Syntheses, Crystal Structures and IR Spectra of Two Mixed Metal Complexes:〔Cr_nFe_(3-n)(μ_3-O)-(μ-O_2CC_2H_5)_6 Py_3〕Cl(n=1,2)

Two mixed metal complexes [Cr2Fe(μ3-O) (μ-O2CC2H5)6Py3]Cl (A)and [CrFe2 (μ3-O) (μ-O2CC2H5 )6Py3] Cl (B) have been prepared in non-aqueous sol-vents. Crystal (A) is monoclinic, space group C2/c, with a= 13. 782(3), b= 18. 381(4), c= 16. 643(2) A, β= 92. 84(5)°, V=4211. 1 (4) A3, Z=4, Mr= 887. 03, Dc= 1. 40 g/cm3, μ= 5. 0 cm-1, F(000) = 1836 and R(Rw) = 0. 057(0. 062) for 2134 unique reflections with I> 3δ(I). Crystal (B) is also monoclinic, space group C2/c ,with a= 13. 793(4), b= 18. 401 (6), c= 16. 657(5) A’, β= 93. 18(3)°, V=4221. 3(5) A3, Z= 4, Mr=890. 88, Dc= 1. 40 g/cm3, μ= 10. 5 cm-1, F(000) = 1844 and R(Rw) = 0. 067 (0. 069) for 2131 unique reflections with I>3δ(I). Both (A) and (B)have been characterized by IR spectra. Besides, the relations between the structuresand IR are discussed.

Syntheses,Crystal Structures and Intermolecular Interactions of Cu(Ⅱ) Complexes with Methyl- benzoic Acid(MBA) and 1,10-Phenanthroline

Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.

Synthesis,crystal structures and luminescence properties of europium and terbium picolinamide complexes

The novel coordination structures of europium and terbium chloride-picolinamide complexes （EuCl3-（C6H6N2O）2.5H2O, Eu-pa and TbCl3.（C6H6N2O）2.5H2O, Tb-pa） are reported. The crystal structures in the solid state are characterized by X-ray single crystal diffraction, FTIR, Raman, FIR, THz and luminescence spectroscopy. In the crystal structures, the pyridyl nitrogen and carbonyl oxygen atoms in picolinamide are coordinated to the metal ions to form a five-membered ring structure. The experimental results indicate the similar coordination structures of Eu and Tb-pa complexes and the changes of hydrogen bonds and conformation provide models for the coordination structures of the ligands induced by complexation. The results of lanthanide ions with ligands having amide groups.

Synthesis and Crystal Structure of a Binuclear Cobalt（Ⅱ） Carboxylate Complex Co2（O2CCMe3）4（C9H7N）2①

Reaction of cobalt carbonate, pivalic acid and quinoline in a refluxing ethanol solvent yielded the dicobalt(Ⅱ) compound, Co 2(O 2CCMe 3) 4(C 9H 7N) 2 (1) (C 9H 7N is quinoline), which has been characterised by elemental analysis, IR and X ray diffraction method. Crystallographic data: monoclinic, P2 1/a, a=9.341(2), b=18.591(4), c=11.822(2) , β=97.71(2), V=2034(1) 3, Z=2, M r=918.19, D c =1.27 g/cm -3 , F(000)=820, μ (Mo Kα )=8.60 cm -1 , T =293K, final R=0 049, R w =0.060 for 2715 observed reflections with I】3.0 σ(I) . The centrosymmetric molecule comprises a pair of cobalt(Ⅱ) atoms connected by four pivalate ligands in syn syn bridging modes. Square pyramidal five coordination of cobalt(Ⅱ) is further completed by a quimoline molecule. The Co Ⅱ-Co Ⅱ distance is 2.784(1) .

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method.

Synthesis，Crystal Structure and Infrared Spectrum of Lanthanum Dinuclear Coordination Compound with Alanine：〔La2（ala）4（H2O）8〕·（ClO4）6

Lanthanum coordination compound with l-alanine[La2（ala）4（H2O）8]·（ClO4）6（ala=l-alanine） was synthesized by reaction of lanthanum perchlorate with l-alanine in aqueous solution and obtained in the form of single crystals.The X-ray crystal structure has been determined and the IR spectrum has been studied.The title compound Cl6La2C12H44O40N4,Mr=1375.2,crystallizes in the triclinic,space group P1 , with parameters: a= 11.227（3）,b=11.445（2）,c=11.014（3）,α=114.46（2）,β=114.51（2）,γ=78.62（2）°,V=1171.73,Z=1,Dc=1.95 g/cm￣3,F（000）=680,μ=22.9 cm￣-1（MoKα）.The final R=0.050,Rω=0.051.In the crystal,two lanthanum ions are coordinated by four alanine molecules via four carboxylate bridges to form a dinuclear coordination compound.Four water molecules are coordinated to each lanthanum ion. There is a symmetric centre between the two lanthanum ions.The IR spectrum of the coordination compound and the relationship between the IR spectrum and the structure have been studied.The mechanism of the configuration inversion of alanine has been proposed.

