Synthesis and Crystal Structure of [(η~5-C_5H_5)(THF)Sm]_2[μ-η_2:η_2-N_2Ph_2]_2·2THF

1 INTRODUCTION Since last decade, the chemistry of divalent organolanthanide complexes has yielded particularly remarkable and striking results. The major break- through in the chemistry of divalent organolan- thanides, especially Sm(II), includes the u…     

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.     

[(η~5-C_5H_5)_2NdCl·THF]_2的合成及其晶体结构

由于歧化反应的存在,以前试图合成二环戊二烯基轻稀土氯化物一直没有成功。我们用NdCl_3·2C_4H_8O和环戊二烯钠(摩尔比为1:1.8)在四氢呋喃中在室温下反应,成功地得到[(η~5-C_5H_5)_2NdCl·OC_4H_8]_2配合物单晶。元素分析、红外光谱和X光电子能谱的数据证实了这一配合物的组成。在—60℃的干燥氮气保护下,收集X光衍射数据,测定了晶体结构,晶体属单斜晶系空间群为P2_1/c,z=2。晶格参数为:a=8.201(3),b=21.589(6),c=8.596(3),β=109.10(3)~0晶体结构是利用Patterson与Fourier技术得到,对1680个反射,经最小二乘修正,最后的R=0.0636。结构表明,该配合物是以两个氯离子桥联的二聚体的方式存在。四氢呋喃分子中的氧原子同金属离子键合,Nd=O键长为2.55,两个环戊二烯分子中的所有碳原子同金属离子间的平均的Nd—C键长为2.76A,Nd—Cl=2.79,Nd—Cl_a=2.86,Nd—Nd_a=4.52,Cl—Nd—Cl_a键角为73.7°。晶体结构分析排除了该配合物是(η~5-C_5H_5)_3Nd与NdCl_3的混合物的可能性。     

Synthesis and Crystal Structure of a Novel Fe(Ⅲ) Schiff Base Complex

A novel Fe(Ⅲ) Schiff base complex,FeⅢ(HL) {H4L = 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane},has been prepared and characterized by elemental analyses,IR spectrum,and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P21/n with a = 12.569(3),b = 12.955(3),c = 17.647(4) ,β = 91.896(9)°,V = 2871.9(1) 3,Z = 4,Dc = 1.391 g/cm3,F(000) = 1252.0,Mr = 601.45,R = 0.0383 and wR = 0.1025.The structural analysis reveals that the Fe(Ⅲ) ions are six-coordinated by imine nitrogen atoms and phenolic oxygen atoms form three pendant arms of Schiff base ligands,and one of the salicylaldimine chelating units remains uncoordinated.Discrete complex molecules were further assembled into 1D supramolecular aggregations by C-H…O hydrogen bonding and C-H…π interactions.     

(η~5-C_5H_5)Ln(η~8-C_8H_8)(THF)_n(Ln=Pr,Nd,Gd)的合成及(η~5-C_5H_5)Pr(η~8-C_8H_8)(THF)_2的晶体结构

自1969年首次报道稀土环辛四烯基化合物Eu(C_8H_8)和Yb(C_8H_8)的合成以来,相继合成K[Ln(C_8H_8)_2],[Ln(C_8H_8)Cl·2THF]_2和[Ln(C_8H_8)·2THF]等,还报     

SYNTHESIS of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF AND CRYSTAL STRUCTURE OF(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF

The reaction of LnCl_3 with K _9H_7(C_9H_7=indenyl)andK_2C_8H_8(C_8H_8=cyclooctatetraene)in tetrahydrofuran(THF)give thecorresponding complexes(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF.The synthesis of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF(Ln=Pr,Nd)and crystal structure of(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF are described.     

Synthesis and Crystal Structure of [(ArO)_2(THF)Sm(μ-OH)]_2·2THF(Ar=C_6H_(2-)~tBu_3-2,4,6)

1 INTRODUCTION Sm(II) chemistry has been extensively studied due to the strong reduction potential of this 4f6 ion[1]. The transformation of unsaturated substrates by Sm (II) complexes into products with unusual structures is one of the most interesting research areas. For the successful examples reported, Sm(II) starting mate- rials were restricted primarily to cyclopentadienyl complexes[2]. The reactivity of Sm(II) complex with phenolate ligands has seldom been explored. Recen- tl…     

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [(η~5-C_5Me_5)_2Mo_2(μ_3-S)(μ-S)_3(CuCl)]

The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.     

