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

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

二重穿插锰配合物Mn2(ADB)2(DMSO)4DMSO的溶剂热合成和结构研究

A novel Mn coordination polymers, Mn₂(ADB)₂(DMSO)₄·DMSO (H₂ADB=4,4′-azodibenzoic acid), has been prepared by solvothermal reaction and characterized by element analysis, IR spectra and single-crystal X-ray diffraction. The crystallographic data shows that the title complex crystallizes in monoclinic space group C2/c. Each Mn(Ⅱ) is six-coordinated to four O atoms from three ADB^2- ligands, two oxygen atoms from two DMSO molecule and forms distorted octahedral coordination geometry. The Mn(Ⅱ) dimers by the carboxyl groups of the ADB^2- ligands were interlinked together by the different carboxylate coordination modes of ADB^2- ligands, to yield scaffolds with 2D network with 4.8² topological structures. CCDC: 745678.     

Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

A mixed-valence dinuclear manganese complex, [MnⅡMnⅢL](ClO4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P21/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N3O3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.     

一个新的噻二唑衍生物H2ADTZ与锰的二维聚合物的合成与晶体结构(英)

A new 1,3,4 thiadiazole-derivative ligand 2,5-(s-acetic acid) dimercapto-1,3,4 thiadiazole (H₂ADTZ) and its one-dimensional manganese polymer Mn(ADTZ)·4H₂O had been synthesized and structurally characterized by X-ray single crystal diffraction in this paper. The Mn(Ⅱ) ion is coordinated with a distorted octahedron by two oxygen atoms from neighboring two deprotonated ligands ADTZ^2- and other four oxygen atoms from four coordinated water molecules. The structural feature of the title compound is the formation of one-dimensional manganese chains polymer through the bridging of dioxygen O-O units. In the solid state structure of the complex, one-dimensional manganese chains are joined together by the weak intermolecular hydrogen bonds and vander Waals interactions forming a two-dimensional supramolecular compound. Furthermore, the UV spectra and electro-chemical properties of the title compound were also investigated. CCDC: 260532.     

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

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

氢键构筑的二维网状结构镍配合物[Ni(en)2(dpas)2]的合成、晶体结构及电化学性质

A new 2D Hydrogen-bonded network complex [Ni(en)2(dpas)2] (Nadpas=sodium diphenylamine sulphonic acid salt,en=ethanediamine) has been synthesized in aqueous solution,and characterized by elemental analysis,IR. The crystal structure was determined by single-crystal X-ray diffraction. The complex crystallizes in space group P21/c,with cell parameters a=0.605 6(5)nm,b=1.448 1(5) nm,c=1.711 9(5)nm,β=93.257(5)°,and V=1.498 9(14) nm3,Dc=1.497 g·cm-3,Z=2,F (000)=708,R=0.027 7,wR=0.072 5. The crystal structure shows that the nickel atom is coordinated with four nitrogen atoms from the two en and two oxygen atoms from two dpas to form a mononuclear complex. Furthermore,the adjacent complex units are extended into a 2D supramolecular network through hydrogen bonds.     

铋(Ⅲ)配合物Bi(1,10-phen)[S2CN(CH3)2]2(NO3),

Three bismuth（Ⅲ） complexes Bi（1,10-phen）[S2CN（CH3）2]2（NO3） （1）, {Bi（S2COCH3）[S2CNC6Hs（CH3）]2}2 （2） and [Bi（S2CNBu2）2（CH3OH）（NO3）]∞ （3） were synthesized and characterized by elemental analysis and IR spectra. Their crystal structures were determined by X-ray single crystal diffraction analysis. Studies show that complex 1 has a monomeric structure with the central bismuth atom eight-coordinated in a capped distorted pentagonal bipyramidal geometry. The complex 2 takes centrosymmetric dimeric structure and the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry.In complex 3, the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry by bridging nitrate O atoms and the resulting structure is onedimensional infinite chain polymer.     

