Crystal Structure and Catalytic Properties of Tetrakis (4-hydroxyphenyl) Porphyrinato Manganese(Ⅲ) Chloride (MnTHPPCl)

The crystal structure of meso-tetrakis(4-hydroxyphenyl)porphyrinato manganese chloride(MnTHPPCl)and its supramolecular architecture based on the hydrogen bonds of one counter Cl anion with four hydrogen atoms of four-OH groups from different MnTHPPCl molecules cooperated by self-assembly of the porphyrin units were first reported.This compound crystallized in the tetragonal space group I4/m with a=1.39928(7)nm,b=1.39928(7)nm,c=0.94498(10)nm,V=1.8503(2)nm3,and Z=2.As a catalyst,MnTHPPCl also showed a high catalytic acti-vity in the conversion from 1-naphthylamine(1-NA)to bis(4-oxo-benzo-2-cyclohexen-1-yl)amine(BOBCHA)via oxidative coupling under mild conditions.     

Synthesis and Structure of {（Tab-Tab）[Ag2（μ-Cl）41.2MeCN}n （Tab = 4-（Trimethylammonio）benzenethiolate）

In the presence of Et4NCl·H2O, reaction of AgCl with TabHPF6 in MeCN afforded the title complex {（Tab-Tab）[Ag2（μ-Cl）4]-2MeCN}n 1. 1 crystallizes in the orthorhombic space group Pbcn with a = 16.782（3）, b = 6.8358（14）, c = 26.194（5） A, V = 3004.9（10） A3, Z = 8,μ = 1.817 mm^-1, Dc = 1.711 g/cm3, T= 223 K, C1lH16AgCl2N2S, Mr= 387.10, F（000） = 1544, S= 1.160, R = 0.0528 and wR = 0.0896 for 2732 observed reflections with I 〉 2σ（I）. 1 contains a 1D linear [Ag2Cl4]n^2n- chain coupled with the [Tab-Tab]2＋ dications. Intermolecular hydrogen bonding interactions between the protons of methyl groups from the Tab-Tab dications and the chlorides result in the formation of a 2D hydrogen-bonded network.     

Synthesis,Crystal Structure and Thermal Stability Properties of the Supramolecular Complex [Co（phen）3][（C6H5）2C（OH）COO]2·7H2O

One new cobalt complex [Co（phen）3][（C6Hs）2C（OH）COO]2·7H2O with benzeneacetic acid （BAA）, 1,10-phenanthroline and cobaltous perchlorate has been synthesized by means of solvent method. It crystallizes in the triclinic system, space group P^-1, with a = 1.14181（13）, b = 1.64417（18）, c = 1.65342（18） nm, α = 74.2830（10）, β= 84.4490（10）, γ = 74.9430（10）°, V = 2.8842（6） nm^3, Dc = 1.359 g/cm^3, Z = 2, F（000） = 1234, R = 0.0621 and wR = 0.1673. The crystal structure shows that the cobalt ion is coordinated with six nitrogen atoms from three 1,10-phenanthroline molecules, giving a distorted octahedral coordination geometry. There are a lot of hydrogen bonds in the complex, from which a two-dimensional network is constructed. The result of TG analysis shows that the title complex is stable below 130.0 ℃.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

Synthesis and Crystal Structure of a New Oxovanadium（V） Multicomponent Complex with Acylhydrazone and Benzoylhydrazine

A new oxovanadium（V） complex with the mixed ligand of 2-oxopropionic acid benzoylhydrazone （C10H10N2O3） and benzoylhydrazine （C7H8N2O）, VO（C7H7N2O）（C10H9N2O3）, has been synthesized. Its structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic system with space group P21/n and cell parameters： a=1.1136（4） nm, b=0.6217（2） nm, c=2.6038（9） nm, β=97.182（6）°, V= 1.7887（11） nm^3, Z=4, F（000）=836, Mr=407.28, Dc= 1.512 g/cm^3,μ （Mo Kα） =0.592 mm^-1, R1 =0.0445, wR2= 0.1203. Vanadium atom is 6-coordinated by carboxyl and carbonyl O atoms and N atom of one tridentate C10H10N2O3 to form two stable five-membered rings with the same edge, and the other coordinated atoms of N and O come from one bidentate benzoylhydrazine C7H8N2O. The title complex has a six-coordinated V center [VO（N2O3）] with a distorted octahedral arrangement. In the crystal lattice, there are hydrogen bonding interactions between two molecules.     

