A NOVEL SYNTHETIC METHOD AND STRUCTURE OF TETRAKIS(BENZOATE)BIS(TRIPHENYLPHOSPHINE OXIDE)DICOPPER(II).OXIDATIVE ADDITION OF DIBENZOYL ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metalliccopper with triphenylphosphine in a mixed solvent(acetone,dichloromethaneand trichloromethane),and affords the binuclear copper complex(Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,withcell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°,V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections.Each copper ion is coordinated by four bridging benzoato ligands and onetriphenylphosphine oxide group to form binuclear complexes.     

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.     

MOLECULAR AND CRYSTAL STRUCTURES OF TETRANUCLEAR MOLYBDENUM CLUSTER[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)~6]■

The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by thereaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal andmolecular structures were determined by the X-ray diffraction method.It crystallizesin the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4),b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm~3,F(OOO)=2704,μ(MoK )=11.0/cm,R=0.074.     

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.     

CRYSTAL STRUCTURE OF LONG CHAIN COMPLEX OF [Cu(TTA)(4,4''''-BIPYRIDINE)]_n

The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(1) A, c=16.032(7) A, β=106.76(3)°,V=3695(3) A~3, Z=8, Dc=1.58g/cm~3, F(000)=1776. Final R and Rw are 0.062 and 0.069, respectively. The local coordination geometry around Cu(I) ion is a distorted tetrahedron. Cu(TTA) are linked with 4,4-bipyridine, forming long chain in the crystal.     

Synthesis,Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2?-Biquinoline and Phosphorous Ligand

Three new copper(Ⅰ) complexes, namely [Cu(DPEphos)(Biq)]CF_3SO_3(1) and [Cu(PPh_3)_2(Biq)]CF_3SO_3(2) and [Cu(PPh_3)_2(Biq)]ClO_4(3)(DPEphos = bis[2-(diphenylphosp hino)phenyl]ether, PPh_3 = triphenylphosphine and Biq = 2,2?-biquinoline), are synthesized and characterized by IR, ~1H NMR, ~(31) P NMR, fluorescence spectra and terahertz time-domain spectroscopy(THz-TDS). Complex 1 crystallizes in triclinic, space group P1 with a = 12.6997(5), b = 13.2813(5), c = 15.3593(6) ?, α = 80.211(3)°, β = 88.752(3)°, γ = 70.113(3)°, V = 2398.85(15) ?~3, C_(55)H_(41.2)CuF_3N_2O_(4.6)P_2S, Mr = 1018.27, Z = 2, Dc = 1.410 g/cm3, F(000) = 1048, μ = 0.628 mm-1, the final R = 0.0450 and w R = 0.1105 for 9419 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group C2/c with a = 19.9961(7), b = 15.9774(5), c = 17.7908(6) ?, β = 119.758(4)°, V = 4982.8(3) ?~3, C_(56.47)H_(47.88)CuF_3N_2O_(4.47)P_2S, Mr = 1040.54, Z = 4, Dc = 1.387 g/cm~3, F(000) = 2154, μ = 0.606 mm-1, the final R = 0.0430 and w R = 0.1218 for 4897 observed reflections(I 2σ(I)). Complex 3 crystallizes in monoclinic, space group C2/c with a = 19.7534(8), b = 15.0797(5), c = 17.8097(7) ?, β = 116.400(5)°, V = 4751.8(3) ?~3, C_(56)H_(45)ClCuN_3O_4P_2, Mr = 984.88, Z = 4, Dc = 1.377 g/cm~3, F(000) = 2040, μ = 0.635 mm-1, the final R = 0.0731 and w R = 0.2180 for 4670 observed reflections(I 2σ(I)). In the emission spectra, shifts of emission peak are derived from ligand-centered(π-π*) transition.     

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [Cu_2(CH_3COO)_4(C_8H_(11)NO)_2] · (C_6H_(11)NO)_2 · (C_8H_(12))

<正> SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [Cu_2(CH_3COO)_4(C_8H_(11)NO)_2] · (C_6H_(11)NO)_2 · (C_8H_(12)), where C6H11 = caprolactam, Mr = 900. 07, triclinic,space group P1, a = 11. 103(4), b= 11. 865(6), c=9. 912(3)(?), α=94. 85(4), β=115.20(2), γ=103. 25(4)°, V = 1125(2)(?)3, Z = l, Dx = 1. 33g. cm-3, λ(MoKa) = 0. 71069(?), T = 295K , μ = 10. 45cm-1, F(000) = 478, final R=0. 063 for 2098 observed reflections with I>3σ (I). The two Cu atoms in the molecule are held together by four carboxylate groups. Each Cu atom is bound in a square-pyramidal configuration to four carboxyl oxygen atoms and to the O atom of a caprolactam molecule.     

