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 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 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
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 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
A new compound (NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-(2'-chlor-5'- nitrophenyl)-3-oxide-l-oxyl) 1 and its complex (Cu(NIT-mNO2)(hfac)2) 2 have been synthesized and structurally and magnetically c...A new compound (NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-(2'-chlor-5'- nitrophenyl)-3-oxide-l-oxyl) 1 and its complex (Cu(NIT-mNO2)(hfac)2) 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798(9), b = 11.2705(9), c = 12.9559(10)A, β = 107.3770(10)°, V = 1488.3(2) A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g(MoKa) = 0.276 mm^-1, F(000) = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit (imidazoline ring) is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699(10), b = 10.6286(11), c = 15.1683(15)A, a = 77.5330(10), ,β = 773080(10), y = 87.3420(10)*, V = 1592.5(3) A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ(MoKa) = 0.888 mm^-1, F(000) = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu(Ⅱ) ion is located at a center of symmetry, and each Cu(Ⅱ) is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu(Ⅱ) ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.展开更多
One novel binuclear Co(Ⅱ) coordination polymer ∞ [Co2(4,4'-bpy)2(L)4] (1, bpy = bipyridine, HL = 2-fluorbenzoic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis...One novel binuclear Co(Ⅱ) coordination polymer ∞ [Co2(4,4'-bpy)2(L)4] (1, bpy = bipyridine, HL = 2-fluorbenzoic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.163(2), b = 21.943(4), c = 9.6381(19) A, β = 113.92(3)°, V= 2158.2(7) A3, Z= 4, Dc = 1.518 g/cm^3, Mr = 493.31, F(000) =1004, R = 0.0303 and wR = 0.0808 for 3614 observed reflections (I〉 2σ(I)). Complex I exhibits a 3D Schlafli symbol (4.62)(4.66.83) topological framework, and the magnetic characterization shows weak antiferromagnetic coupling exchange between two Co ions.展开更多
Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in sit...Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in situ synthesized under solvothermal conditions and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analysis, and magnetic analysis. Single-crystal X-ray diffraction indicates that the complexes crystallize in monoclinic C121 space group. Each lanthanide center is coordinated with four oxygen and four nitrogen atoms from two salen^2- ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 kOe magnetic field.展开更多
A novel metal-organic coordination polymer [Mn3(2,2′-dipha)3(phen)6]n·3nH2O (2,2′-dipha = 2,2′-diphenic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characteri...A novel metal-organic coordination polymer [Mn3(2,2′-dipha)3(phen)6]n·3nH2O (2,2′-dipha = 2,2′-diphenic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The crystal crystallizes in triclinic, space group P1 with a = 16.921(5), b = 18.307(5), c = 18.450(5)A , α = 113.369(5), β = 108.529(5), γ = 102.984(5)°, V = 4553(2)A^ 3, C114H72Mn3N12O14.25, Mr = 2002.66, Dc = 1.461 g/cm^3, μ(MoKα) = 0.488 mm^-1, the final F(000) = 2058, Z = 2, R = 0.0491 and wR = 0.0980 for 9087 observed reflections (I 〉 2σ(I)). In the crystal structure, the manganese atom is six-coordinated with two carboxylate oxygen atoms from different carboxylate groups of the same dipha and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Fur- thermore, it exhibits a zero-dimensional structure with dipha-Mn-phen- as building units. Variable- temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.展开更多
A new cobalt(II) compound, {(Me2NH2)4[Co(SIP)2]·2(DMF)·3(H2O)}n(1, H3 SIP =5-sulfoisophthalic acid), has been synthesized under solvothermal condition and structurally characterized by single-cry...A new cobalt(II) compound, {(Me2NH2)4[Co(SIP)2]·2(DMF)·3(H2O)}n(1, H3 SIP =5-sulfoisophthalic acid), has been synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system,space group P 4 21 m, with a = 14.3080(7), b = 14.3080(7), c = 12.1837(9) ?, V = 2494.2(3) ?~3, Z =2, CHNOSCo, Mr = 929.87, Dc = 1.238 g/cm, μ = 0.496 mm, F(000) = 982, flack parameter of 0.007(9), the final R = 0.0767 and wR = 0.2110 for 2391 observed reflections with I >2σ(I). The tetrahedral Co(II) ions are linked by carboxylate groups of the 5-sulfoisophthalate ligands to form an anionic two-dimensional(2D) layer displaying a(4,4) square network, which was charge-balanced by the [MeNH] + cations occupying the spaces between the 2D layers. Magnetic properties of 1 have been investigated in detail using direct-current and alternating-current susceptibility measurements.展开更多