Crystal Structure,Thermal Behavior and Luminescence of a One-dimensional Coordination Polymer [Zn（4-CPOA）（Phen）（H2O）]n

A novel coordination polymer of [Zn（4-CPOA）（Phen）（H2O）]n （C21H16N2O6Zn,1,4-CPOA = 4-carboxylato-phenoxyacetate dianion and Phen = 1,10-phenanthroline） has been synthesized and characterized by elemental analysis,IR,TG,PL and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system,space group of P1 with a = 9.622（3）,b = 9.631（3）,c = 11.526（4）A,α = 67.719（5）,β = 71.203（5）,γ = 83.552（6）o,V = 935.5（5） A^3,Z = 2,Dc = 1.625 g/cm^3,μ = 1.357 mm^-1 and F（000） = 468. The Zn（II） ion is surrounded by three carboxylate O atoms from two different 4-CPOA groups,two N atoms from the Phen ligand and one water molecule,forming a distorted octahedral coordination configuration. The Zn（II） ions were alternately interlinked by carboxylate groups of 4-CPOA with chelating bisbidentate and monodentate modes into a one-dimensional zigzag chain having an intrachain distance of ca. 9.631（1） . Under the direction of supramolecular recognition and attraction,the adjacent chains yield a double-stranded chain through π-π stacking between the phen ligands,which was further expanded into a 2-D framework via strong C–H–π interaction （ca. 2.95（1） ） between the 4-CPOA ligands and into a 3-D supramolecular network by strong hydrogen bond between terminal water molecule and carboxyl group. TG/DTG shows that its chain skeleton is thermally stable up to 419 oC and the blue fluorescent emission of the complex was determined at 471 nm in a solid state with its long decay lifetime of 1.83 ns.     

Synthesis and Crystal Structure of a Copper（Ⅱ） Compound Constructed by N-（4,6- Dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea

A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.     

Synthesis and Crystal Structure of Tetra（o-cyanobenzyl）tin

The tetra（o-cyanobenzyl）tin compound has been synthesized by the reaction of cyanobenzyl chloride with tin, and its molecular structure was characterized by elemental analysis, IR spectra, ^1H NMR and X-ray diffraction. Crystal data for this compound： monoclinic, space group C2/c, Mr = 583.24, a = 1.9629（2）, b = 1.05967（13）, c = 1.41249（18） nm, β= 118.180（2）^o, V = 2.5898（5） nm^3, Z = 4, Dc =1.496 g/cm^3, μ（MoKa） = 1.015 cm^-1, F（000） = 1176, R = 0.0189, wR = 0.0497 （observed reflections with I 〉 20（I）） and R = 0.0218, wR = 0.0513 （all reflections）. The molecular structure adopts a distorted tetrahedral geometry around the tin atom. The Sn＇＂N weak interaction between the Sn and N atoms of cyano forms an intermolecular H-bonding, and the bond length is 0.3570 nm; the interaction between hydrogen of methylene and benzene ring of benzyl forms C-H…C with its bond length of 0.2817 nm; and the interaction among hydrogen of benzene ring and carbon of cyano forms Ph-H…C bond （0.2897 nm） Of the σ…π interaction. A 3D chain structure is formed by the above weak intermolecular interactions.     

Synthesis and Crystal Structure of a New Cadmium（Ⅱ） Supramolecular Network Containing Chelating Imidazole-4-carboxylate Ligand

A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.     

Crystal Structure,Electrochemical and Fluorescent Properties of a New Cadmium（II） Complex [Cd（C12H6O4N2）（Phen）2（H2O）]·3H2O

A new Cd（II） complex [Cd（C12H6OaN2）（Phen）ffH2O）]＇3H2O with 2,2＂-bipyridine- 3,3＂-dicarboxylic acid as a ligand has been synthesized. Crystal data for the title complex are as follows： monoclinic, space group P2dn, a = 12.8458（5）, b = 17.9131（7）, c = 15.2960（6） A, β = 111.7430（10）°, V = 3269.3（2） A3, Dc = 1.581 g/cm3, Z = 4,/a（MoKa） = 0.731 mm-1, F（000） = 1580, the R = 0.0244 and wR = 0.0605. In the title complex, the central Cd（ll） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties of the title complex were studied. The results show that the electron transfer of the title complex is irreversible in the electrode reaction and it has a broad emission peak in the range of 470-508 nm with the excitation wavelength of 488 nm.     