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.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn(NAA)2(4,4’-bipy)(H2O)4]n has been synthesized with α-naphthaleneacetic acid, 4,4’-bipy and manganese(II) sulfate as raw ma-terials. Crystal data for this complex: monoclinic, space group P21/c, a = 1.1421(2), b = 1.6337(3), c = 0.94177(19) nm, β = 112.15(3)o, V = 1.6275(6) nm3, Dc = 1.407 g/cm3, Z = 2, μ(MoKα) = 0.467 mm-1, F(000) = 722, S = 1.007, R = 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese(II) ions are linked together by one 4,4?-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese(II) ion is coordinated with two oxygen atoms of two α-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4?-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

{[Mn2(μ3‐Tda)2(μ‐H2O)(H2O)2(bipy)]·DMF}n – a 2D Manganese(II) Coordination Polymer involving Six‐membered Binuclear Metallacycle Nodes

The single crystal X‐ray analysis of a novel thiophene‐2,5‐dicarboxylic acid (H₂Tda) Manganese(II) coordination polymer, {Mn₂(μ₃‐Tda)₂(μ‐H₂O)(H₂O)₂(bipy)]·DMF}_n, shows two different types of Mn²⁺‐ions with environment of Mn1O₆ and Mn2O₄N₂, and the complex is a two‐dimensional polymer as a result of bridging (Tda)^2? ligands and by connecting the carboxylate‐ and water‐bridged {Mn₂(μ‐Tda)₂(μ‐H₂O)} nodes.     

Assembly of a New Cyano‐bridged 4f‐3d Dimer Sm(DMSO)4‐ (H2O)3Cr(CN)6 and Crystal Structure of [K3(18‐crown‐6)3‐(H2O)4]Cr(CN)6·3H2O

A new cyano‐bridged binuclear 4f‐3d complex Sm(DMSO)₄‐(H₂O)₃Cr(CN)₆ was synthesized and characterized by single crystal structure analysis. It crystallizes in monoclinic, space group P2₁ with a=0.9367(2) nm, b = 1.3917(3) nm, c = 1.1212(2) run, β = 99.88(3)° and Z = 2. In this binuclear complex, Sm atom is eight coordinated and linked to the Cr atom by a cyano bridge. The molecules packs to form 3D structure due to the hydrogen bonds among them. [K₃(18‐C‐6)₃(H₂O)₄]Cr(CN)₆·3H₂O (18‐C‐6 represents 18‐crown‐6‐ether) that was synthesized as a byproduct in the preparation of a Gd—Cr complex is also structurally characterized. Crystal data: triclinic, space group P‐l with a = 1.0496(7) nm, b= 1.1567(14) nm, c = 1.3530(13) nm, a = 94.15(9)°, β = 96.04(8)°, γ = 95.25(9)° and Z = l. [K₃(18‐C‐6)₃(H₂O)₄]‐Cr(CN)₆·3H₂O consists of ionic [K₃(18‐C‐6)₃(H₂O)₄]³⁺ and [Cr(CN)₆]^3‐ pairs, of which the [K₃(18‐C‐6)₃(H₂O)₄]³⁺ ion is a trinuclear duster connected by water, and K atoms are eight coordinated by eight oxygen atoms of one 18‐C‐6 and two water molecules.     

A pentanuclear bimetallic complex of manganese(II) and aluminium(III) ions: tetra‐μ2‐iodido‐iodidobis(μ3‐2‐methoxyethanolato)bis(μ2‐2‐methoxyethanolato)dimethyl(tetrahydrofuran‐κO)aluminium(III)tetramanganese(II)

The molecule of the title compound, [Mn₄Al(CH₃)₂(C₃H₇O₂)₄I₅(C₄H₈O)], contains one Al^III and four Mn^II ions. Two Mn atoms are five‐coordinate in the form of a trigonal bipyramid or a square pyramid. The two other Mn atoms are six‐coordinate with an octahedral geometry. The fourcoordinate Al atom is linked to the manganese core by μ‐O_alkoxo bridges, forming an almost planar five‐membered ring.     

Crystal Structures of [Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O and [Mn(H2O)2(bpy)(C8H12O4)2/2] · H2O with bpy = 2,2′‐bipyridine

Reaction of MnSO₄ · H₂O, 2,2′‐bipyridine (bpy), suberic acid and Na₂CO₃ in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] · 2 H₂O ( 1 ) and [Mn(H₂O)₂‐ (bpy)(C₈H₁₂O₄)_2/2] · H₂O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H₂O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] complex molecules in 1 and 1D [Mn(H₂O)₂(bpy)(C₈H₁₂O₄)_2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H₂O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H₂O molecules located in tunnels along [010]. Crystal data for 1 : P2₁/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P2₁/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8.     

