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.     

SYNTHESIS, MAGNETIC PROPERTY AND X-RAY CRYSTAL STUCTURE OF MIXED VALENT COBALT COMPLEX SALT [Co~Ⅲ Cl_2(py)_4][Co~Ⅱ Cl_3(py)]

Complex salt Co_2Cl_5(py)_5 (py=pyridine) was obtained by the reaction of CoCl_2·6H_2O with Bu_4NMnO_4 in pyridine in the presence of benzoic acid. It is monoclinic and crystallizes in space group P2_1/n, fw=690.64, a=28.652(5), b=14.108(4), c=7.424(3) ;β=90.09(1); V=3001(2)~3; Z=4, Dc=1.53g/cm~3. Final R factor is 0.041. The structure consists of a discrete cation [Co~ⅢCl_2(py)_4]~+ and an anion [Co~Ⅱ Cl_3(py)]~-. The Co~Ⅲ ion is coordinated by two Cl~- and four pyridine nitrogen atoms to form an octahedral geometry, and Co~Ⅱ is coordinated by three Cl~- and one pyridine nitrogen atom to form the apices of a tetrahedron. The variable-temperature magnetic susceptility measurement shows no magnet-exchange interaction between Co~Ⅲ and Co~Ⅱ ions.     

CRYSTAL STRUCTURE OF BIS-ETHYLENEDIAMINE TRITHIOCYANATE OF COPPER(Ⅱ) AND SILVER(Ⅰ) Cu(en)_2Ag(SCN)_3

Cu(en)_2Ag(SCN)_3 crystallizes in space group P2_12_12_1 with its cell parameters, a=7.126(2), b=12.587(5), c=17.585(5). There are four formula units per unit cell(ρ_obs.=1.90g/cm~3, ρ_(calc.=1.96g/cm~3). Diffraction data are collected on a CAD4 four-circle diffractometer using Mo-Ka radiation. The structure is determiued by heavy atom method, then refined by leastsquare method to a final R=0.036. It is shown that in the crystal the coordination of Cu atoms is square pyramidal with four N atoms of en groups in the square plane and oue Natom of thiocyanate group in the apical position. The Ag atom is coordinated tetrahedrally by four S atoms of thiocyanate groups, one of which links up two AgS_4 together, thus forming the infinite AgS_4 tetrahedron chains along a axis.     

Syntheses and Structures of Two Ruthenium(III)Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh_3)_3Cl_2] with tetraethylthiuram disulfide[Et_2NCS_2]_2 or tetra-iso-pmpylthiumm disulfide[~iPr_2NCS_2]_2 afforded mthenium(Ⅲ)complexes[Ru(PPh_3)_2(S_2CNR_2)cl_2]·CH2Cl2(R=Et 1,~iPr 2)which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group Pīwith a=11.5065(6),b=12.1458(7),C=18.0034(9)(A),α=109.380(4),β=95.279(4),γ=97.969(4)°,ν=2324.8(2)(A)~3 and Z=2.Complex 2 belongs to the monoclinic system,space group P21/n with a=12.5752(3),b=20.7562(5),e=17.6821(3)(A),β=105.934(1)°,ν=4437.94(17)(A)~3 and Z=4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh_3 ligands in mutually tram and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2)and 2.369(2)(A) for 1,and 2.376(2),2.414(1)and 2.383(2)(A) for 2,respectively.The electrochemical properties of these two complexes were studied in CH_2Cl_2 solution by cyclic voltammetry.     