The reaction of Co^II ions with 1,4-bis(imidazol)butane(bimb) or 1,4-bis(triazol)butane(bitb) in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co(bimb)3]·2ClO4}n...The reaction of Co^II ions with 1,4-bis(imidazol)butane(bimb) or 1,4-bis(triazol)butane(bitb) in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co(bimb)3]·2ClO4}n(I) and {[Co(bitb)3]·2ClO4}n(II). Single-crystal X-ray analysis indicates that both complexes I and II show the same α-Po topological structures. However, complex I exhibits a 2-fold interpenetrating network, while complex II features a 3-fold interpenetrating network. In addition, solid-state properties such as thermal stabilities and magnetic properties of two complexes were also investigated.展开更多
A dinuclear Tb(Ⅲ) compound, Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2(1, Hanthc = 9-anthracenecarboxylic acid and 1,10-phen = 1,10-phenanthroline), was synthesized under solvothermal condition and structural...A dinuclear Tb(Ⅲ) compound, Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2(1, Hanthc = 9-anthracenecarboxylic acid and 1,10-phen = 1,10-phenanthroline), was synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1, with a = 12.5061(12), b = 13.3168(10), c = 15.0079(12) ?, α = 110.620(7), β = 102.941(7), γ = 107.036(7)o, V = 2081.8(3) ?~3, Z = 1, C_(114)H_(70)N_4O_(12)Tb_2, M_r = 2005.58, D_c = 1.600 g/cm^3, μ = 1.759 mm^(-1), F(000) = 1008, the final R = 0.0294 and w R = 0.0608 for 8900 observed reflections with I 〉 2s(I). In compound 1, two Tb(Ⅲ) ions are linked by four carboxylate groups of the bridging anthc– ligands to give a dinuclear Tb_2(μ_2-anthc)_4 unit wherein each Tb(III) ion is further capped by a terminal anthc– ligand and a 1,10-phen ligand in a chelating fashion. Detailed direct-current and alternating-current susceptibility measurements showed no slow magnetism relaxation phenomenon was observed for 1.展开更多
A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089...A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089(13), b = 10.2897(5), c = 12.0024(6)A, β = 111.864(4)°, Mr = 715.49, V = 3141.5(3) A3, Dc = 1.513 g/cm^3, Z = 4, μ(Mo Kα) = 0.694 mm^-1, F(000) = 1456, the final R = 0.0473 and w R = 0.1146. In the title complex, the central Ag(I) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495-520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.展开更多
Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a=1...Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a=12.845(4), b=3.862(4), c=13.001(2)(A), V=645.0(7)(A)3,Z=4, F(000)=880,μ(MoKα)=27.794 mm^-1, the final R=0.0528 and wR=0.0562 for 1070observed reflections with I 〉 3σ(I). The CaEr2S4 structure forms a three-dimensional framework that consists of interconnected tetra-octahedral Er4S18 fragments. Ca^2+cations, in a monocapped trigonal prism geometry, are stuffed in two parallel rows into the one-dimensional channels along the b direction. CaEr2S4 is an infrared-transparent semiconductor with a band gap of 1.81 eV. Magnetic susceptibility measurements over 6~300 K indicate a Curie-Weiss paramagnetic behavior for the phase, with an effective magnetic moment of 9.64(1) μB per Er^3+ ion.展开更多
Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis...Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis of the two compounds, the results show that compound 1 features one-dimensional (1D) double-strand coordination arrays, while 2 presents the 63-hcb layers. Both compounds are further constructed into a 3D supramolecular structure with the aid of weak secondary interactions. Thermal stabilities and magnetic properties of compounds 1 and 2 were also investigated.展开更多
