CRYSTAL STRUCTURE INVESTIGATION OF VANADYL COMPLEXES OF TRIDENTATE LIGAND (Ⅱ)——SYNTHESE AND CRYSTAL STRUCTURE OF 1-(2-PYRIDYLAZO)-2-NAPHTHOLATO-DIOXOVANADIUM (Ⅴ) DIMER [VO_2(C_(15)H_(10)N_3O)]_2(H_2O_2)(CHCl_3)_2 AND PYRIDINE-(1-(2-PYRIDYLAZO)-2-NAPH

The title complexes crystallize in space groups C(?)-P(?) and C_(2h)~5-P2_1/c, and with unit cell parameters a=8.488. b=10.100, c=11.974. α=72.73°, β=78.56°, γ=73.55°, and a=11.496, b=9.883. c=16.360, β=100.18°, respectively. All the V coordinates are obtained from Patterson and direct methods, respectively, and then Fourier and difference Fourier methods are employed to deduce other non-hydrogen atoms. Structural parameters are refined with least-squares technic, yielding final discrepancy factors R=0.081 and 0.067, respectively. Structural analyses demonstrate that the dimer of VO_2~+ complex is formed through the sixth-position bonding of a bridge oxygen atom of one VO_2~+ group with another VO_2~+, and the formation of VO(O_2)(C_(15)H_(10)N_3O)(C_5H_5N) shows that VO~(2+) complex with strong chelating tridentate PAN-seems less difficult to transform into the pentagonal bipyramid VO~(3+) complex. Since no peroxo species has been used in the synthesis, the fact that a peroxo group forms in the     

THE CRYSTAL AND MOLECULAR STRUCTURE OF DIPOTASSIUM TRIS(HYDROXYACETATO) VANADYL(ⅠⅩ) MONOHYDRATE

The title compound has been prepared by reaction of VOSO_4 with hydroxyacetic acid in aqueous solution, adding KOH to a suitable pH value. The crystals are monoclinic, space group P2_1/b with cell parameters: α=10.075(2), b=9.857(3), c=14.314(3), γ=115.29(2)°, Z=4. Intensities of 1714 independent reflexions having I≥3σ(I) were collected on a CAD4 diffractometer with MoKα radiation. The structure was solved by Patterson and direct methods and refined by full matrix least-squares method to R=0.060. In the complex the ratio of centric V atom to hydroxyacetate ligands is M:L=1:3, two hydroxyacetate ligands are chelated to V atom in a cis arrangement, the other is monodentate ligand with a carboxyl O atom to grasp the cation VO~(2+).     

THE CRYSTAL AND MOLECULAR STRUCTURE OF THE VIOLET ISOMER OF (⊘P)2[(CF3)2C2S2] RuCO

Abstract

The crystal structure and the details of the molecular configuration of the violet isomer of (?₃ P)₂ [(CF₃)₂ C₂ S₂] -RuCO were established from three dimensional, single crystal, X-ray diffraction data. This isomer crystallizes in the orthorhombic system, space group D¹⁵ ₂h-Pbca, in a cell whose dimensions are: a = 22.394(8), b = 19.107(6) and c = 17.480(5)Å. The measured and calculated densities are 1.56(2) and 1.56 gm-cm^?3 and z = 8 molecules/ unit cell. The shape of the polyhedron of ligands around the central Ru atom is a square pyramid distorted principally by the fact that the Ru—C bond length is shorter than the four bonds to the nearly equidistant phosphorus and sulfur ligands. The dithiolene sulfur atoms occupy adjacent positions in the basal plane; the two triphenylphosphine ligands occupy a basal plane site and the unique axial position while the carbonyl carbon occupies the fourth basal plane site.