Crystal Structures,Characterizations and Fluorescence Properties of Two 3D Ca(Ⅱ)/Sr(Ⅱ) Coordination Polymers Based on 2-Sulfoterephthalate

Two alkaline earth metal coordination polymers[M(2-Hstp)(H_2O)](M=Ca~(2+)(1)and Sr~(2+)(2),2-H_3stp=2-sulfoterephthalate)were synthesized under hydrothermal conditions by the precursor[Mn(2-Hstp)_2(4,4?-Hbpy)_2]and alkaline earth metal salts.The two alkaline earth complexes are not isomorphic.Complex 1 crystallizes in the monoclinic space group P2_1/m,while2 in the monoclinic space group P2_1/c,despite of their similar formulas.In 1,the Ca~(2+)ion lies in a seven-coordinated pentagon bipyramidal configuration,coordinated with five 2-Hstp~(2-)anions and one water molecule.However,the Sr~(2+)ion in 2 is coordinated by nine oxygen atoms to form a single-capped square antiprism polyhedron.Both 1 and 2 exhibitπ-π*emission of the 2-sulfoterephthalate ligand.     

Synthesis and Structure Study of Molybdenum Complex Mo[o-NHCOCH_3-m-NO_2C_6H_3COOH]_2_O2Cl_2·PhCl

The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.     

Cyanide-bridged One-dimensional Heterobimetallic Complex cis-[Fe~Ⅱ(phen)_2(CN)_2Mn~Ⅲ(salen)](PF_6): Synthesis,Crystal Structure and Magnetic Properties

Dicyanide building block cis-Fe(phen)_2(CN)_2 and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a cyanide-bridged complex, resulting in a heterobimetallic one-dimensional(1D) zigzag chain complex 1, [cis-Fe(phen)_2(CN)_2Mn(salen)](PF_6)(phen =1,10-phenanthroline, salen=N,N?-ethylenebis-(salicylideneaminato) dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in the monoclinic P2_(1/c) space group and the asymmetric unit contains one [-NC-Fe(phen)_2(μ-CN)-Mn~Ⅲ-(salen)-]~+ cation and one PF_6~- anion. In the cationic structure of 1, each Fe~Ⅱ(phen)_2(CN)_2 connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each [Mn~Ⅲ(salen)]~+ unit links two Fe~Ⅱ(phen)2(CN)_2 building blocks in a trans-conformation, resulting in a 1D [-NC-Fe~Ⅱ-CN-Mn~Ⅲ-]n chain. Furthermore, the electronic absorption spectra and electrochemical and magnetic properties of complex 1 have also been studied.     

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper(Ⅱ) coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4'-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756(10),b= 1.57756(10),c=2.1438(3)nm,V=5.3352(8) nm3,Dc=1.524 g/cm3,Z=4,F(000)=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper(1) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry;the copper(2) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.     

SYNTHESIS AND STRUCTURE OF AN ASYMMETRIC TRICOBALT COMPOUND Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3

Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2,o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms aretriangularly arranged and asymmetrically bridged by four S and one O atoms from the fourH_2mp ligands and terminally ligated by one O and three P atoms.Two free hydroxyl groupsform two internal hydrogen bonds with adjacent oxo donor atoms.     

以甲酸为配体的无限三维配位聚合物[Zn(HCOO)2(H2O)2]∞的水热合成和热分析

The coordination polymer [Zn（HCOO）2（H2O）2]∞ has been synthesized using hydrothermal method and characterized by X-ray single crystal diffraction, elemental analysis, FTIR spectroscopy and TG-DTG analyses. The coordination polymer crystallizes in monoclinic, P21/c space group with crystal parameters of α=0.8688（1） nm, b= 0.7143（6） nm, c=0.9305（2） nm, β=97.61（5）°, V=0.5724（2） nm^3, Z=4, μ（Mo Kα）=42.50 cm^-1. The polymer features with two kinds of zinc centers： one is hexa-coordinated by four water ligands, two oxygen atoms of two formates and the other is coordinated by six oxygen atoms of six formates. By the formates as space linkers, three-dimensional frameworks were formed. Based on thermal analyses, thermal decomposition mechanisms were predicted that at the first step the polymer lost two coordination water molecules and at the second step lost two formates companied by the formation of some kinds of materials.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Study of a Novel 1D Polymer [Zn(HMICD)(bpy)]_n·2nH_2O

A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]_n·2n H_2O(1, H_3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2?-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) ?, V = 3325.8(11) ?~3, Dc = 1.700 g/cm~3, M_r = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm~(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.     