(η~5-C_9H_7)_2Yb(THF)_2的晶体结构

双(茚基)镱(Ⅱ)四氢呋喃配合物(η~5-C_9H_7)_2Yb(THF)_2的晶体属单斜晶系,C_c空间群,晶体学参数a=13.506(4),b=11.081(2),c=15.577(5),β=92.68(3)°,V=2329(1),D_c=1.56g/cm~3,Z=4,μ=42.4cm~(-1),F(000)=1088,最终编离因子R=0.029,R_w=0.031。中心离子Yb~(2+)与两个茚基以η~5形式成键且与两个四氢呋喃中的氧成键,茚基的两个质心和四氢呋喃中的两个氧形成扭曲的四面体,Yb~(2+)在四面体的中心。Yb~(2+)的配位数为8。Yb~(2+)到质心In1的距离为2.52,到质心In2的距离为2.40。Yb~(2+)到O(1)的键长为2.356(7),到O(2)的键长为2.417(5)。     

Synthesis and Characterization of syn-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2].0.5anti-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2]

1 INTRODUCTION The complexes of syn- or anti-[(5-C5Me5)2- W2(S)2(-S)2] could be prepared in several ways[1~5]. For example, a mixture consisting of [Et3NH][(5-C5Me5)WS3] and anti-[(5-C5Me5)2- W2(S)2(-S)2] was generated from the reactions of [(5-C5Me5)WCl4] with H2S in the presence of NEt3[2]. The reactions of [(5-C5Me5)W(NO)I2] with H2S led a mixture of [(5-C5Me5)W(S)(S2)I] and anti-[(5-C5Me5)2W2(S)2(-S)2][3]. [(5-C5Me5)W- (StBu)3] was degraded in THF at room temperat…     

(η~5-C_5H_5)_3Nd·OC_4H_8和(η~5-C_5H_5)_3Pr·OC_4H_8的合成及其晶体结构

本文用LnCl_3(Ln=La,Pr,Nd)同环戊二烯钠在THF溶液中反应,制备出(η~5-C_5H_5)_3Ln·OC_4H_8化合物单晶.采用低温技术,在—60℃的干燥氮气保护下,收集(η~5-C_5H_5)_3HPr·OC_4H_8[(η~5-C_5H_5)Nd·OC_4H_8]的单晶X射线衍射数据,解出了晶体结构.它们同属单斜晶系,P2_1/n 空间群.结构表明,THF分子中的氧原子与金属离子键合,Pr—O键长为2.56(1)A,Nd—O键长为2.54(1)A.三个环戊二烯分子中的所有碳原子与金属离子的间距,均在成键范围,其平均键距Pr—C为2.80(2)A,Nd—C为2.78(2)A.它们同已报道的(η~5-C_5H_5Ln·OC_4H_8(Ln=Y,La,Gd)结构一起,可很好地解释镧系收缩理论,同时为研究稀土元素的价态和键,提供了有用的结构信息。     

Synthesis and Crystal Structure of a Di-μ_2-phenolic Bridged Binuclear Manganese(Ⅲ) Schiff Base Complex

A new complex [Mn(L)(NCS)]2·0.5CH3CN (H2L = N,N'-bis(chlorosalicylidene)-1,2-diaminoethane) has been synthesized,and its structure (C70H51Cl8Mn4N13O8S4,Mr = 1833.84) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883(2),b = 12.3320(13),c = 13.5951(16) ,β = 112.906(2),V = 3997.2(7) 3,Z = 2,Dc = 1.524 g/cm3,μ(MoKα) = 1.050mm-1,F(000) = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 2σ(Ⅰ). The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn(Ⅲ) centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C(3)-H(3)···N(3) hydrogen bonds stabilize the crystal structure.     

Synthesis and Crystal Structure of [(ArO)2(THF)Sm(μ-OH)]2·2THF (Ar = C6H2-tBu3-2,4,6)

The title complex [(ArO)2(THF)Sm(μ-OH)]2·2THF (Ar = C6H2-tBu3-2,4,6) was obtained by the hydrolysis of divalent (ArO)2Sm(THF)3·THF in toluene. It crystallizes in monoclinic, space group P21/c with a = 14.7968(14), b = 18.6981(15), c = 16.8264(17) (A), β = 109.366(2)°, V = 4392.0(7) (A)3, Z = 2, C88H150O10Sm2, Mr = 1668.78, Dc = 1.262 g/cm3, F(000) = 1764 and μ(MoKα) = 1.377 mm-1. The final R and wR are 0.0318 and 0.0749, respectively for 9038 observed reflections with I > 2(σI). The complex possesses a dimeric structure with two centrosymmetric hydroxyl bridges. The samarium atom is coordinated by five oxygen atoms to form a distorted square pyramidal geometry with the average Sm-O(Ar) distance of 2.1757(19) (A). There are H-bond interactions be- tween the molecules.     