Spectral Analysis and Crystal Structure of Tris（benzoyl－trifluoroacetonate）bis（triphenyl－phosphine oxide）Europium（Ⅲ）

C6H5COCHCOCF3)3[(C6H5)3PO]2Eu,Mr=1354.01,triclinic P1,a=11.244(3),b=12.252(3),c=23.784(1),α=79.66(2),β=76.38(3),γ=71.44(3)°,V=2999.33,Z=2,Dc=1.499g/cm3,μ(MoKα)=11.79 cm-1,final R=0.066(Rw=0.069) for 7899 observed reflections with I】3σ(Ⅰ),The europium ion(Ⅲ) is coordinated by eight oxygen atoms,of which six from C6H5COCHCOCF3 and the other two from (C6H5)3PO,to form a dodecahedral configuration with the average distance of Eu-O(C6H5COCHCOCF3) of 2.410 and that of Eu-O[(C6H5)3PO] of 2.385.The coordination of Eu(Ⅲ) with the ligands was characterized by IR and Raman spectroscopy.The molecular rigidity,which effects luminescence of the complexes,was discussed by fluorescence spectroscopy of the Eu(Ⅲ) complexes.

Solid State Synthesis and Structural Characterizationof Binuclear Cu( I)-Sb Ph_3 Co m plex 〔 Cu( Sb Ph_3)_2 I〕

Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space group P2 1/a (#14), a = 20 436(5), b=14.125(3), c=24.683(3) , β=110.67(1)°, Z=4, V =6666(2)  3; C 72 H 60 Sb 4I 2Cu 2, M r = 1792, D c = 1.787 g·cm -3 , μ (Mo Kα ) = 31.88 cm -1 , F(000)=3440, R= 0.038 and R w= 0.043 for 5632 observed reflections ( I≥3.0σ(I) ) and 361 refined parameters. The result reveals the copper and the bridging iodide atoms form an approximately planar rhomboid array. Effects of the bulkiness of the ligands upon the structures of the analogous complexes are discussed.\;

The preparation, structure and spectra properties of dual μ3-oxo bridged tetranuclear complexes containing the [CrnFe4-nO2]8+ core(n=0,2,4)

The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on differentiation of coordination bond strengths and electronic environment of metal atoms in these complexes.

超分子化合物{[Mn_2(pda)(phen)_4(H_2O)_2]·2H_2O·2ClO_4^-}的构筑及表征

利用间苯二乙酸、1,10-邻菲啰啉和高氯酸锰在水热条件下反应制备了一种新型超分子配合物{[Mn2(pda)(phen)4(H2O)2]·2H2O.2ClO4-}(H2pda=间苯二乙酸,phen=1,10-邻菲啰啉).通过X单晶衍射测定了晶体结构,并用元素分析、红外光谱等技术对其进行了表征.配合物属3斜晶系,空间群为P-1,a=1.129 0(2)nm,b=1.705 0(2)nm,c=1.734 5(1)nm;α=110.559(1)°,β=107.588(9)°,γ=93.102(12)°;Z=1,R1=0.071 0,wR2=0.202 9.晶体结构分析表明2个锰在1个间苯二己酸的连接下形成了一个双核结构,再在船型六元环氢键和π…π堆积共同作用下,双核结构单元被连成2维网络结构.毗邻的2维结构之间又通过氢键的支撑,拓展为3维网状超分子体系.

Cu(Ⅱ)-牛磺酸缩水杨醛席夫碱-邻菲咯林三元配合物的合成、晶体结构及性质

The title complex was synthesized by reaction of taurine salicylic schiff base(TSSB), O-phenanthroline(phen) and cupric acetate in water-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 498.00. The crystal structure of the title complex belongs to orthorhombic system with space group Pbcn and cell parameters: a=3.107 2(4) nm, b=1.289 09(18) nm, c= 1.034 78(14) nm; and V=4.144 7(10) nm3, Z=8, Dc=1.596 g·cm-3, μ=1.197 mm-1, F(000)=2 048. The compound is an one-dimensional chain complex of infinite length which are connected with hydrogen bonds. The Cu(Ⅱ) was coordinated by two oxygen atoms and three nitrogen while the o atoms of Ac- groups did not participate in the coordination. The Cu(Ⅱ) formed a distorted tetragonal pyramid and the capacities of coordination to Cu(Ⅱ) of atoms was discussed. Besides, the TG-IR of the complex was analyzed. The kinetics of the thermal decomposition reaction of the complex was studied under a non isothermal condition by TG-IR. TG and DTG curves indicate that the complex decomposed in three stages: [Cu(TSSB)(Phen)]·1.5H2O Cu(TSSB)(Phen) Cu(TSSB) CuO The kinetic parameters were obtained from the analysis of TG,DTG cures by OZAWA-Flynn-Wall method, and the activation energy and the value of A of the three stages are 74.98 kJ·mol-1, 286.65 kJ·mol-1, 87.55 kJ·mol-1; 9.66×108 s-1,1.82×1028 s-1, 3.09×103 s-1, respectively.

