ entries (TCNQ-1 and TCNQ^0) in agreement with the IR spectra analysis of the compound. The temperature dependence of the magnetic susceptibility (2-300 K) for 2 exhibits spin gap of singlet-triplet feature, and the best fit gave △/kB = 1523.4 K. In order to understand both magnetic behavior and local charge distribution of [(TCNQ)2]-unit, the molecular orbital calculations and analysis based on extended Hückel method were performed, and the results support the analyses of both crystal structure and IR spectra.
基金Supported by the Natural Science Foundation of Guangxi Province(No.2017GXNSFAA198268)the Foundation of Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials(EMFM20161102)the National Natural Science Foundation of China(No.61765005)
文摘One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(Hbtc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.
基金This project was supported by the NNSFC (No. 20471061) the Science & Technology Innovation Foundation for the Young Scholars of Fujian Province (No. 2005J059)
文摘A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)A, V = 2074.42(7)A^3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm^3, μ = 0.670 mm^-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ〉 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.
文摘A new complex [Co(4,4'-bpy)2(H2O)2(4-FBA)2]·(4,4'-bpy)(1) has been hydro-thermally synthesized using cobalt,4,4'-bipyridyl(4,4'-bpy) and 4-fluorobenzoic acid(4-HFBA),and characterized by thermal analysis,single-crystal X-ray diffraction and magnetic property.The complex crystallizes in the triclinic system,space group P,Z = 1.Crystal data:C54H44CoF2N8O6,Mr = 997.90,a = 9.134(2),b = 11.555(2),c = 12.867(3) ,α = 66.02(3),β = 77.96(3),= 73.11(3)°,V = 1180.9(4) 3,Dc = 1.403 g/cm3,μ(MoKα) = 0.433 mm-1,F(000) = 517,the final R = 0.0633 and wR = 0.1171 for 2152 observed reflections(I 〉 2σ(I)).The title complex is assembled into 1D supramolecular chains parallel to [001] based on the adjacent molecular ··· stacking interactions and hydrogen bonds.The variable temperature magnetic measurements show a weak ferromagnetic behavior over 300-160 K followed by antiferromagnetic behavior below 160 K for the title complex.
文摘The title compound, Na 2Co(CO 3) 2·4H 2O, was synthesized by dropwise addition of 1.0 mL of 1 mol/L Co(CH 3COO) 2 to 50 mL of aqueous solution containing 7.0 g(66.0 mmol) of Na 2CO 3 and 2.5 g(29.8 mmol) of NaHCO 3 under stirring. A rose colored rhombohedral crystal grew by the slow evaporation of the solution of the title compoud at room temperature. The crystal structure was established on the basis of the single crystal X ray diffraction data. Na 2Co(CO 3) 2·4H 2O crystallizes in the monoclinic space group C2/c with a =0.856 6(1) nm, b =0.714 6(1) nm, c = 1 438 7(2) nm, β =97.59(1)° , V =0.873 0(2) nm 3 , D x=2.260 g/cm 3, F (000)=596, M r=296 99, μ (Mo K α)=21.06 cm -1 , Z =4 and the final R(F) =0.032 and wR(F 2) =0.068 on the basis of 947 reflections ( F 2 ≥ 2σ(F 0 2)). The crystal consists of H 2O molecules, Na + ions and 2D 2 ∞[Co(CO 3) 2] 2- layers extending parallel to (001). H 2O molecules and Na + cations are located between the 2D layers. Each Co atom is tetrahedrally coordinated by four O atoms from four CO 2- 3 groups with d (Co\_O)=0.206 5(2) nm, 0.207 6(2) nm and the angle of O\_Co\_O is in the range of 97.7(1)°—128.5(1)°. The CO 2- 3 group bridging two Co atoms via two O atoms deviates from D 3h symmetry with d (C\_O)=0.127 2(3)\_0.129 9(3) nm and the angle of O\_C\_O is in the range of 119.5(2)°\_123.4(2)°. Each Na atom, with two close Na neighbours at 0.338 4(2) nm and 0 346 7(2) nm, respectively, is octahedrally coordinated by six O atoms from four H 2O molecules and two carbonate groups belonging to two layers with d (Na\_O)=0.232 7(2)\_0.241 1(2) nm. Of two crystallographically different H 2O molecules, one forms hydrogen bonds to two CO 3 2- groups of one 2D layer, and the other to those from two different 2D layers. Na 2Co(CO 3) 2·4H 2O is antiferromagnetic below 16 K, and between 30\_300 K its magnetic behaviour obeys Curie Weiss law χ m(cm 3·mol -1 )=2.625/( T -12.1) with μ eff =4.5 B.M. at 298 K.
