PREPARATION AND CRYSTAL STRUCTURE OF CYCLOPENTADI-ENYL TETRAMETHYLETHENE-BRIDGED DICYCLOPENTA-DIENYLSAMARIUM(Ⅲ) TETRAHYDROFURANATE

<正> (CH3)4C2(C5H4)2Sm(C5H5)(OC4H8),Mr=499.4,orthorhom-bic,Cc2a,a=11.696(6),b=12.539(5),c=29.432(15)A,V=4316(4)A3,Z=8,Dc=1.54g/cm3,μ(MoKa)=27.8cm-1,F(000)=2024,R=0.077 for 1833 observed reflections.The samarium atom in the molecule is bonded to three cyclopen-tadienyl rings and one oxygen atom of tetrahydrofuran(THF)to form a tetrahedral configuration.The average Sm-C(η5-Cp)distances for the three cyclopentadienyl groups are 2.72(3),2.76(3)and 2.78(3)A,respectively,and the Sm-O bond is 2.53(1)A.     

MOLYBDENUM-IRON MIXED METAL CLUSTERS (Ⅰ)——THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF (η~5-C_5H_5)_2Mo_2Fe_2(μ_4-Te)(μ_3-Te)_2(CO)_6

The reaction of Fe_2(μ_3-Te)_2(CO)_9 with Mo_2(CO)_6(η~5-C_5H_5) affords the title compound. Its X-ray analysis shows a butterfly structure for the Mo_2Fe_2 core; the two molybdenum atoms occupy the hinge with a Mo—Mo bond distance of 2.819 and the two iron atoms are on the tops of the wings with an average Mo—Fe bond distance of 2.932(2). Each molybdenum is bonded to a Cp ring, and three CO ligands are terminally bonded to each iron atom. One tellurium atom quadruply bridges Mo_Fe_2 with Mo—Te(μ_4)=2.625(2). and Fe—Te(μ_4)=2.713(2). Two tellurium atoms triply bridge the two triangular Mo_2Fe faces with Mo—Te(μ_3)=2.678(1) and Fe—Te(μ_3)=2.513(3). The molecule has C_(2v) symmetry and a bicapped triangle bipyramidal skeleton. Crystallographic parameters are as follows: space groupImm2(orthorhombic), a=14.562(3), b=10.391(1), c=7.139(4), V=1080.2(i)~3, Z=2, ρ(cald)=1.819g·cm~(-3). The final R factor was 2.2％ for 620 independent reflections(I>2σ(I)).     

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     

STUDIES ON RARE EARTH COMPLEXES OF QUARTERNARY AMMONIUM SALT——SYNTHESIS AND CRYSTAL STRUCTURE OF TETRAKIS-(TRIMETHYL-HEXADECYL AMMONIUM)DECANITRATO DINEODYMATE,((CH_3)_3C_(16)H_(33)N)_4Nd_2(NO_3)_(10)

A series of binuclear eleven-coordinated rare earth complexes with long chain quarternary ammonium salt have been synthesized. The general formula of the complexes may be represented by((CH_3)_3 C_(16)H_(33)N)_4Ln_2(NO_3)_(10) where Ln is La, Ce, Pr, Nd, Sm, Eu, Ga, Ho, Er or Y. The TG curve, the magnetic moment and the dissociation degree of the Nd complexes in alcoholic solution have been determined.((CH_3)_3C_(16)H_(33)N)_4 Nd,_2NO_3)_(10) was chosen as a representative of the complexes for the crystal structure determination. The crystal is monoclinic with space group P. Each Nd atom is coordinated by four terminal nitrate groups bidentately, and two Nd atoms are connected through two O atoms of the nitrate groups forming binuclear complex. Therefore, each Nd atom is surrounded by eleven oxygen atoms. The average bond length of the eleven Nd-O bond is 2.57, while the Nd-O bond length on the oxygen-bridge is 2.62.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURES OF (Et_4N)_2[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_2Cl_5]