Synthesis and Characterization of a New Symmetric Dinucleating Ligand and Its Dizinc(Ⅱ)Complex with Alkoxo and Carboxylate Bridges

<正>A novel dinuclear zinc(Ⅱ)complex[Zn_2L(μ-OAc)](PF_6)_2(CH_3OH)has been synthesized from a new symmetrical compartmental ligand HL in which the pendant arms,bearing pyridyl groups,are bridged by 1,3-diaminopropan-2-ol.X-ray crystal structure shows that the two zinc atoms reside within the adjacent ligand compartments and are bridged by the endogenous alkoxo-O from ligand and one exogenous carboxylate from acetate with a syn-syn mode.The coordination geometry of two zinc atoms is a distorted trigonal bipyramid with the pyridyl-N atoms and bridging alkoxo-O atom providing the equatorial donor set.Such coordination geometry observed in this complex is similar to that found in the dinuclear unit of phospholipase C.     

Vanadium(Ⅳ)dimer complexes containing [V(o-C_6H_4OS)_3]~(2-)fragment and caged sodium ions

Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A=Ph_4P~+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared bythe reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N~+,L=L'=MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com-plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti-bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space groupP1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V=2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono-clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8,and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)3]~(2-) fragmentslinked by sodium ions through the μ_3-O bridges with a crystallographic center of symmetry.The V(IV)atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.     

CRYSTAL STRUCTURE OF ORGANOLANTHANIDE [{Li(THF)_2}_2 (μ-Cl)_4(η~5-C_5H_5)Pr(THF)]

<正> The title complex crystallizes in the orthorhombic space group Pna21 with Mr = 570. 8, a = 16. 927(6), b = 18.942(7), c=10. 618(5)(?) and Z = 4. The structure was solved by Patterson and Fourier techniques and refined by block-diagonal least squares techniques to R = 0. 090 and Rw = 0. 093 for 1553 reflections with I>1. 5σ(I). The Pr3+ ion is bonded to five carbon atoms of cyclopentadi-enyl ring, four μ-chlorine atoms and one oxygen atom of THF in an octahedral geometry with the Pr-C distances in the range 2. 6.7 - 2. 79(?)(av. 2. 76(?)) , the Pr-Cl distances in the range 2. 81 - 2. 92(?) (av. 2. 86(?)) and the Pr -O distance of 2. 51 (?). Each Li+ ion is coordinated by two μ-chlorine atoms and two oxygen atoms from THF in a tetrahedral geometry with the Li-Cl distances in the range 2. 24 - 2. 61(?) (av. 2. 43(?)) and the Li -O distances in the range 1. 86-1. 94(?)(av. 1. 91(?)). The Pr atom and the two Li atoms are bridged asymmetrically by the chlorine atoms.     

Syntheses and Structures of Two Ruthenium(Ⅲ) Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh3)3Cl2] with tetraethylthiuram disulfide [Et2NCS2]2 or tetra-iso-propylthiuram disulfide [iPr2NCS2]2 afforded ruthenium(Ⅲ) complexes [Ru(PPh3)2(S2CNR2) Cl2]·CH2Cl2(R=Et 1,iPr 2) which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P with a = 11.5065(6),b = 12.1458(7),c = 18.0034(9) ,α = 109.380(4),β = 95.279(4),γ = 97.969(4)°,V = 2324.8(2) 3 and Z = 2.Complex 2 belongs to the monoclinic system,space group P21/n with a = 12.5752(3),b = 20.7562(5),c = 17.6821(3) ,β = 105.934(1)°,V = 4437.94(17) 3 and Z = 4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh3 ligands in mutually trans and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2) and 2.369(2)  for 1,and 2.376(2),2.414(1) and 2.383(2)  for 2,respectively.The electrochemical properties of these two complexes were studied in CH2Cl2 solution by cyclic voltammetry.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Complex Cu(o-Methylbenzoic acid)_2(2,2′-bipy)·(H_2O)