碱金属复合氟化物的红外光谱研究

用傅立叶变换红外光谱法研究了ＫＩｎＦ４、ＫＡｌＦ４、ＲｂＡｌＦ４、ＣｓＡｌＦ４、ＲｂＧａＦ４、ＣｓＧａＦ４等六种碱金属复合氟化物的远红外及中红外光谱，对部分谱带进行了指认，并探讨了远红外光谱与其晶体结构的关系。

苯甲酸根为桥的双核Eu(Ⅲ)配合物的合成及晶体结构

在EtOH：H2O=2:1的溶剂中，以Eu（NO3）3·6H2O、C6H5COONa和Phen（邻菲哈啉）为原料，合成了四桥双核配合物［Eu2（Phen）2（C6H5COO）6］．晶体属三斜晶系，空间群P1，a=1．08156（7）nm，b=1．19331（7）nm，c=1.24401（8）nm，a=104.972（5）°，β=93．661（5）°γ=113.297（5）°，Z=1．R=0.0437．晶体中2个Eu原子处于晶体学等效位置，配位数为9，Eu-Eu间距离为0．4052nm．讨论了标题化合物的UV－Vis谱与其它Eu3+离子谱的异同．

以2,2′-联嘧啶为副配体的铱配合物的合成、晶体结构和发光性质研究

利用环金属配体2-(4′,6′-二氟苯基)吡啶(dfppy)和副配体2,2′-联嘧啶(bpm)合成了一个铱配合物[Ir(dfppy)2(bpm)]Cl,通过1HNMR,质谱,元素分析及红外光谱对其进行了表征,并且测定了其晶体结构。同时利用得到的中间配合物[Ir(dfppy)2(bpm)]+[Ir(dfppy)2(Cl)2]-晶体结构讨论了配合物形成过程。对配合物[Ir(dfppy)2(bpm)]Cl的紫外可见吸收光谱和发光光谱的研究表明,其常温发射位于609nm处,初步推测该磷光发射可能来自金属到配体的电荷转移(MLCT)跃迁和配体自身π→π*跃迁(LC)的混合。

Schiff碱与锰(Ⅲ)的单核和双核配合物的合成与结构

本文报道合成了以水杨醛及邻香草醛缩丙醇胺 Ｓｃｈｉｆｆ 碱与锰（ Ⅲ） 的六个新型配合物，其中［ Ｍｎ２（ｓａｌｐａ）２ （ Ｐｈ Ｃ Ｏ Ｏ）２ ］·２ Ｃ Ｈ２ Ｃｌ２ ，［ Ｍｎ２ （ｖａｎｐａ）２ （ Ｐｈ Ｃ Ｏ Ｏ）２ ］·２ Ｃ Ｈ Ｃｌ３ ，［ Ｍｎ２ （ｖａｎｐａ）２ （ Ｃｌ Ｃ Ｈ２ Ｃ Ｏ Ｏ）２ ］（ Ｈ２ｖａｎｐａ 为邻香草醛缩丙醇胺； Ｈ２ｓａｌｐａ 为水杨醛缩丙醇胺） 三个为双核，［ Ｍｎ（ Ｈｓａｌｐａ）２（ Ｈ２ Ｏ） Ｃｌ］ ，［ Ｍｎ（ Ｈｖａｎｐａ）２（ Ｈ２ Ｏ） Ｂｒ］ 和［ Ｍｎ（ Ｈｓａｌｐａ）２（ Ｎ Ｃ Ｓ）］ 三个为单核。并对配合物的合成进行了讨论，同时对配合物的红外光谱进行了归属。对配合物［ Ｍｎ２（ｖａｎｐａ）２（ Ｐｈ Ｃ Ｏ Ｏ）２］·２ Ｃ Ｈ Ｃｌ３ 进行了单晶结构测定，其锰与锰间的距离为２ ．８４８ 〓，对配合物的磁距也进行了测定。