配合物[Cu(H2biim)2]Br2的合成和晶体结构

The complex [Cu(H₂biim)₂]Br₂ (H₂biim=2,2′-biimdazole) has been synthesized and structurally charac-terized. It crystallizes in the Monoclinic system, space group C2/c with a=1.422 5(4) nm, b=0.931 2(2) nm, c=1.343 1(3) nm, β=116.227(4)°, V=1.595 9(7) nm^-3, R₁=0.060 2, wR₂=0.152 8 and Z=4. The copper ion has a sligh-tly distorted square planar coordination configuration with four nitrogen atoms from two H₂biim ligands. The complex has a one-dimensional chain structure, which is formed by hydrogen bonds and semi-coordinate bonds. CCDC: 624679.     

二氯四(苯丙酮-1, 2, 4-三唑)合钴六水配合物晶体结构

0IntroductionRecently,thecompoundscontaining1H-1,2,4-tr-iazolegrouphaveattractedmuchinterestbecauseoftheirexhibitingsomefungicidalactivityandplantgrowthregulatingactivity犤1犦,andshowingantibacterialactivityagainstPucciniareconditeandrootsgrowthregulationforcucumber犤2犦.Also,suchcompoundsareincreasinglybeingstudiedbecauseofthecoordinationchemistryofazolesactingasligandsintransitionmetalcompounds.Asamatteroffact,thetriazolederivativeshavebeenextensivelyusedasterminalandbridgingligands,andthey…     

原位产生的SO42-配位的二维无机钴配合物K2[Co3(OH)2(SO4)3(H2O)2]的水热合成及晶体结构

相同的水热反应条件下4-氨基-二(2-吡啶基)-1,2,4-三氮唑(abpt)、KSCN与钴盐(CoCl2·6H2O)反应合成了2种新的钴配合物:零维的单核配合物[CoSCN(abpt)](1α)和二维的无机层状配合物K2[Co3(OH)2(SO4)3(H2O)2](1β),并通过元素分析和红外光谱对其进行了表征.配合物1α的晶体属于单斜晶系,P21/c空间群.配合物1β晶体属于正交晶系,Cmc21空间群.在配合物1α中,abpt和SCN-配体都参与配位与Co(Ⅱ)离子形成了2个不同的单核单元,这些单核单元又通过S原子和N原子之间的氢键作用连成了三维超分子结构;在配合物1β中,abpt配体没有参与配位,而SCN-配体则被氧化成了SO42-离子并与Co(Ⅱ)离子配位形成了二维配位层状结构,相邻层之间进一步通过氢键作用形成了沿c轴方向有孔道的三维超分子网络,这些孔道里面填充着反离子K+.     

双核银化合物:六乙烯基硫脲二高氯酸合银的合成和晶体结构

The crystal and molecular structure of [Ag₂(ETU)₆]·(ClO₄)₂ has been determined by X-ray crystallography. It crystallizes in the monoclinic, space group P2₁/c, with lattice parameters a=0.63270(9)nm, b=2.4264(2)nm, c=1.2128(1)nm, β=92.721(9)°, V=1.8597(3)nm³, Z=4, D_c=1.835Mg·m^-3, F(000)=1032, μ=1.591mm^-1. The molecule is built up of centro-symmetric dimeric entities, in which the four-membered Ag₂S₂ ring is planar and the angle of S(3)-Ag(1)-S(3A) is 107.70(2)° for symmetry requirements. The silver atoms have slightly distorted tetrahedral coordination environment, and the sulfur atoms of the ETU group occupy four coordi-nation sites. The two percholate anions in general position balance the charge. In the solid state, the title compound forms three dimensional network structures through hydrogen bonds. The intermolecular hydrogen bonds and ex-tensive intermolecular interaction connect the [Ag2(ETU)₆]²⁺ ion and two ClO₄^- anions to contribute to the stability of the structure. CCDC: 208731.     

配合物Pb(cbba)_2(phen)_2的水热合成、晶体结构与荧光性能研究(英文)

A new metal-organic complex Pb(cbba)2(phen)2 (1, H2cbba=2-(4′-chlorine-benzoyl)benzoic acid, phen= 1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a=1.474 49(7) nm, b=0.953 90(4) nm, c=3.031 65(14) nm, V=4.264 1(3) nm3, C52H32Cl2N4O6Pb, Mr=1 086.91, Dc=1.693 g·cm-3, μ(Mo Kα)=4.141 mm-1, F(000)=2 144, Z=4, the final R=0.018 3 and wR=0.045 7 for 3 582 observed reflections (I2σ(I)). In the crystal structure, the lead atom is six-coordinated with two carboxylate oxygen atoms from different cbba ligands and four nitrogen atoms from different phen ligands, showing a distorted octahedral geometry. Furthermore, 1 shows yellow photoluminescent property at room temperature.     