SYNTHESIS AND CRYSTAL STRUCTURE OF PYRROLIDINONE COPPER ACETATE

The title complex [Cu(CH_3COO)_2(C_4H_7NO)]_2 has been synthesized and its structure hasbeen determined by X-ray diffraction method.The compound crystallizes in the triclinic spacegroup P .The cell dimensions are:a=0.7775(4),b=0.8229(3),c=0.8913(5)nm,a=101.85(4)°,β=110.36(4)°,v=90.61(3)°,z=1.The struture has been refined to a R valueof 0.089.The two copper atoms are bridged by four acetate groups.Pyrrolidinone cooridinates tocopper at the apical site through its oxygen atom.     

THE SYNTHESIS AND STRUCTURE OF 4,5-BIS(2,4-DINITROPHENYLTHIO)-1,3-DITHIOLE-2-ONE (BNPT-DTO)~(**)

The title compound BNPT-DTO (C_(15)H_6N_4O_9S_4, Mr=514.51) has been synthesized and Its crystal structure determined. It is crystallized in orthorhombic system, space group P2_12_12_1, a=10.078(1), b=19.352(1),     

A Heterometallic Cu(Ⅰ)-Sr(Ⅱ) Coordination Polymer Based on Isonicotinic Acid Ligand: Synthesis,Crystal Structure,Luminescence and Photocatalytic Performance for Methylene Blue Degradation

Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, Sr(NO_3)_2 and isonicotinic acid. The crystal structure is of triclinic system, space group P1 with a = 7.111(2), b = 14.934(4), c = 18.0255(11) ?, α = 83.137(15), β = 87.155(15), γ = 79.75(2)°, V = 1869.4(8) ?~3, C_(30)H_(29)Br_2Cu(3)N_5O_(14)Sr_2, Mr = 1209.27, Z = 2, Dc = 2.148 g/cm~3, F(000) = 1178, μ = 6.725 mm~(-1), R = 0.0500 and wR = 0.1008 for 4688 observed reflections(I 2s(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a 3 D heterometallic framework stabilized by bifunctional isonic ligands. In addition, the luminescent and photocatalytic properties of compound 1 were also investigated at room temperature.     

STUDIES OF RARE EARTH METAL COMPLEXES OF AMINO ACIDS AND PEPTIDES. SYNTHESES AND CRYSTAL STRUCTURES OF TRIAQUO TRIS (N-ACETYLGLYCINE) LANTHANIDE Ln(CH_3CONHCH_2COO)_3(H_2O)_3(Ln = Nd~(3+),Eu~(3+) and Er~(3+))

<正> The title complexes were synthesized and their crystal structures were determined. These complexes crystallize in trigonal space group R3 with 3 molecules in a unit cell and are isostructural to each other. Crystallographic data: complex 1, Nd(CH3CONHCH2COO)3(H2O)3, Mr = 546. 6, a= 16. 582(4), c = 5. 982(2)(?), V= 1424. 5(8)(?)3, Dc=1. 91gcm-3, F (000) = 819, μ = 28.06cm-1, R(Rw) = 0. 048(0. 061); complex 2, Eu (CH3CONHCH2COO)3 (H2O)3, Mr = 554.3, a = 16.564(10), c=5.974(3)(?), V = 1418(2)(?)3,Dc= 1. 95gcm-3, R (Rw) = 0. 018 (0. 025), F (000) = 828, μ= 33. 83cm-1; complex 3, Er-(CH3CONHCH2COO)3(H2O)3, Mr = 569. 6, a = 16. 476(7), c=5. 946(6)(?), V = 1398(2) (?)3, D, = 2. 03gcm-3, R (Rw ) = 0. 020 (0. 027) , F (000) = 843, μ= 46. 25cm-1. These complexes adopt mononuclear structure, in which Ln(Ⅲ) ion is coordinated to six oxygen atoms from three ligands and three oxygen atoms from water molecules with the polyhedron of 4,4,4-tricapped triangular prism. The carboxy-lato group of the ligand bonds to Ln     

Solvent Dependent Assembly,Structural Diversity and Topology Analysis in Two Novel Ni Coordination Polymers