The two Ru—S bond lengths are 2.298(3) and 2.287(3) Å, while the two Ru—P distances are 2.353(3) and 2.274(3) A in length, the latter being the basal plane Ru—P bond. The Ru—C and C—O bond lengths are 1.849(11) and 1.133(11) Å, respectively. The bonds within the triphenylphosphines are normal and the phenyl rings are planar, nearly equilateral hexagons. The dithiolene ligand has C—S and (ethylene C)—(ethylene C) distances of 1.719(10) and 1.358(12) Å, respectively, which conform more closely to values expected from an unsaturated cis-dithiol than a dithioketone. The closest inter or intramolecular contact between the Ru atom and the phenyl hydrogens is 3.08 A, which is about 0.5 Å longer than the sum of van der Waals' radii. When refinement was complete, the unweighted and weighted R(F) factors, for 2386 observed reflections, were 0.060 and 0.055, with an error of fit of 1.16.     

THE CRYSTAL STRUCTURE OF BIS(N-METHYLIMIDAZOL)- PALLADIUM OXALATE MONOHYDRATE

<正> INTRODUCTION. In recent years, Zhang Liangfu et al. were successful in using complexes composed of chelate ligand of diphosphine, dinitrogen and transition metal elements of lower valence multi-electrons to activate C-H bond. Recently, we synthesized complexes of bis(N-methylimidazol) ligand with palladium(Ⅱ) or platinum(Ⅱ) oxalate. These compounds activate also     

NICKEL(II) AND EUROPIUM(III) COMPLEXES OF THE AMINOPHENOL LIGAND: 2-(DIETHYLAMINO)METHYLPHENOL (N∼OH). CRYSTAL STRUCTURES OF THE Ni(N∼O)2 AND [Eu(NO3)3(HN∼O)2]2 COMPLEXES

Abstract

The first Ni(II) compounds with aminophenol ligands were synthesized by reaction of 2-diethylaminomethylphenol and 2-diethylaminomethyl-4-methylphenol (N ～ OH) with dehydrated NiCl₂ in ethanol. They were characterized as tran-square planar Ni(N ～ O)₂ complexes by NMR and IR spectroscopies, mass spectrometry, elemental analysis and X-ray structure determination. When the ligand was reacted with Eu(NO₃)₃, the new dimeric complex [Eu(NO₃)₃(HN ～ O)₂]₂ was isolated. Elemental analysis, IR, magnetic moment and X-ray diffraction indicated that in this case formally neutral aminophenol ligands, in their zwitterionic form, are attached to the metal center through the phenolato oxygen and act either as bridging or as terminal groups. Their protonated amino substituents are involved in strong N—H—O hydrogen bridging. The metal shows nine-coordination, the coordination sphere of each europium being completed by three NO₃ groups.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS (1,1,1 TRIFLUORO 3-2-2'''' THENOYLACETONATO) COPPER (II) WITH PYRIDINE

<正> Mr=666.12, triclinic, Pl, a=8.868(1), b=9.719(2), c=10.861(1) A,α=58.23(1)°, β =64.06(1)° r =71.63(1)°; V =711.2 A3; 2=1, Dc=1.555 g.cm-3,for 3724 reflections with I≥ 3σ(I). In the title compound, the copper atomhas a distorted octahedral coordination with four Cu-O long bonds and twoCu-N short bonds. ,     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS [4, 4, 4-TRIFLUORO-1-(2-THIENYL) BUTANEDIONE-1, 3] NICKEL (Ⅱ) WITH DIMETHYLSULFOXIDE, [Ni(TTA)_2(DMSO)]

<正> The title complex [Ni(TTA)2(DMSO)] (TTA = thenoyl trifluo-roacetone, DMSO=dimethyl sufloxide) belongs to triclinic, space group P1, parameters of crystal cell: a = 9.447(l), b = 10.505(1), c=11. 912(1)(?) , α=97. 42(1), β= 84. 00(1), γ = 102. 08(1)°, V = 1143. 3(?)3, Z = 2, Mr = 581. 22 [Ni (C8H4O2F3S)2(CH3)2SO)], Dc=1. 688g. cm-3, F(000) = 588, final R = 0. 065 and Rw = 0. 072 for 2873 reflections with I≥3σ(I). In the title complex the nickel atom has a square pyramidal geometry with four short Ni-O bonds and one long Ni -O (DMSO) bond.     