The title compound forms black crystals shaped like pseudo-octahedrons, which belong to the orthorhombic system The space group is Pna 2_1 with unit cell parametrs of a=17.815(1), b=16.629(2), c=12.003(1), and with Z=4, D_(obs)=1.80g·cm~(-3), and D_(calc)=1.804g·cm~(-3). The crystal structure was solved by the heavy atom method and refiened by fullmatrix least-squares to a final conventional R factor of 0.048 for 2584 unique reflections with I≥σ(Ⅰ). The investigation confirms that the crystal structure consists of tetraethylammonium cations and trinuclear Mo cluster anions. The anion is a μ_3-O monocapped trinuclear cluster with an average Mo-Mo bond length of 2.60 (2). On the side of the Mo_3 triangular plane opposite to the μ_3-O atom, each two Mo atoms are bridged by a Cl atom with the result that these seven atoms (3 Me, 1 O and 3 Cl atoms)form an apex-deficient quasicubane configuration. In addition, each Mo atom is coordinated to three additional atoms resulting in a pseudo-octahedral geome     

Syntheses of (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, Er, Yb) and crystal structure of [(C_5H_9C_5H_4)_2-LnCl(THF)_n]_2(Ln=Sm, n=1; Ln=Er, n=0)

Reactions of lanthanoid trichlorides with sodium cyclopentylcyclopentadienyl in THFafford bis(cyclopentylcyclopentadienyl) lanthanoid chloride complexes (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, n=1; Ln= Er, Yb, n= 0). The compound [CP'_2SmCl(THF)]_2 (2) (Cp' =cyclopentylcy-clopentadienyl) crystallizes from mixed solvent of hexane and THF in monoclinic space group P_2_1/cwith a = 11.583 (3), b = 23.019(6), c = 8.227 (2), β= 90.26 (2)°, V= 2194 (1)~3, D_c= 1.59 g/cm~3.μ= 28.6 cm~(-1), F(000) = 1060, Z= 2 (dimers). Its crystal molecule is a dimer with a crystallographicsymmetry center. The central metal atom Sm is coordinated to two Cp' rings, two bridging chlorineatoms and one THF forming a distorted trigonal bipyramid. The crystal of [Cp'_2ErCl]_2 (3) belongs tothe triclinic space group P with a = 11.264 (2), b= 13.296(5), c = 14.296(6), a = 96.99 (3), β=112.47(2), γ= 102.78(2)°, V= 1865(1)~3, D_c= 1.67 g /cm~3, μ= 48.0 cm~(-1), F(000) = 924, Z = 2 (dimers).The molecule is a dimer consisting of two Cp'_2 ErCl species bridged by two Cl atoms. The centralmetal atom Er is coordinated to two Cp' rings and two bridging chlorine atoms forming a pseudo-tetrahedron. All these complexes are soluble in THF, DME, Et_2O, toluene and hexane.     

Hydrothermal Synthesis and Crystal Structure of a New Manganese(Ⅱ) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2'-Bipyridine Ligands

A new metal-organic complex [Mn_2(PDC)_2(bipy)_2(H_2O)_2] (H_2PDC=2,4-pyridinedicarboxylic acid,bipy=2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic,space group P~(-)1 with α=7.376(3),b=9.990(4),c=11.950(5)(A),α=75.217(5),β=78.052(5),γ=70.655(5)°,V=796.0(5)(A)~3,C_(34)H_(26)Mn_2N_(6O)O_(10),M_r=788.49,D_c= 1.645 g/cm~3,μ(MoKa) = 0.866 mm~(-1),F(000)=235,Z=1,the final R=0.0425 and wR=0.0700 for 1971 observed reflections (Ⅰ > 2σ(Ⅰ)). In the crystal structure,the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands,one aqua ligand,and three nitrogen atoms from 2,2'-bipy and PDC ligands,giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

CRYSTAL STRUCTURE OF SEVEN-COORDINATE ZIRCONOCENE COMPLEX (CH_3C_5H_4) Zr(S_2CNBz_2)_3 (Bz=CH_2C_6H_5)

(CH_3C_5H_4)Zr(S_2CNBz_2)_3, Mr=987.55, space group P1, a=13.002(4), b=13.659(3), c=29.685(8); α=100.72(2)~o,β=97.23(2)~o, γ=105.36(2)~o; V=4909(2)~3, Z=4, Dc=1.34gcm~(-3), Mo-K(λ=0.71073A) radiation, μ=5.0cm~(-1), R=0.069, Rw=0.078 for 6100 reflections. The title complex has pentagonal bipyramid configuration in which the zirconium atom is coordinated by one CH_3C_5H_4 group and three bidentate dibenzyldithiocarbamate ligands.     