A 1,2,4‐Triazole‐based Polynuclear Mixed‐valence MnIIMnIII Complex: Synthesis,Characterization, and Magnetic Property

A mixed‐valence Mn complex {[Mn^IIMn^III(HL)₂(4,4′‐bpy)(H₂O)₂] · (ClO₄)(DMF)₃(4,4′‐bpy)_0.5}_n ( 1 ) [H₂L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] was synthesized and characterized by X‐ray single‐crystal structure analysis and magnetic susceptibility. Single‐crystal X‐ray analysis revealed that complex 1 has a dinuclear core, in which adjacent central Mn^III atoms are linked by 4,4′‐bipyridine to form an infinite one‐dimensional (1D) molecular configuration. According to the Mn surrounding bond lengths and bond valence sum (BVS) calculations, we demonstrated that the Mn atom coordinated to the pyridine N atoms is in the +2 oxidation state, while another Mn atom coordinated to the phenolic oxygen atoms is in the +3 oxidation state. Magnetic susceptibility data of the complex 1 indicate that the ferromagnetic interaction dominates in this complex.     

Synthesis and crystal structure of heteronuclear La( III )‐Cu(II ) complex { [LaCu2(NTA)2(4,4′‐bpy)(H2O)3]NO3·5H2O}n

A novel La( III )‐Cu( II ) heterometallic coordination polymer {[LaCu₂(NTA)₂(4,4′‐bpy)(H₂O)₃]NO₃·5H₂O]_n, where H₃NTA denotes nitrilotriacetic acid and 4,4′‐bpy denotes 4, 4‐bipyridine, was synthesized and characterized by IR spectrum, elemental analysis and X‐ray diffraction. The complex crystallizes in the triclinic space group Pi with cell parameters a = 1.33710(10) nm, b = 1,44530(10) nm, c =1.0949(2) nm, α = 71.905(7)°, β = 74.327(7)°, γ = 64.427(9)°, V = 1.7912(4) nm³and Z = 2. It consists of heterometallic units, in which each La( II ) ion is coordinated in a distorted monocapped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA^3? ions, and each Cu( I ) ion is coordinated by one nitrogen atom from 4,4′‐bpy and one nitrogen atom, three oxygen atoms from NTA^3?. In the title complex, La( I ) ions and Cu( II ) ions are connected by the heterometallic bridging of NTA^3?, constructing a two‐dimensional network structure along the [110]. And it is extended into an infinite three‐dimensional network structure by the formation of homometallic bridging of Cu‐4, 4′‐bpy‐Cu, exhibiting a certain inclusion ability.     

A Tri‐µ‐O‐S‐O Manganese Dimer: Synthesis,Structral and EPR Study

A Tri‐µ‐O‐S‐O coordinative manganese dimer: [Mn₂(SO₄)₂(phen)₄]·CH₃OH (phen1,10‐phenanthroline) ( 1 ) was yielded by the reaction of 1,10‐phenanthroline and MnSO₄·H₂O in a mixed solvent of methanol and acetonitrile under room temperature and was structurally characterized. Single crystal analysis shows that complex 1 has polymeric structure based on binuclear Mn(II) units bridged by O‐S‐O groups of two SO₄²⁻ anion. The UV spectrum of the complex clarifies that each metal‐organic building unit parallels with each other through the Π‐Π interactions of face‐to‐face separations of two 1,10‐phen planes among the complex, forming a layered structure. And the electronic paramagnetic resonance (EPR) signal clearly indicates that those manganese atoms in complex 1 are in +2 oxidation states.     

Poly[[bis(pyridin‐3‐ol)manganese(II)]‐di‐μ‐pyridin‐3‐olato]

In the title complex, [Mn(C₅H₄NO)₂(C₅H₅NO)₂]_n or [Mn(μ‐3‐PyO)₂(3‐PyOH)₂]_n (3‐PyO⁻ is the pyridin‐3‐olate anion and 3‐PyOH is pyridin‐3‐ol), the Mn^II atom lies on an inversion centre and has octahedral geometry, defined by two N atoms and two deprotonated exocyclic O atoms of symmetry‐related pyridin‐3‐olate ligands [Mn—N = 2.3559 (14) Å and Mn—O = 2.1703 (11) Å], as well as two N atoms of terminal 3‐PyOH ligands [Mn—N = 2.3482 (13) Å]. The Mn^II atoms are bridged by the deprotonated pyridin‐3‐olate anion into a layer structure, generating sheets in the (01) plane. These sheets are linked by O—H⋯O hydrogen bonds. There are also π–π and C—H⋯π interactions in the crystal structure.