STUDY ON THE STRUCTURES OF COMPLEXES OF LANTHANIDE WITH BIDENTATE HETEROCYCLIC AMINE——THE STRUCTURE OF BIS[TRI(TRICHLOROACETATO)-1,10-PHENANTHROLINE-BTHANOL-GADOLINIUM]

<正> (GdC12H8N2(CCl3CO2)3C2H5OH)2,Mr=870.60,monoclinic,space group P21/n, a= 12.489(1), b= 18.5194(1),c=13.399(1)A,β=92.9(1)°,V=3095.2A3,Dc=1.868g/cm3 and Z=2. The structure was solved by Patterson and Fourier methods,and refined by full matrix least squares method to R=0.078 for 1619 observed reflections with I>3σ(I).The molecule of the complex is a dimer located at the crystallographic center and each Gd(Ⅲ) atom is eight-coordinated with the coordination polyhedron being a distorted square antiprism.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRACHLORO-BIS[BIS(2-ETHYLHEXYL)-SULFIDE]-PLATINUM(IV)

<正> C32H68Cl4S2Pt, Pt[(BEHS)2Cl4], Mr=853.9, space group P21/a, a =10.445(3), b=15.012(4), c = 13.506(5) A,β=101.43(3)°,V=2076(1) A3, Z=2, DC=1.37 g·cm-3, MoKa radiation, u= 39.3 cm-1, F(OOO) = 876 e, R = 0.053 for 1790 reflections. Pt(IV) is coordinated by four chloro atoms and two S atoms of BEHS, forming a somewhat distorted octahedron with Pt-S of 2.366 and Pt-Cl of 2.309A. The packing pattern of the long BEHS chain may allow the existence of conformational disorder.     

CRYSTAL AND MOLECULAR STRUCTURE OF DIPOTASSIUM TRIS(HYDROXYACETATO)VANADYL (IV) MONOHYDRATE

<正> Preliminary information. The vanadyl complexes are found to be increasingly used in the areas of catalysis, new materials research as well as in bio chemistry. Therefore, more attentions have been paid to such compounds. The title complex K_2[VO(C_2H_3O-3)_2(C_2H_2O_3)] H_2O has been prepared by reaction of VOSO_4 with hydroxyacetic acid in aqueous solution, with KOH added to a suitable PH value.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE HEXANUCLE-AR DIAZENIDO-OXOMOLYBDATE [(n-C_4H_9)_4N]_3[Mo_6O_(18)-(N_2C_6H_3-2,4-(NO_2)_2]

<正> Crystal of the title complex [(n-C4H9)4N]3[Mo6O18(N2C6H3-2,4-(NO2)2](Mr= 1710. 5) is orthorhombic with space group P21cn (Pna21), a = 17. 304(3), b = 17.580(2), c=24. 355(4) (?), V = 7409(2)(?)3, Z = 4, Dc=1. 60g/ cm3, μ=10. 29cm-1, F (000) = 3647. The structural solutions and refinements based on 3900 reflections (I≥3σ(I)) converged at R = 0. 0575, Rw =0. 0498. The atoms of Mo(3), Mo(4), O(1), O(5), O(9), O(11) and the [N2C6H3-2,4-(NO2)2] unit in the complex anion locate approximately in a plane about which the complex anion is nearly symmetrical.     