Two new Schiff base complexes, [NiL]ClO4 1 and [CuL]ClO40.5H2O 2, were synthesized and characterized, where L is the 1:1 condensation product of salicylaldehyde and diethylenetriamine. Their crystal structures and ma...Two new Schiff base complexes, [NiL]ClO4 1 and [CuL]ClO40.5H2O 2, were synthesized and characterized, where L is the 1:1 condensation product of salicylaldehyde and diethylenetriamine. Their crystal structures and magnetic properties were determined and investigated. The H-bonding interactions concern just in neighbor cation and anion, do not extend into network for both 1 and 2. The temperature dependence of the magnetic susceptibilities (2-300K) showed that 1 is diamagnetism and 2 is paramagnetism with weak antiferromagnetic exchange interactions between adjacent spin carriers, no magnetic ordering taking place in these two complexes.展开更多
X-ray powder diffraction, resistivity and magnetization studies have been performed on polycrystalline Nd(FexMn1-x)2Si2 (0≤x 〈 1) compounds which crystallize in a ThCr2Si2-type structure with the space group 14/...X-ray powder diffraction, resistivity and magnetization studies have been performed on polycrystalline Nd(FexMn1-x)2Si2 (0≤x 〈 1) compounds which crystallize in a ThCr2Si2-type structure with the space group 14/mmm. The field-cooled temperature dependence of the magnetization curves shows that, at low temperatures, NdFe2Si2 is antiferromagnetic, while the other compounds show ferromagnetic behaviour. The substitution of Fe for Mn leads to a decrease in lattice parameters a, c and unit-cell volume V. The Curie temperature of the compounds first increases, reaches a maximum around x=0.7, then decreases with Fe content. However, the saturation magnetization decreases monotonically with increasing Fe content. This Fe concentration dependent magnetization of Nd(FexMn1-x)2Si2 compounds can be well explained by taking into account the complex effect on magnetic properties due to the substitution of Mn by Fe. The temperature's square dependence on electrical resistivity indicates that the curve of Nd(Fe0.6Mn0.4)2Si2 has a quasi-linear character above its Curie temperature, which is typical of simple metals.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
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(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 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.
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.
基金the National Natural Science Foundation of China (No. 20471026)Natural Science Foundation of Henan Province (No. 0311021200) the Foundation of Education Committee of Henan Province (2006150017)
文摘A new compound (NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-(2'-chlor-5'- nitrophenyl)-3-oxide-l-oxyl) 1 and its complex (Cu(NIT-mNO2)(hfac)2) 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798(9), b = 11.2705(9), c = 12.9559(10)A, β = 107.3770(10)°, V = 1488.3(2) A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g(MoKa) = 0.276 mm^-1, F(000) = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit (imidazoline ring) is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699(10), b = 10.6286(11), c = 15.1683(15)A, a = 77.5330(10), ,β = 773080(10), y = 87.3420(10)*, V = 1592.5(3) A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ(MoKa) = 0.888 mm^-1, F(000) = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu(Ⅱ) ion is located at a center of symmetry, and each Cu(Ⅱ) is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu(Ⅱ) ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.
基金supported by the National Natural Science Foundation of China(51343003)the Scientific Research Projects of Zhejiang Provincial Education Department(Y201224707)
文摘One novel binuclear Co(Ⅱ) coordination polymer ∞ [Co2(4,4'-bpy)2(L)4] (1, bpy = bipyridine, HL = 2-fluorbenzoic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.163(2), b = 21.943(4), c = 9.6381(19) A, β = 113.92(3)°, V= 2158.2(7) A3, Z= 4, Dc = 1.518 g/cm^3, Mr = 493.31, F(000) =1004, R = 0.0303 and wR = 0.0808 for 3614 observed reflections (I〉 2σ(I)). Complex I exhibits a 3D Schlafli symbol (4.62)(4.66.83) topological framework, and the magnetic characterization shows weak antiferromagnetic coupling exchange between two Co ions.