Structural Probing on the Sn-C_(C5 ring) Bond of the Sn(Ⅱ) Metallocenes in Both the Solid State and the Temperature-dependent Solution Relaxation State

Various bond modes of the M-C_(C5 ring) exist in metallocene compounds of group 14 heavier elements,mostly due to an intricate interaction between the lone electron pairs at the M center and the 6 p-electrons of the C_5 ring.The tin(Ⅱ) metallocene complexes LSn R(L = HC[CMe(N-2,6-iPr_2C_6H_3)]_2,R = cyclopentadienyl,C_5H_5(1); indenyl,C_9H_7(2); fluorenyl,C_(13)H_9(3)) stabilized by the β-diketiminato ligand were prepared and utilized in the study on their solid and solution state structures.X-ray single-crystal diffraction data revealed an η~1-mode of the Sn-C_(C5 ring) bond in each 1~3.However,the room temperature ~1H NMR spectral studies disclosed such a fluxional bonding mode in solution.The 119 Sn NMR studies suggested a quadruple coordination nature of the Sn center in 1 while the triple coordination manner was for the Sn atom in both 2 and 3.Then the variable-temperature(25~–75 ℃) ~1H NMR spectral studies for each 1~3 were performed,which detected the relaxation state structures of 1~3 at lower temperature.All of these results indicate a stereochemical activity of the lone electron pairs at the tin(Ⅱ) atom that definitely has an electronic interaction with the 6 p-electrons of the C_5 ring.The observed Sn-C_(C5 ring) bond modes appear influenced by either the metallocene size or the compound state existed.     

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl) Ether: Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis(2-dimethylaminoethyl) ether(BDMAE) with nickel acetate afforded a novel 3D nickel(Ⅱ) complex [Ni(BDMAE)(H_2O)_3·(CH_3COO)_2·(H_2O)_2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823(2), b=13.932(3), c=17.563(4) ?, V=2158.9(8) ?~3, Z=4, C_(12)H_(36)N_2NiO_(10), Mr=427.14, Dc=1.314 g/cm~3, F(000)=920 and μ=0.944 mm~(-1). Single-crystal X-ray diffraction reveals that the mononuclear nickel(Ⅱ) ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.     

Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond [η~5-RC_5H_4Cr(CO)_2]_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η~5-CH_3C(O)C_5H_4Cr(CO)_2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072(?).     

STUDY ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF THE TWO TRINUCLEAR MOLYBDENUM CLUSTERS(C_5H_7S_2)[Mo_3(μ_3-O )(μ-X)_3(μ-OAc)_3Cl_3](X=Cl,Br)

The crystal structure of two isomorphic cluster compounds with formula (C_5H_7S_2)-[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (X=Cl for compound (Ⅰ) and compound (Ⅱ)) has been investigated by X-ray diffraction method. The parameters of two crystals are: a=10.423(1),b=17.095(4), c=14.062(7), β=97.54(4)(°); Dc=2.20gcm~(-3), D_o=2.17g cm~(-3) for compound (Ⅰ). and a=10.511(3), b=11.213(2), c=14.053(3), β=96.12(2)(°); D_c=2.52g cm~(-3), D_o=2.53gcm~(-3) for compound (Ⅱ). The space groups are P2_1/C. Z=4. The 2621 and 2548 independent reflections with I>3σ(I) were collected on a CAD-4 four-circle diffractometer by means of MoKα radiation. The crystal structures were solved by heavy atom method and refined by full-matrix least-squares technique to a final discrepancy factors of R=0.061 and 0.051 respectively. The results of investigation show that the molecule consists of the cation (C_5H_7S_2)+ and the trinuclear Mo cluster anion, the configuration of which is similar to that of (Et_4N)_2[Mo_3(μ_3-O)(μ     