OPEN METALLOCENE(X)CRYSTAL STRUCTURE OF BIS(2,4-DIMETHYLPENTADIENYL)-MONOCARBONYLTITANUIM

<正> The crystal structure of the complex [2,4-(CH3)2C5H5)2TiCO has been determined by X-ray analysis, belonging to orthorhombic systen, space group P212121 with lattice parameters a = 10.078(2), b = 11,907(2), c = 11.946(3) A, V = 1433.7 A3 and Z = 4. Several cycles of block matrix least-squares refinement gave the final R = 0.054. The results of the X-ray diffraction study confirm the open sandwich configuration of the compound with two ligand planes nearly parallel and eclipsed.     

CRYSTAL AND MOLECULAR STRUCTURES OF 2-ACETYLDIFER-ROCENYLMETHANE AND 3'''' - ACETYLDIFERROCENYLMETHANE

<正> 2 - acetyldiferrocenylmethane, C5H5FeC5H4CH2C5H3 (COCH3) FeC5H5 ( I ),Mr=426. 1,violet-red prism-like crystal,m. p. 163. 7~166. 3℃,obtained from benzene-ligroin solution (benzene : ligroin=1 : 3). A crystal of approximate dimensions 0. 20×0. 40×0. 45 mm was selected for data collection from a CAD4 diffractometer with graphite monochromated MoKa radiation (λ=0. 71069A). Compound Ⅰ crystallized in the triclinic space group P1 with unit cell dimensions;a = 9. 597(2),b=9. 768 (2),c=11.540(1) A ,α= 111-93(1),β=111. 42(1),γ= 92. 46(2)°,V = 913. 9 A3, Z= 2, and Dc= 1. 548 g/cm3. 3' - Acetyldiferrocenylmethane, C5H5FeC5H4CH2C5H4FeC5 H4-COCH3(Ⅱ) ,is an isomer of compound Ⅰ ,yellow needle-like crystal,m. p. 110. 5~ 111. 0℃ ,obtained by the same method. A crystal of approximate dimensions 0. 025×0. 01×0. 45 mm was selected for data collection. Compound Ⅱ crystallized in monoclinic space group P21/c with a = 10. 930 (2), b= 5. 907(6) ,c= 27. 729(5) A ,β= 92. 64 (1)°,V=1788. 4A3,Z=4,Dc=1. 583 g/cm3.     

CRYSTAL STRUCTURE OF THE N-[4-ACETYL-1-(2-CYCLOHEXYLETHYL)-4-PIPERIDINYL]-N-PHENYLPROPANAMIDE(1509)OXALATE

<正> The crystal structure of N-[4-acetyl-l-(2-cyclohexyl-ethyl)-4-piperidinyl]-N-phenylpropanamide oxalate was determined by X-ray analysis. C24H36N2O2.CaO4H2, orthorhombic, space group Pbac, a=11.372(3), b=18.584(7) c=24.204(8) A, V=5115.2(3)B3, Z=8, F(000)=2048,Dc=1.23g/cm3, R=0.074.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A HETERODINUCLEAR COMPLEX OF PALLADIUM SILVER WITH BRIDGING BIS-( DIPHENYLPHOSPHINO ) METHANE [ 1 ]

<正> A heterodinuclear complex, trans- dicyano- palladium (Ⅱ)- bis [β- bis (diphenylphosphino)methane]-nitritosilver(Ⅰ),has been prepared by treatment of trans-(NC)2Pd(dppm)2 with AgNO2 and characterized by elementary analysis, ir, nmr, and X-ray crystal structure determination. AgPdC52H44N3O2P4,Mr= 1081. 12,monoclinic,space group P21/c,a=14. 745(7),b= 19. 208(7),c= 17. 486(6) A ,β=94. 99°(2) ,and Z = 4. The final R=0. 032 for 8673 unique reflections. In the molecule,the Pd -Ag distance is 3. 205 A. The palladium moiety has an approximately square planar geometry, and the silver moiety has a severely distorted tetrahedral geometry.     