基金supported by the National Natural Science Foundation of China(21101090 and 21561021)
文摘Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in situ synthesized under solvothermal conditions and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analysis, and magnetic analysis. Single-crystal X-ray diffraction indicates that the complexes crystallize in monoclinic C121 space group. Each lanthanide center is coordinated with four oxygen and four nitrogen atoms from two salen^2- ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 kOe magnetic field.
基金The project was supported by the Education Office of Jilin Province (No. 0047)
文摘A novel metal-organic coordination polymer [Mn3(2,2′-dipha)3(phen)6]n·3nH2O (2,2′-dipha = 2,2′-diphenic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The crystal crystallizes in triclinic, space group P1 with a = 16.921(5), b = 18.307(5), c = 18.450(5)A , α = 113.369(5), β = 108.529(5), γ = 102.984(5)°, V = 4553(2)A^ 3, C114H72Mn3N12O14.25, Mr = 2002.66, Dc = 1.461 g/cm^3, μ(MoKα) = 0.488 mm^-1, the final F(000) = 2058, Z = 2, R = 0.0491 and wR = 0.0980 for 9087 observed reflections (I 〉 2σ(I)). In the crystal structure, the manganese atom is six-coordinated with two carboxylate oxygen atoms from different carboxylate groups of the same dipha and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Fur- thermore, it exhibits a zero-dimensional structure with dipha-Mn-phen- as building units. Variable- temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.
基金Supported by the NNSFC(21361011 and 21561015)the Natural Science Foundation of Jiangxi Province(20151BAB203002)the Open Project Program of Key Laboratory of Functional Small Organic Molecule,Ministry of Education,Jiangxi Normal University(KLFS-KF-201412)
文摘A new cobalt(II) compound, {(Me2NH2)4[Co(SIP)2]·2(DMF)·3(H2O)}n(1, H3 SIP =5-sulfoisophthalic acid), has been synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system,space group P 4 21 m, with a = 14.3080(7), b = 14.3080(7), c = 12.1837(9) ?, V = 2494.2(3) ?~3, Z =2, CHNOSCo, Mr = 929.87, Dc = 1.238 g/cm, μ = 0.496 mm, F(000) = 982, flack parameter of 0.007(9), the final R = 0.0767 and wR = 0.2110 for 2391 observed reflections with I >2σ(I). The tetrahedral Co(II) ions are linked by carboxylate groups of the 5-sulfoisophthalate ligands to form an anionic two-dimensional(2D) layer displaying a(4,4) square network, which was charge-balanced by the [MeNH] + cations occupying the spaces between the 2D layers. Magnetic properties of 1 have been investigated in detail using direct-current and alternating-current susceptibility measurements.
基金Supported by the National Natural Science Foundation of China(Nos.21301106,21201109 and 21373122)
文摘The reaction of Co^II ions with 1,4-bis(imidazol)butane(bimb) or 1,4-bis(triazol)butane(bitb) in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co(bimb)3]·2ClO4}n(I) and {[Co(bitb)3]·2ClO4}n(II). Single-crystal X-ray analysis indicates that both complexes I and II show the same α-Po topological structures. However, complex I exhibits a 2-fold interpenetrating network, while complex II features a 3-fold interpenetrating network. In addition, solid-state properties such as thermal stabilities and magnetic properties of two complexes were also investigated.