两个N,N′-亚乙基双(1-苯基-3-亚氨基-1-丁酮)锰(Ⅲ)配合物的合成、表征和晶体结构

合成了两个 N,N′-亚乙基双 ( 1 -苯基 -3 -亚氨基 -1 -丁酮 ) (简写为 H2 bzacen)的锰配合物 Mn( bzacen)·( NO2 ) ( Et OH) ( 1 )和 Mn( bzacen) ( NO2 ) ( Me OH) ( 2 ) .晶体结构分析表明 :配合物 1晶体属正交晶系 ,空间群 Pbca,晶胞参数 a=2 .81 73 ( 6) nm,b=2 .1 94 6( 4) nm,c=0 .7683 ( 6) nm,V=4 .750 ( 5) nm3 ,Z=8,μ=5.71 cm-1,R=0 .0 540 .配合物 2晶体属正交晶系 ,空间群 Pbca,晶胞参数 a=2 .764 1 ( 6) nm,b=2 .1 83 2 ( 4) nm,c=0 .770 5( 2 ) nm,V=4 .650 ( 3 ) nm3 ,Z=8,μ=5.81 cm-1,R=0 .0 564 .在这两个配合物中 ,Mn( )原子均具有畸变的 N2 O4 八面体配位构型 ,整个晶体通过分子间氢键作用形成一维的无限链状结构 .红外光谱表明 ,配体在形成配合物后 ,νC=N,νC=O和νC=C谱带移向低频 ,NO-2 以一个 O原子与 Mn( )配位 .电子光谱表明存在 d-d* ,π-π*和

氢键在构建超分子[Cu(C_6H_4NO_2)_2(H_2O)_3·H_2O]中的作用

采用水热合成反应,合成了含有多种氢键网络的Cu(Ⅱ)的配合物[Cu(C6H4NO2)2(H2O)3·H2O].对配合物的单晶进行了X光衍射分析.结果表明,在化合物中存在着3种氢键,使化合物晶体构成了无限延伸的三维网络结构,形成了超分子.晶体结构数据:晶体属三斜晶系,空间群为P1,晶胞参数为a=0.69577(5)nm,b=0.71428(10)nm,c=0.86691(6)nm;α=68.3860(12)o,β=68.439(5)o,γ=62.717(3)o,V=0.34554(6)nm3,Z=2,F(000)=193,Dc=1.816g/cm3,最终收敛因子:R=0.0269,ωR=0.0759.讨论了氢键在构建[Cu(C6H4NO2)2(H2O)3·H2O]超分子中所起的作用.并对化合物的红外吸收光谱和紫外可见吸收光谱进行了分析指认.

复合固体超强酸催化剂WO_3-ZrO_2-SO_4^(2-)的研究(Ⅱ)——晶体结构及其表面结构

复合固体超强酸催化剂 WO_3-ZrO_2-SO_4^(2-)具有 H_0≤-16.04的酸强度,XRD 研究证明其具有四方晶体结构,各组分间形成混合物;XPS 和 AES 研究发现 W(+6),Zr(+4),S(+6)和 O(-2)之间存在强的相互作用,红外光谱研究表明其存在 OH 基,表现强的 B 酸性,表面附载硫具有和金属离子螯合配位的结构形式.

［Cu（C_（14）H_（11）O_3）（C_（10）H_8N_2）_2］NO_

合成了［Ｃｕ（Ｃ_（１１）Ｈ_（１１）Ｏ_３）（Ｃ（１０）Ｈ_８Ｎ_２）_２］ＮＯ_３·Ｃ_２Ｈ_５ＯＨ化合物并测定其晶体结构。晶体属Ｐ１空间群，ａ＝１．１９１１（２）ｎｍ，ｂ＝１．５３２２（２）ｎｍ，ｃ＝１．０４９２（２）ｎｍ，ａ＝１０８．９８（１）°，β＝１０７．０４（１）°，γ＝７０．２５（１）°，Ｚ＝２．在［Ｃｕ（Ｃ_（１１）Ｈ_（１１）Ｏ_３）（Ｃ_（１０）Ｈ_８Ｎ_２）_２］￣＋配合阳离子中，２个２，２’－联吡啶的４个氮原子和二苯羟乙酸的１个羧基氧原子位于铜原子周围，从而使铜原子子具有畸变的三角双锥配位构型。对红外光谱进行了归属。

[CoL_2]NO_3的合成、晶体结构和红外光谱

将水杨醛与N-2-羟乙基乙二胺按1∶1物质的量混合,缩聚得到配体L,再分批加入等摩尔的Co(NO3)2·6H2O,制备出硝酸二(水杨醛N-2-羟乙基乙二胺缩席夫碱)合钴(Ⅲ),该配合物分子式[CoL2]NO3,属正交晶系,空间群为Fdd2,α=1.8576(8)nm,b=5.696(2)nm,c=0.9874(4)nm,V=10.448(8)nm3,α=β=γ=90.00°,Z=16.