氯化六咪唑合铁四水分子的结构表征和电化学性能研究(英)

The crystal structure of the title compound, [Fe(Im)₆]Cl₂·4H₂O, (Im=imidazole) was determined by X-ray analysis. The crystal structure consists of Fe(Im)₆²⁺ cation, two Cl^- anions and four non-coordinated water molecules. It crystallizes in the triclinic system, space group P1, with lattice parameters a=0.879 7(2) nm, b=0.906 8(2) nm, c=1.058 1(2) nm, α=75.35(3)°, β=83.20(3)°, γ=61.85(3)°, and Z=1; The Fe(Ⅱ) ion assumes centrosymmetric octahedron geometry with the FeN₆ core. Six imidazole molecules are coordinated to each iron(Ⅱ) ion through its tertiary nitrogen atom. The bond distances of Fe-N are in range of 0.212 8(1) nm to 0.220 4(1) nm. In the solid state, [Fe(Im)₆]²⁺, H₂O molecules and chlorine anions form three dimensional hydrogen bonds network which stabilized the crystal structure. Elemental analysis and electronic spectrum are in agreement with the structural data. The thermal gravity (TG) data indicate that thermal decomposition of the title compound takes place in five steps. In these cases, the residue may be Fe. From the cyclic voltammogram measurement in EtOH/H₂O, we know that electrode reaction was a quasi-reversible process. CCDC: 215335.     

稀土氧化膦取代杯芳烃配合物的合成与结构

合成了一种新的氧化膦取代杯芳烃衍生物的稀土离子(La³⁺,Eu³⁺)硝酸盐配合物.通过元素分析和红外光谱对配合物进行了表征.在无水甲醇中培养出了配合物的单晶,用X射线单晶衍射法测定了其晶体结构.硝酸镧配合物晶体[L·La(OH₂)(NO₃)₂]NO₃{L为四(亚甲基二苯基氧化膦)杯[4]芳烃}属四方晶系,空间群P4₃2₁2,晶胞参数a=b=1.8977(4)nm,c=3.1087(11)nm;Z=4;V=11.196(5)nm³;D_c=1.097g/cm³,F(000)=3712,μ=0.491mm^-1,R₁=0.1181,wR₂=0.1930.硝酸铕配合物晶体[L·Eu(OH₂)(NO₃)₂]NO₃·CH₃OH属单斜晶系,空间群C2/c,晶胞参数a=2.88172(11)nm,b=5.4015(2)nm,c=2.01189(7)nm;β=133.4067(9)°,Z=8;V=22.7511(14)nm³,D_c=1.106g/cm³,F(000)=7464,R₁=0.0671,wR₂=0.1794.2个配合物的晶体结构相类似,配合物中配体的4个磷氧键上的氧原子、2个双齿配位的硝酸根中的4个氧原子还有1个水分子中的氧原子分别参与了配位.中心离子配位数为9,配位多面体为单帽四方反棱柱体.另外在铕配合物的杯芳烃中还包合了1个甲醇分子.     

二维层状水合酸式硫酸铈H3O[Ce(SO4)2·(H2O)3]·H2O的水热合成与结构表征

镧系金属硫酸盐由于在稀土分离等方面具有重要的应用而受到广泛关注。但是，因其适于结构测定的单晶相对难以得到，迄今，关于稀土硫酸盐的结构报道仍然较少，且主要局限于水合硫酸盐和三元硫酸盐．近几年中，基于硫酸根与磷酸根在结构上的相似性，借鉴在水热／溶剂热体系中采用有机胺作模板剂大量合成具有空旷骨架结构的微孔磷酸盐的成功经验，以有机胺为模板剂合成具有空旷骨架结构的镧系金属硫酸盐的工作也已见诸报道．在这些化合物中，由于硫酸根配位方式的多样性和稀土元素配位数和配位构型的可调变性，展现出了一些有趣的结构特征．     

Synthesis and properties of one-dimensional Ni(Ⅱ) and Ni(Ⅱ)Cu(Ⅱ) complexes linked by hydrogen bond

Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.