Syntheses of(C_8H_8)Ln(C_9H_7)·(THF)_2(Ln=Pr,Nd)and crystal structure of(C_8H_8)Pr(C_9H_7)·(THF)_2

This paper reports two lanthanide complexes of formula (C_9H_7)Ln(C_8H_8)·(THF)_2 whereLn is Pr or Nd,C_9H_7 is indenyl,and C_8H_8 is cyclooctatetraene (COT).The complexes were preparedby the reaction of LnCl_3 with K(C_9H_7) and K_2(C_8H_8) in THF.(C_9H_7)Pr(C_8H_8)·(THF)_2 crystallizes inTHF at - 15℃ in the monoclinic space group P2_1:with unit cell dimensions a=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)~3,Dc=1.52g/cm~3 and Z=2.The final R valueis 0.033,R_w value is 0.030,respectively.In (C_9H_7)Pr(C_8H_8)·(THF)_2 a five-membered ring centroid ofC_9H_7,the C_8H_8 ring centroid and the two oxygen atoms from the two THF molecules form a distortedtetrahedral geometry around the metal.     

Two New Coordination Complexes Based on 2,2'-H2biimidazole: Synthesis,Structure, Luminescent Property and Theoretical Calculation

Two new coordination complexes [Cd(L)_2(1,2,3-HBTC)]·3H_2O(1) and {[Zn(L)(1,2-BDC)]-H_2O}_n(2) were synthesized under hydrothermal conditions(1,2,3-H_3 BTC=1,2,3-tricarboxybenzene,1,2-H_2 BDC=1,2-dicarboxybenzene and L=2,2'-H_2 biimidazole).1 crystallizes in monoclinic,space group P2_1/c with a=12.256(5),b=11.620(5),c=17.479(5) A,β=95.548(5)°,V=2477.6(16) A~3,Z=4,C_(21)H_(22)N_8 O_9 Cd,M_r=642.86,D_c=1.724 g/cm~3,F(000)=1296,μ(MoKa)=0.950 mm~(-1),R=0.0546 and wR=0.1724.2 belongs to the monoclinic system,space group P2_1/c with a=7.408(4),b=20.743(10),c=10.194(5) A,β=95.648(6)°,V=1477.3(12) A~3,Z=4,C_(14)H_(12)N_4 O_5 Zn,M_r=381.65,D_c=1.716 g/cm~3,F(000)=776,μ(MoKa)=1.698 mm~(-1),R=0.0574 and wR=0.1632.The central Cd(Ⅱ) ion in 1 is coordinated with five atoms,forming a slightly distorted square-pyramidal geometry.The central Zn(Ⅱ) ion in 2 is four-coordinated by two nitrogen atoms from one L ligand and two oxygen atoms from two different 1,2-BDC anions.In addition,luminescent property of 1 has been investigated,and natural bond orbital(NBO) analysis of 2 has been calculated by the B3LYP/LANL2DZ method.     

Synthesis,Characterization, Optical Property and Bioactivity of the Eu(Ⅲ) Complex with Aromatic Carboxylic Triazole

A novel complex{[Eu(H_5TIA)(C_2O_4)_(0.5)(H_2O)_3]·H_2O}_(n )of Eu(Ⅲ)with aromatic carboxylic triazole(H_7TIA=5-(4H-1,2,4-triazol-4-yl)isophthalic acid,H_2C_2O_4=oxalic acid)was hydrothermally synthesized and characterized by IR,UV-Vis,emission spectra and optical activity,and its crystal structure was determined.It crystallizes in triclinic system,space group P1 with a=7.4452(13),b=10.776(2),c=11.286(2)?,α=110.546(3)°,β=106.604(3)°,γ=99.031(3)°,V=486.0,GOOF=1.096,the final R=0.0196 and w R=0.0527 for 3081 observed reflections with I≥2σ(I),R=0.0209 and wR=0.0535 for all data with(Δ/σ)_(max)=0.001,(Δρ)_(max)=0.48 and(Δρ)_(min)=–0.46 e·?~(-3).The natural bond orbital(NBO)charges,electrostatic potential(ESP)and frontier orbital of this complex were also analyzed.The results of anti-bacterial activity against Gram positive(S. aureus)and Gram negative(E. coli)bacteria reveal that the studied complex possesses a moderate inhibiting effect,and the inhibition effect on E.coli is better.     