The title complex (C26H24CuN2O5, Mr = 508.01) has been synthesized by o-me- thylbenzoic acid, 2,2′-bipyridine (bipy) and copper perchlorate in the mixed solvent of water and methanol. It crystallizes in orthorhombic, space group P212121 with a = 0.70814(10), b = 1.6953(3), c = 1.9539(3) nm, V = 2.3457(6) nm3, Dc = 1.439 g/cm3, Z = 4, μ = 0.971 mm-1, F(000) = 1052, R = 0.0432 and wR = 0.0860. The structural determination shows that the copper atom is coordinated by three oxygen atoms from two o-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The cyclic voltammetric behavior of the complex is also discussed.     

Synthesis,Crystal Structure,Magnetic Property and DFT Study of a Novel 2D Polymer [Cu(pdc)(bpy)]·H_2O

A new copper complex [Cu(pdc)(bpy)]·H2 O(1, H2 pdc = 3,5-pyridinedicarboxylic acid, bpy = 2,2-bipyridine) has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectroscopy and magnetic measure- ments. Complex 1 crystallizes in monoclinic system, space group P21 /c, a = 10.893(2), b = 7.3641(15), c = 1.9921(4), β = 92.16(3), V = 1596.9(6)3, Dc = 1.676 g/cm3, Mr = 402.84, Z = 4, F(000) = 820, μ = 1.404 mm-1, the final R = 0.0237 and wR = 0.0693. The Cu(II) ion is five-coordinated by two O atoms from two pdc ligands, one N atom from another pdc ligand and two N atoms from the bpy ligand. The pdc anion, which acts as a tridentate ligand, links three Cu ions, forming(3,3)-connected two-dimensional(2D) sheets. We also studied the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with UV-vis spectrum.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3[Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]

The space group of the title crystal is Pnam. The unit cell parameters are: a=17.226(4), b=14.306(7), c=15.074(4); z=4, Dobs=2.03g·cm~(-3), D_(calc)=2.063g·cm~(-3). The crystal structure was solved by the heavy atom method and refined by the full-matrix least-squares until the final conventional discrepancy factor was reduced to 0.068. The results of the investigation show that the crystal consists of trinuclear Mo cluster anions [Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]~(3-) together with planar (C_5H_7S_2)~ monocations, surrounding the cluster anions. In the cluster anion three Mo atoms, forming a nearly equilateral triangle (2.755(1), 2.755(1), 2.743(1)), are bound by a μ_3-S bridging atom, while each pair of Mo atoms is bridged further by a μ_2-S_2 ligand. Besides, each Mo atom is coordinated to two terminal Cl atoms, so that the coordination sphere of each Mo atom approaches closely a pentagonal bipyramid. In addition, a single Gl atom, not at all involved in the coordination spheres of the three Mo atom     

CRYSTAL STRUCTURE OF TRIGALLIUM TRIS(OBTHOPHOSPHATE) 2-ETHANOLANINE HYDRATE, Ga_3(PO_4)_3·H_2NCH_2CH_2OH·H_2O

<正> Trigallium tris(orthophosphate) hydrate-2-ethanolamine was synthesized from the ethanolamine(EAN)-Ga2O3-P2O5-H2O system. The compound crystallizes in monoclinic system, space group P21/n, with a = 8.669(2), b = 17.932(4), c = 9.097(2) A,β= 108.32(1)°,V=1342.4 A3, Z = 4. The structure was solved by direct methods and refined to final R of 0.048. For the three gallium atoms in an asymmetric unit, the coordination tetrahedron of Ga(3) is nearly regular, while Ga(l) and Ga(2) are each coordinated by five oxygen atoms and their coordination polyhedra show some distortion from a trigonal bipyramid. The three-dimensional net in the crystal lattice is built of two-dimensional nets which are composed of irregular triangles, quadrilaterals, pentagons and octagons formed by Ga and P atoms. Moreover, the corrugated 2D nets running along [101] are linked together by two double-crank-shaft chains of GaPO4, one of which runs along [101] while the other along [101]. The ethanolamine molecule, so called the template,