Solvent dependent assembly obtained two novel Ni coordination polymers with H_2 tbtpa and flexible 1,2-bix ligand(H_2tbtpa = tetrabromoterephthalic acid and 1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene),formulated as [Ni_(0.5)(tbtpa)_(0.5)(1,2-bix)·(H_2O)]_n(1) and [Ni(tbtpa)(1,2-bix)(H_2O)_2]_n(2).They have been structurally characterized by single-crystal and powder X-ray diffraction,elemental analysis,FT-IR spectra and TGA.Compound 1 crystalizes in triclinic,space group P1 with a = 9.0276(4),b = 10.0012(6),c = 11.4955(5) ?,α = 69.121(5),β = 76.398(4),γ = 89.668(4)o,C_(36)H_(32)Br_4 Ni N_8O_6,Mr = 1051.04,V = 939.05(8) ?~3,Z = 1,Dc = 1.859 g·cm~(-3),μ = 6.222 mm~(-1),F(000) = 520,8.502≤2θ≤134.16°,λ(Cu Kα) = 1.54184 ?,T = 294(6) K,the final R = 0.0750,w R = 0.1988 and S = 1.033.Compound 2 crystalizes in triclinic,space group P1 with a = 11.1257(7),b = 11.5062(6),c = 12.3529(4) ?,α = 88.861(3),β = 84.572(4),γ = 64.235(6)o,C_(22)H_(18)Br_4 Ni N_4O_6,Mr = 812.75,V = 1417.36(1) ?~3,Z = 2,Dc = 1.904 g·cm~(-3),μ = 7.968 mm~(-1),F(000) = 788,7.2≤2θ≤134.1°,λ(Cu Kα) = 1.54184 ?,T = 294(6) K,the final R = 0.0414,w R = 0.0865 and S = 1.025.1 shows a two-dimensional(4,4)-sql topology and 2 manifests a three-dimensional 6~58 Cd SO_4 topology coordination polymer network.     

SYNTHESIS AND STRUCTURE OF （Me4N）[Mo（OC6H4S—o）3]

<正> (Me_4N)[Mo(OC_6H_4S-o)_3] ,Mr=542. 57,orthorhombic,space group Pnb21 with a = 22. 708(1),b = 9. 737(4),c=10. 486(2) A;V=2318. 6A3;Z=4,Dc = 1. 55g/cm3,final R=0. 064 and Rw=0. 074.μ=8. 3cm-1, F(000) = 1108,The atom Mo( V ) of the anion issix-coordinated to three oxygen and three sulfur atoms in a distorted octahedral geometry.     

SYNTHESIS AND STRUCTURE OF TETRANUCLEAR MOLYBDENUM CLUSTER COMPOUND[Mo_4S_4(μ-O_2CC_6H_5)_2(dtp)_4]

The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)wasobtained by the ligand substitution reaction of tetranuclear molybdenum cluster[Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in thepresence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c,Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4;Dc=1.78g/cm~3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]clustercore and t-(dtp)~(-1)ligands are retained and only μ-bridged(dtp)~(-1)ligands aresubstituted by(C_6H_5CO_2)~(-1)in the substitution reaction,thus producing the newtitle cluster compound,the structure of which contains two species of bidentateligand.     

1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(HPMBP)的金属离子配合物的结构研究——Ⅰ.HPMBP及其配合物Cu(PMBP)_2的晶体结构

本文研究了Cu(PMBP)_2和HPMBP的单晶体结构,晶体学参数为:(1)HPMBP,C_(17)H_(14)0_2N_2,M=278.31,单斜晶系,空间群P2_1/a,a=11.406(5),b=9.087(1),c=13.467(3)(?),β=90.76(3)°,V=1395.7(?)~3,Z=4,D_c=1.324g cm~(-3),μ=0.95cm~(-1).(2)Cu(PMBP)_2,C_(34)H_(26)O_4N_4Cu,M=618.16,单斜晶系,空间群P_2_1/c,a=6.809(3),b=23.722(8),c=9.102(3)(?),β=108.94(4)°,V=1390.7(?)~3,Z=2,D_c=1.476g cm~(-3) μ=8.67cm~(-1).结果表明,HPMBP具有烯醇式结构,其中两个给体氧原子处于有利于形成六元螯合环的几何位置;在配合物Cu(PMBP)_2中,Cu原子为对称中心,两个配体中的四个氧原子形成以Cu为中心的近似平面正方形的配位结构,Cu-O距离分别为1.906和1.896(?).     

Ionothermal Synthesis and Fluorescence Property of a Complex Constructed by Seven Nuclear(CH_3COO)_2Co_7(OH)_2] Clusters and 4,4'-Oxybisbenzoic Acid Ligand

A new 3D cobalt metal-organic framework [C_7H_(13)N_2]_2[(CH_3COO)_2Co_7(oba)_5-(Hoba)_2(OH)_2]·H_2O has been synthesized under ionothermal conditions and characterized by elemental analysis, FT-IR, XRD, and TG. This complex crystallizes in monoclinic system, space group P21/c with a = 19.4499(4), b = 10.8839(2), c = 27.7796(5) ?, β = 104.467(2)o, V = 5694.22(19) ?~3, Z = 2, C_(116)H_(92)Co_7N_4O_(42), M_r = 2626.45, D_c = 1.532 g/cm~3 , F(000) = 2682, μ = 1.085 mm-1, R = 0.0387 and wR = 0.1177. Its structure is characterized as a 3D open framework constructed by seven nuclear clusters [(CH_3COO)_Co_7(OH)_2] and the 4,4?-oxybisbenzoic acid ligand. The used ILs cations are located in the middle of the pore and compensate for the negative charges of framework. Furthermore, its fluorescence property has also been studied.     