基金supported by the Natural Science Foundation of Fujian Province(No.2015J05045)the National Natural Science Foundation of China(No.21373222,21231006)
文摘A new mixed metal iodate, namely Ag Cu(IO3)3, has been prepared using hydrothermal method. Ag Cu(IO3)3 crystallizes in the triclinic group P1 with a = 7.3063(6), b = 7.8050(6), c = 8.2447(6) A, α = 67.212(7), β = 74.978(7), γ = 80.972(7)°, V = 417.80(6) A^3 and Z = 2. The structure features one-dimensional [Cu(IO3)3]n^n- anionic chains that are separated by Ag~+ cations. Such [Cu(IO3)3]n^n- chain is composed of [Cu2O(11)]n chain decorated by unidentate hanging and bidentate bridging iodate groups. Thermal study implies that Ag Cu(IO3)3 is thermally stable up to 460 oC and the optical measurement determined the optical band gap of 3.11 eV with a broad absorption band centered at 765 nm. Magnetic investigations show that Ag Cu(IO3)3 is a soft ferromagnet.
基金Supported by the Natural Science Foundation of Mongolian Autonomous Region,China(No.2014MS0215)
文摘A new dinuclear iron(Ill) complex has been synthesized and structurally charac- terized by X-ray crystallography: [Fem2(L)(C6HsCOO)(SO4)(CH3OH)2]·CH3CN'CH3OH (1, H3L = N,N'-bis(salicylidene)q,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400(8), b = 22.9705(2), c = 12.5712(9)A, V= 3303.5(4)A3, Z= 4, F(000) = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.
基金supported by the National Natural Science Foundation of China (Nos. 20471026 and 20771054)the Henan Tackle Key Problem of Science and Technology (No. 0524220001)
文摘A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13)A, β = 103.904(2)°, V = 1919.6(5)A^3, Dc = 1.528 g/cm^3, μ(MoKα) = 1.579 mm^-1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I〉 2σ(I). X-ray analysis reveals that the Zn(Ⅱ) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.
基金supported by the National Natural Science Foundation of ChinaNatural Science Foundation of High Learning Institutions of Anhui ProvinceScience Supported Foundation of Nanjing Xiaozhuang College(No.21201103,KJ2012ZD11 and 2014XZRC01)
文摘Two metal-dithiolene compounds with a formula of[4-ClBz-l-APy][Ni(dmit)2](1)and[4-NO2Bz-l-APy][Ni(dmit)2](2,4-ClBz-1-APy = 1-N-(4'-chlorobenzyl)pyridinium,4-NO2Bz-1-APy = l-N-(4'-nitrobenzyl)pyridinium,dmit^(2-)= 1,3-dithiole-2-thione-4,5-dithiolate) were synthesized and characterized.Two compounds crystallize in triclinic space group P1 and P1,respectively,but with different cell parameters and packing structures.The[Ni(dmit)2]^- anions and cations of 1 form mixed column stacks along the a axis and alternately layered alignments in the crystal of 2,which are parallel to the crystallographic(110) plane.Two compounds show a similar magnetic behavior,the magnetic exchange natures are mainly antiferromagnetic,and the magnetic susceptibility data can be fitted to the simple Curie-Weiss law.For 1 and 2,the fitted Curie constants are much less than the spin-only value expected for an S =1/2 system,and the fitted Weiss constants marking magnetic interaction are also very smaller.This fact implies that the weak CurrieWeiss-type paramagnetism is not the intrinsic characteristics of two compounds.
基金supported financially by the Scientific Research Program Funded by Shaanxi Provincial Education Department(No.16JK1598,16JK1612,17JK0606)the Natural Science Foundation of Shaanxi Province(No.2017JQ2009)
文摘A 2D coordination polymer, [Co(NPA)(H_2 O)_2]_n(1, H_2 NPA = 3-nitrophthalic acid), has been synthesized by solvothermal method and characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. Complex 1 crystallizes in orthorhombic space group Pbca with a = 7.2261(2), b = 14.6450(5), c = 19.6671(7) ?, V = 2081.31(11) ?~3, Z = 8, C_8 H_7 CoNO_8, M_r = 304.08, D_c = 1.941 mg/m^3, μ = 1.686 mm^(-1), S = 1.054, F(000) = 1224, the final R = 0.0248 and wR = 0.0603 for 1834 observed reflections(I 〉 2σ(I)). The crystal structural analysis demonstrates that the Co(Ⅱ) ions in 1 are linked by single and double μ_2-1,3-bridging carboxylate bridges, forming a 2D layer structure. Moreover, magnetic property of 1 was also discussed.