CRYSTAL STRUCTURE OF (μ-OXO)-BIS[BIS(DIETHYLDITHIOCARBAMATO)- OXO-MOLYBDENUM]

<正> INTRODUCTION. The reaction oF MoCl_3·3H_2O with dithiocarbamate in organic solvents is a interesting research area. Thus, several dinuclear and trinuclear molybdenum complexes have been synthesized The dinuclear oxo-dridged molybdenum compound was obtained by this reaction in acetonmethanol mixed solvent. The molecular configuration has been characterized     

STUDY OF THE CRYSTAL STRUCTURE OF BIS(2,4-DIMETHYL-PENTADIENYL) MONOCARBONYL-VANADIUM USING A LOW TEMPERATURE X-RAY DIFFRACTION TECHNIQUE

<正> The single crystal X-ray diffraction data of (2,4-(CH3)2C5H5]2VCO have been collected under low temperature (-60℃) and the crystal structure has been solved by heavy atom method. It belongs to orthorhombic system, space group P212121, a =9.921(6), b =9.899(6), c=14.491(8) A, Z=4. Several cycles of block matrix least-squares refinement gave the final R=0.087.     

SYNTHESES, PROPERTIES AND CRYSTAL AND MOLECULAR STRUCTURES OF THE COMPLEXES OF LANTHANIDE THIOCYANATES WITH 1,8-NAPHTHO-16-CROWN-5

Complexes formed from lanthanide thiocyanates (except Pm, Tm and Lu) and 1,8-naphtho-16-crown-5 have been synthesized and characterized by elemental analyses, IR spectra, TG-DTA and electrical conductivity measurements. A single crystal structural analysis for the complex of Er(NCS)_3 with 1,8-naphtho-16-crown-5 has been performed. The result shows that Er(Ⅲ) ion is coordinated simultaneously by five oxygen atoms of the crown ether and three nitrogen atoms of thiocyanates. The coordination number of Er(Ⅲ) ion is eight.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(PPh_3)_3(Cu_3S_3MoBr)O]-0. 5CH_2C1_2

<正> [(Ph3P)3 (Cu3S3MoBr)O] 0. 5CH2C12, Mr = 1308. 00, monoclinic, P21/c,a=11. 831(3),b = 28. 471(8),c=19. 232(5) A ,β= 101. 05(3)°,V = 6358 A3,Z = 4,DC=1.37 g/cm3,F(000) = 2620,μ(MoKa) = 20. 47 cm-1. Final R=0. 085 for 4271 observede reflections. The core [Cu3S3MoBr] has a distorted cubic configuration. Two dichloromethane molecules distribute statistically in a unit cell.     

STUDIES ON DERIVATIVES OF 2, 3-DIHYDRO-4 H-1, 3, 2-BENZOXAZAPHOSPHORINE——THE DETERMINATION OF THE CRYSTAL AND MOLECULAR STRUCTURE OF 2, 3-DISUBSTITUTED-2, 3-DIHYDRO-4H-1, 3, 2-BENZOXAZAPHOSPHORIN-4-ONE (THION)-2-SULFIDE(OXIDE)

The two crystal structures of C_(17)H_(17),N_2O_2Cl_2PS (NP-8) and C_(17)H_(19)N_2O_2PS (NP-10-Ⅱ) have beendetermined by Patterson method. The crystals belong to monoclinic system with space group of P2_1/aand P2_1/n respectively. There are four molecules in the unit cell. Cell parameters: a = 26.622 (7)A, b = 7.711 (2) A., c = 9.461 (3) A, β = 94.90°(4) and a = 18.879(3) A, b = 10.199 (13) A, c = 8.948(3) A, β= 94.30°(3) for the two cells. After refinement by block diagonal matrix least squares me-thod, R factors are 0.046 for 2971 reflections of NP-8 and 0.076 for 1711 reflections of NP-10-Ⅱ. Referring to molecular structures of NP-8 and NP-10-Ⅱ spectra data have been satisfactorilycxplained. The characteristic features of the structures have been discussed.