Self-assembly of a Mixed-valence Cu(Ⅰ)/Cu(Ⅱ) Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand

Reaction of a tripodal ligand, N,N?,N??-tris(3-pyridinyl) phosphoric trimide(TPPA) and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) ?, V = 933.01(9) ?~3, Z = 2, C_(30)H_(24)Br_4Cu_3N_(12)O_2P_2, M_r = 985.02, D_c = 1.753 g/cm~3, F(000) = 4072 and μ(MoKα) = 0.746 mm~(-1). The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 2σ(I). Cu(Ⅰ) is tetrahedrally coordinated and Cu(Ⅱ) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H···O and N–H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.     

Synthesis,Crystal Structure and Catalytic Activity of a Hexa-μ-chloro-tetrakis-(1-triphenylmethyltriazole)-μ4-oxo-tetracopper(Ⅱ)

A new Cu(Ⅱ) complex,[Cu_4Cl_6O(1-TrTz)_4]where 1-Tr Tz is 1-trityl-1H-[1,2,4]triazole,was synthesized by the reaction of 1-trityl-1H-[1,2,4]triazole with two hydrated cupric chlorides,and its structure was characterized by X-ray single-crystal diffraction.[Cu_4Cl_6O(1-TrTz)_4]is of monoclinic system,space group P21/c,a=12.5024(13),b=26.400(3),c=28.588(3)?,β=112.807(4)°,V=8698.1(16)?~3,Z=4,ρ_(calc)=1.411 g/cm~3,μ=1.265 mm~(–1),F(000)=3772,the final R=0.1293 and w R=0.3644 for 55774 observed reflections (I2s(I)),R(all data)=0.1972,w R(all data)=0.3989,completeness to theta of 25.242 is 99.9%and GOF=1.103.In the structure of[Cu_4Cl_6O(1-TrTz)_4],the central O atom is tetrahedral and is coordinated with four Cu atoms.The distance between copper and oxygen bond is 1.909(6)?.In addition,the catalytic property of this complex was investigated and it could effectively catalyze the Ullmann coupling reaction of various (hetero)aryl chlorides with azoles.     

A SIMPLE ACCESS TO UNSOLVATED MONOMERIC COMPLEXES OF EARLY LANTHANIDE IODIDES(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)VIA THE REACTION OF[(CH_3OCH_2CH_2C_5H_4)_2LnCl]_2 WITH NaI AND X-RAY CRYSTAL STRUCTURE OF THE LANTHANUM COMPLEX

(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have beensynthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2in THF;A single crystal X-ray study has shown that the lanthanumcomplex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonalbipyramidal coordination geometry if the cyclopentadienyl ring isregarded as occupying a single polyhedral vertex.     

Synthetic and structural chemistry of nickel(Ⅱ) complexes containing dithiolato and phosphine ligands Ⅰ. Preparation and crystal structure of Ni_2(PPh_3)_2(edt)_2

A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2(edt = SCH_2CH_2S~(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizesin the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α=102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A~3; D_c = 1.439g.cm~(-3) for Z=2; the final con-ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfuratoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinatedby one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average:length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra havealso been recorded.     

CRYSTAL STRUCTURE OF BINUCLEAR Y(Ⅲ) COMPLEX WITH p-METHYLBENZOIC ACID, Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2

Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2, Mr=1349.08, triclinic, space group P, a=13.00(3), b=19.743(2), c=12.754(3)A, α=97.94(1), β=106.24(2), γ=91.66(1)°, V=3177(1)~3, Z=2, Dc=1.41gcm~(-3), λ(MoKα)=0.71069, μ=18.92 cm~(-1), F(ooo)=1384, T=295K, final R=0.073 for 6504 observed reflections with Ⅰ>36(Ⅰ). There are two nonidentical binuclear molecules with different bridging connection patterns in a cell. One has four bridging carboxyl groups bound two Y(Ⅲ) ions and another only has two. The Y-Y distance is 4.196 for the former and 5.302 for the latter respectively.