基金supported by the Scientific Research Start-up Funds of Shangrao Normal Universitythe Fourth Characteristic Specialty Foundation of University from Ministry of Education(TS11524)the Natural Science Foundation of Jiangxi Province(No.20122BAB203002)
文摘An iron(Ⅱ) coordination polymer, [Fe(Haip)2(H2O)2]n (1, Haip = 5-ammoniumiso- phthalato), has been hydro/solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectrum and magnetic measurement. Compound 1 crystalizes in monoclinic, space group P2/c with a = 6.9874(14), b = 9.960(2), c = 12.894(4) A, β = 117.47(2)°, Fe(C8H6NO4)2(H2O)2, Mr = 452.16, V= 796.2(3) A3, Z = 2, Dc = 1.886 g.cm-3, p = 1.017 mm-1, F(000) = 464.0, 2.71〈0〈28.42°, R = 0.0307, wR = 0.0840 and S = 1.005. Single-crystal X-ray diffraction analysis reveals that 1 features an infinite one-dimensional loop-like chain structure and Haip ligand in 1 is of zwitterionic form. Magnetic measurement results show the dominated ferromagnetic interactions among Fe11 atoms.
文摘A new 2D compound,{[Mn6 L3(H2O)8]·0.69(C3 H7 NO)·3.31H2O}n(1,H4 L=1,1’-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylic acid)),was synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group C2/c with a=26.468(5),b=19.750(4),c=13.660(3)A,β=92.73(3)°,V=7132(2)A^3,Z=4,Mr=1824.12,Dc=1.699 g/cm3,F(000)=3705,R=0.042 and w R=0.117 for 8965 observed reflections(I>2σ(I)).In compound 1,all of the Mn(II)atoms are six-coordinated and take the octahedral geometry of[MnNO5].The 2D compound consists of secondary building unit[Mn3(μ2-O)(R-COO)3](SBU),in which two of the Mn^2+ions exhibit the same coordinated environments while another Mn^2+ion has a different one.The SBUs further connect with each other to form a 1 D inorganic chain which is connected with L^4-ligands to construct a 2D layer.Finally,strong O–H···O hydrogen bonds among the rich carboxyl molecules and O atoms from free DMF and guest water molecules connect the two-dimensional coordination network into a three-dimensional framework.Variable temperature magnetic measurements indicate the antiferromagnetic behavior in the Mn3 core in compound 1.
基金supported by the National Natural Science Foundation of China(No.21071006)the Natural Science Foundation of Henan Province(No.102102210457)the Natural Science Foundation of the Henan Higher Education Institutions of China(No.2010B150001)
文摘A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurally as well as magnetically in detail. The crystal belongs to the monoclinic system, space group P2_1/c with a = 9.6896(1), b = 20.539(4), c = 12.147(2) ?, β = 93.84(3)°, M_r = 997.65, V = 2412.1(8) ?~3, Z = 2, Dc = 1.374 g/cm, F(000) = 1038, m = 0.635 mm^(-1), the final R = 0.0539 and w R = 0.1289 for 5998 observed reflections(I 〉 2σ(I)). The Co(Ⅱ) ion is coordinated by two nitrogen atoms of quinoxaline rings from two NITQs and four oxygen atoms from two acac ions to complete a distorted octahedral coordination environment. Compound 1 is further linked into a three-dimensional(3D) supramolecular network by hydrogen-bonding, Cl×××O weak contact and π···π stacking interactions. The magnetic measurements show compound 1 exhibits weak ferromagnetic interactions.
基金This work was supported by the National Natural Science Foundation of China (No. 20471026) and Natural Science Foundation of Henan Province (No. 0311021200)
文摘A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.
基金financially supported by the Key Scientic Research Projects of Colleges and Universities,Henan Province(No.18A150020)Anyang Key Laboratory for Chemical Biosensing(No.21302003)
文摘One new mixed-valence heptanuclear manganese complex, [Mn^ⅡMn^Ⅲ6O2L6-(NaCH3COO)2(CH3COO)4](1)(L = 3-ethoxy-6-((2-hydroxyethyl)imino)methyl) phenol, was synthesized by treating the Schiff-base ligand with Mn(acac)3·4H2O and characterized by elemental analysis, IR spectra, thermogravimetric analyses and X-ray single-crystal diffraction. 1 has a similar new mixed-valence heptanuclear structure. The magnetic measurements indicate that 1 exhibits the antiferromagnetic interactions.