基金Supported by the National Natural Science Foundation of China(No.21361011 and 21101081)Science Founds of State Key Laboratory of Structural Chemistry(20130011)
文摘A dinuclear Tb(Ⅲ) compound, Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2(1, Hanthc = 9-anthracenecarboxylic acid and 1,10-phen = 1,10-phenanthroline), was synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1, with a = 12.5061(12), b = 13.3168(10), c = 15.0079(12) ?, α = 110.620(7), β = 102.941(7), γ = 107.036(7)o, V = 2081.8(3) ?~3, Z = 1, C_(114)H_(70)N_4O_(12)Tb_2, M_r = 2005.58, D_c = 1.600 g/cm^3, μ = 1.759 mm^(-1), F(000) = 1008, the final R = 0.0294 and w R = 0.0608 for 8900 observed reflections with I 〉 2s(I). In compound 1, two Tb(Ⅲ) ions are linked by four carboxylate groups of the bridging anthc– ligands to give a dinuclear Tb_2(μ_2-anthc)_4 unit wherein each Tb(III) ion is further capped by a terminal anthc– ligand and a 1,10-phen ligand in a chelating fashion. Detailed direct-current and alternating-current susceptibility measurements showed no slow magnetism relaxation phenomenon was observed for 1.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089(13), b = 10.2897(5), c = 12.0024(6)A, β = 111.864(4)°, Mr = 715.49, V = 3141.5(3) A3, Dc = 1.513 g/cm^3, Z = 4, μ(Mo Kα) = 0.694 mm^-1, F(000) = 1456, the final R = 0.0473 and w R = 0.1146. In the title complex, the central Ag(I) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495-520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.
基金This work was partially supported by the NSF of Fujian Province (Z0513020, A042002)the NSF for Distinguished Young Scientist of China (20425104) and the NSF of CAS (KJCX2-SW-h05)
文摘Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a=12.845(4), b=3.862(4), c=13.001(2)(A), V=645.0(7)(A)3,Z=4, F(000)=880,μ(MoKα)=27.794 mm^-1, the final R=0.0528 and wR=0.0562 for 1070observed reflections with I 〉 3σ(I). The CaEr2S4 structure forms a three-dimensional framework that consists of interconnected tetra-octahedral Er4S18 fragments. Ca^2+cations, in a monocapped trigonal prism geometry, are stuffed in two parallel rows into the one-dimensional channels along the b direction. CaEr2S4 is an infrared-transparent semiconductor with a band gap of 1.81 eV. Magnetic susceptibility measurements over 6~300 K indicate a Curie-Weiss paramagnetic behavior for the phase, with an effective magnetic moment of 9.64(1) μB per Er^3+ ion.
基金supported by the National Natural Science Foundation of China(Nos.21671119,21301106 and 21673127)
文摘Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis of the two compounds, the results show that compound 1 features one-dimensional (1D) double-strand coordination arrays, while 2 presents the 63-hcb layers. Both compounds are further constructed into a 3D supramolecular structure with the aid of weak secondary interactions. Thermal stabilities and magnetic properties of compounds 1 and 2 were also investigated.
文摘Two new Schiff base complexes, [NiL]ClO4 1 and [CuL]ClO40.5H2O 2, were synthesized and characterized, where L is the 1:1 condensation product of salicylaldehyde and diethylenetriamine. Their crystal structures and magnetic properties were determined and investigated. The H-bonding interactions concern just in neighbor cation and anion, do not extend into network for both 1 and 2. The temperature dependence of the magnetic susceptibilities (2-300K) showed that 1 is diamagnetism and 2 is paramagnetism with weak antiferromagnetic exchange interactions between adjacent spin carriers, no magnetic ordering taking place in these two complexes.
基金Project supported by the National Basic Research Program of China (Grant No 2006CB601101)
文摘X-ray powder diffraction, resistivity and magnetization studies have been performed on polycrystalline Nd(FexMn1-x)2Si2 (0≤x 〈 1) compounds which crystallize in a ThCr2Si2-type structure with the space group 14/mmm. The field-cooled temperature dependence of the magnetization curves shows that, at low temperatures, NdFe2Si2 is antiferromagnetic, while the other compounds show ferromagnetic behaviour. The substitution of Fe for Mn leads to a decrease in lattice parameters a, c and unit-cell volume V. The Curie temperature of the compounds first increases, reaches a maximum around x=0.7, then decreases with Fe content. However, the saturation magnetization decreases monotonically with increasing Fe content. This Fe concentration dependent magnetization of Nd(FexMn1-x)2Si2 compounds can be well explained by taking into account the complex effect on magnetic properties due to the substitution of Mn by Fe. The temperature's square dependence on electrical resistivity indicates that the curve of Nd(Fe0.6Mn0.4)2Si2 has a quasi-linear character above its Curie temperature, which is typical of simple metals.
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.