PREPARATION AND CRYSTAL STRUCTURE OF TETRAMETHYLETHENE-BRIDGED DICYCLOPENTADIENYLSAMARIUM (Ⅲ) COMPLEX

(CH_3)_4C_2(C_5H_4)_2Sm(C_5H_5)OC_4H_, Mr=499.4, orthorhombic, Cc2a, a=11.696(6), b=12.539(5), c=29.432(15), V=4316(4)~, Z=8, Dc=1.54g. cm~(-3), μ (MoKα)=27.8cm~(-1), F(000)=2024, R=0.077 for 1833 observed reflections. In the molecule the samarium atom is bonded to three cyclopentadienyl rings and an oxygen of tetrahydrofuran(THF). The three centroids of the cyclopentadienyl rings and the oxygen form a tetrahedral configuration around the Sm(Ⅲ) atom, The average Sm-C(η~) bond distances for the three cyclopentadienyl groups are 2.72(3), 2.76(3), 2.78(8) respectively, and Sm-0 bond is 2.53(1).     

SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_2OS(μ-S)_2[S_2CNC_4H_8]_2

Mo_2OS(μ-S)_2[S_2CNC_4H_8]_2, Mr=612.61, triclinic, PI, a=8.666(2)(?), b=17.366(6)(?), c=6.708(1)(?), α=98.29(2)°, β=97.27(2)°, γ=79.36(2)°, V=976.5(5)(?)~3, Z=2, Dc=2.03g/cm~3, MoKα(λ=0.71069(?)), μ=19.75cm~(-1), F(000)=588, Final R=0.064, Rw=0.073 for 1517 unique intensity data (I>3σ(I)). The binuclear unit of [Mo_2OS_3] has a new asymmetrically terminal coordinated configuration with Mo-Mo distance of 2.807(3)(?).     

双μ_3-O四核过渡金属簇合物的研究——Ⅰ.[M_2M′_2O_2(C_2H_5COO)_7(bipy)_2]·ClO_4(M=Fe;M′=Fe或Cr)簇合物的合成和晶体结构

本文采用2,2-联二吡啶与氧心三核物[M_3O(C_2H_5COO)_6(H_2O)_3]·NO_3(M=Fe,Cr)在乙腈中反应的方法制备了两个簇合物:[Fe_4O_2(C2_H_5COO)_7(bipy)_2]·ClO_4(1);[Fe_2Cr_2(C_2H_5COO)_7(bipy)_2]·ClO_4(2).从测定的单胞参数可确定它们为异质同晶,进而测定了簇合物1的结构.晶体属三斜晶系,空间群PI,单胞参数a=1.5328(2),b=1.6325(2),c=1.3017(2)nm,α=113.49(1),β=115.12(1),γ=94.11(1)°;V=2.5882nm~3,D_c=1.51g·cm~(-3),Z=2,R=0.063,R_W=0.094.     

Synthesis,Crystal Structure and Properties of a 1D Heteronuclear Cobalt-sodium Polymer with Bridging Ligand 2-(2-Hydroxy-3-methoxybenzylidene) Hydrazinecarbothioamide

A new cobalt-sodium coordination polymer [CoNa(C_9H_9N_3O_2S)_2·H_2O]_2·C_2H_3N·H_2O(1) has been synthesized with cobalt chloride,2-(2-hydroxy-3-methoxybenzylidene)hydrazinecarbothio amide(L) and sodium hydroxide.It crystallizes in the triclinic space group P1,with a = 9.972(4),b = 10.923(4),c = 13.489(5) ?,α = 108.005(10),β = 92.728(10),γ = 93.16(1)o,V = 1392.0(9) ?~3,Mr = 1151.95,Dc = 1.374 g/cm~3,Z = 2,F(000) = 592,the final GOOF = 1.126,R = 0.1091 and wR = 0.2412.Each unit molecule consists of two cobalt ions and two sodium ions bridged by four 2-(2-hydroxy-3-methoxybenzylidene)hydrazinecarbothio amide anions.The coordination environment of Co ion is CoO_2N_2S_2,giving a distorted octahedral geometry and the Na(1) ion is NaO_4N,giving a distorted square pyramidal geometry.The results show that 1 shows one strong intense fluorescence emission wavelength of 429 nm with an excitation wavelength of 376 nm,and the electron transfer of 1 is irreversible in electrode reactions.