THE FORMATION AND CRYSTAL STRUCTURE OF (η~5-C_5H_5)_3Nd·OC_4H_8 AND (η~5-C_5H_5)_3Pr·OC_4H_8

Under suitable reactant ratios without sublimation or reerystallization, single crystals of(η~5-C_5,H_5)_3 Ln-OC_4H_8(In = La, Pr, Nd) could be prepared by the reaction of cyclopentadienylsodium with respective lanthanide trichlorides in THF. Using low temperature technique wehave collected the X-ray data of single crystals of the title compounds at -60℃ under N_2and determined crystal structures. (η~5-C_5H_5)_3 Pr·OC_4H_8, [(η_5-C_5H_5)_3 Nd·OC_4H_8] recrystallizesin the monoclinic space group P2_1/n[P2_1/n] with unit cell parameters a = 8.406(3) [8.364(3)],b = 24. 510(9) [24.467(9)], c = 8. 284(3) [8.254(3)] A, β= 101.60(3) [101.42 (3)], D_c = 1. 62 [1.65]gem~(-3) for z = 4 [4]. Least-square refinement has led to a final R value of 0.056 [0.063],R_W = 0.049 [0.062]. The THF molecule is coordinated to the Pr [Nd] atom at a Pr-O [Nd-O]bond length of 2.16(1) [2.54(1)], A. The Pr-C (Cp) [Nd-C(Cp)] bond distances average 2.80(2) [2.78(2)] A. The title compounds are isostructaral with (η~5-C_5H_5)_3     

Synthesis and Crystal Structure of Complex [Pb(qina)_2(DMSO)]·H_2O

A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized,of which qina-is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis,IR spectra,and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system,space group P121/n1,with a=7.1553(17),b=17.543(2),c=17.306(2) ,β=91.671(4)°,C22H20N2O6PbS,Mr=647.65,Z=4,V=2171.5(6) 3,Dc=1.981 g/cm3,μ=7.908 mm-1,F(000)=1248,–9≤h≤6,–23≤k≤19,–22≤l≤22,R=0.0221 and wR= 0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ) . There are also weak interactions,such as π-π interaction,hydrogen bonds and so on,among the complex molecules.     

SYNTHESIS AND CRYSTAL STRUCTURE OF {C(η~5-C_5H_5)_4Nd_4(μ_4-O) (μ_2-Cl)_8)]·[Li(dme)_2THF]_2

<正> The reaction of (η5-C5H5)3Nd·THF and NdCl3·2LiCl·nTHF in solution at room temperature gave rise to[(η5-C5H5)4Nd4(μ4-O)(μ2-Cl)8][Li(dme)2THF]2 (Mr = 1654.44). Crystals of the compound were obtained at about - 10℃. The intensity data were collected under nitrogen atmosphere at-60℃. The crystal belongs to the rhombic system with space group Pna21 and the unit cell parameters : a=19. 010(7),b = 23. 231(6) ,c= 14. 180(4) A ;V = 6261. 91 (A3) , DC= 1. 67 (g/cm3), λ(MoKa) = 0. 71069A,F(000) = 3240,μ(mm-1) = 3. 660;Z = 4. Least-squares refinement with anisotropic temperature factors for all non-hydrogen atoms led to the final R=0. 054, Rw = 0. 056. The molecule is made up of the anion group and the cation. The oxygen atom links four Nd3+together as μ4-bridge. The eight chlorine atoms form the eight chlorine-bridge bonds among four Nd3+ions. The average bond length is : Nd-O=2. 374,Nd-Cl = 2. 811,Nd-C=2. 777,Nd(a)- Nd(b) = 3. 872A.The bond angles of Nd(a) -Nd (b)-Nd(c) fall in the range of 62~63°,th     

Synthesis and Characterization of the Chiral Skeleton Cluster [NiRuMo(CO)_5(μ_3-S)(η~5-C_5H_5)(η~5-C_5H_4COCH_3)]

1 INTRODUCTION The chemistry of transition metal cluster has enjoyed an exceptional growth since the mid 1970s[1, 2], especially in recent years the structural and bonding aspects of mixed-metal tetrahedral skeleton clusters have been extensively studied[3]. One important reason is that such chiral cluster can induce an asymmetric catalysis potentially. In our research group, considerable efforts have been directed to the synthesis of chiral tetrahedral clusters containing four different…     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

Crystal and Molecular Structure of(η~5-C_5H_5)_2Yb(NC_4H_4)(OC_4H_8)

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_５）_２Ｙｂ（ＮＣ_４Ｈ_４）（ＯＣ_４Ｈ_８）ＷａｎｇＳｈａｏ－Ｗｕ；ＹｕＹｏｎｇ－Ｆｅｉ；ＨｕＪｉ－ｐｉｎｇ；ＹｅＺｈｏｎｇ－Ｗｅｎ（ＩｎｓｔｉｔｕｔｅｏｆＯｒｇａｎｉｃＣｈ...     

Crystal Structure of Bridged Dimer Complex of [Yb (H_2O)) (acac)_2 (Ac)]_2

1INTRODUCTIONTheacetylacetonatoisanexcellentbidentateligand.Withittherareearthmetalionscanformsomeseriesofcomplexes,suchasLn(acac)3.nH,O(n=1～4)andLn-(acac)4etc.[1-5i.lntheeventletasampleofthecomplexLn(acac)3.3H,Odis-solveinacetylacetonewhichmixeswithaceticacidforrecrystallization.Asaresultasubstitutionreactionofligandsinthesolutionarises.Anacetylacetonatoandacoor-dinatedwatermolecu1eofLn(acac),.3H,Oaresubstitutedbytwoacetatosandanon-coordinatedwatermoleculeisremoved.Amixedligandandbr…