CYCLOADDITION REACTION OF THE AZIDO-BRIDGED CYCLOMETALLATED COMPLEX [Pd(dmba)N3]2 WITH CS2. CRYSTAL AND MOLECULAR STRUCTURE OF DI(μ, N,S-l,2,3,4-THIATRIAZOLE-5-THIOLATE)BIS[(N,N-DIMETHYLBENZYL-AMINE-C2,N)PALLADIUM(II)]

Abstract

The 1,3-dipolar cycloaddition of carbon disulfide to the coordinated azide in the cyclometal-lated compound [Pd(dmba)(N₃)]₂ (1), dmba = N,N-dimethylbenzylamine, was investigated. The compound obtained di(μ, N, S-l,2,3,4-thiatriazole-5-thiolate)-bis[(N,N-dimethylbenzylamine-C², N)palladium(II)] (2), was characterized by IR spectroscopy and X-ray diffraction. Complex (2) is dimeric with the two [Pd(N,N-dimethylbenzylamine)] moieties being connected by the two vicinal bridging N, S-l,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination for the palladium atoms.     

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     

CRYSTAL STRUCTURE OF BIS(μ-SULFIDO)-BIS[OXO-DIETHYL-DITHIOCARBAMATO-MOLYBDENUM(V)]

<正> INTRODUCTION. Reaction of MoCl_3·3H_2O with dithio-carbamate to synthesize dinuclear or trinuclear molybdenum complexes is an interesting topic. We have obtained sulfido-bridged molybdenum(V) complex Mo_2(μ-S)_2O_2(S_2CNEt_2)_2 by reacting MoCl_3·3H_2O with NadtcEt_2 in MeOH solvent. The molecular structure of the title compound was characterized by, X-ray structure determination. We report the result of the structure determination in this paper.     

THE STRUCTURE OF TETRABUTYLAMMONIUM BIS(1,3-DITHIO-2-THION-CYCLOPENTENE-4, 5-DITHIOLATE)PALLADIUM(Ⅱ)

<正> Mr=984.05 monoclinic P21/c a=8.474(1),b=14.768(3), c=19.494(3) A,6=96.42(1)0, V=2424.5(7)A3, Z=2, (Mokα)=8.Hem-1, F(000)=1039.91, room temperature. The final R=0.0357 for 2696 independant reflections. The Pd(C3S5)22-ion is nearly planar and the Palladium(Ⅱ)-sulfur coordination polyhedron is square planar with Pd-S distances of 2.315A and 2.311A.     

CRYSTAL AND MOLECULAR STRUCTURE OF BIS(O,O'-DICYCLOHEXYLDITHIOPHOSPHATO)-NICKEL(Ⅱ)

<正> Ni[(C6H11O)2PS2]2, Mr=627.39, Monoclinic, P21/n, a=11.802(7), b= 9.336(2), c=14.177(5) A,B=96.72(4)°,V=1551.3A3, Z=2, Dc=1.343g·cm-3, MoKα radiation λ=0.71073A, F(000)=648e, R=0.068 for 2642 reflections. Ni(Ⅱ) atom is surrounded by four sulfur atoms, forming a square.     

PREPARATION, PROPERTIES, AND MOLECULAR STRUCTURE OF trans-DICYANO BIS[BIS(DIPHENYLPHOSPHINO) METHANE]PALLADIUM (Ⅱ)

<正> The crystal structure of the title compound has been determined. PdC52H44N2P4, Mr = 927. 2, monoclinic, space group P21 /n, a =12. 102(2), b = 9.997(2), c=20. 254(5)(?),β=93. 80(2)°, V = 2445. 0(?)3, Z = 2, R =0. 075 and Rw = 0. 095 for 3535 observed reflections (I>3σ(I)), The palladium atom is located on the symmetric center and adopts a square planar coordination surroundings with two biphosphine ligands and two cyanide groups. The molecular structure in crystals is different from that in solution in which the molecule is very fluxional, probably due to the rapid alteration in coordination sites between the coordinated and uncoordinated phosphorus atoms of the biphosphine ligands. Their properties are also reported.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF Ni(TAAB)(BF_4)_2WITH PYRIDINE

The crystal structure of [Ni(TAAB)(py)_2](BF_4)_2,where TAAB is thetetradentate macrocyclic ligand tetrabenzo[b,f,j,n] [1,5,9,13]tetraazacyclohexadecine,has been determined from X-ray diffraction analysis.The crys.tai beiongs to monoclinic,space group P2_1/n with cell parameters     

CRYSTAL AND MOLECULAR STRUCTURE OF THE ADDUCT OF BIS [4,4,4-TRIFLUOR-1-(2-THIENYL) Butandion-1,3] COPPER (Ⅱ) WITH DIMETHYLFORMAMIDE, [Cu(TTA)_2(DMF)]

<正> [Cu(C8H4F3O2S)2(C3H7NO)], Mr = 579. 0, monoclinic, P21/c, a = 9. 4851(6), b = 26. 6574(6), c=9.2619(6) A ,β=96.08(3)°, V = 2328.7A3, Z=4, Dc=1. 65gcm-3, μ(MoKa) = 7. 2cm-1, F (000) = 1172, MoKa radiation, final R = 0. 074 and Rw = 0. 068 for 1841 reflections with I≥3σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by five oxygen atoms, one of which from DMF is in the axial position, to form a square pyramidal geometry. That the thenoyl groups in the ligands take the cis-form around the Cu(Ⅱ) atom is explained by the hydrogen bonding effect.     

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. ,     

THE CRYSTAL STRUCTURE OF DI-μ-CHLORO-HEXACHLORO-BIS (ETHYL-CYANOFORMATE-N) DITITANIUM (IV)

Abstract

Crystals of the adduct titanium tetrachloride-ethylcyanoformate (1–1) are monoclinic a =9.06 Å, b =18.36 Å, c =13.83 Å, β =113°.2, space group C2/c, Z =8. The structure was solved by application of X-Ray diffraction techniques at room temperature. Atomic positions were refined by a full-matrix least-squares method to a final R of 0.049 using 829 non-zero independent reflections. This compound is dimeric with a double chlorine bridge between titanium atoms. Titanium is octahedrally coordinated to five chlorine atoms and to the nitrogen atom of the nitrile group and not to the oxygen atom of the carbonyl group. Thus in this complex the nitrogen atom is a better donor than the carbonyl oxygen.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-SPh) (μ-SCH2CH2CN)Fe_2 (CO)_6

<正> The crystal and molecular structure of (μ-SPh)(μ-SCH2CH2CN)Fe2-(CO)5 has been determined by X-ray diffraction method. The crystals of this complex are triclinic, space group P1,with a=ll.175(1), b=ll.877(2), c= 15.640(2)1,α=106.20(1),β=103.15(1),γ=98.46(1)°; Z=4; Dc=1.67g/cm3. The final structure refinement converged with unweighted and weighted R factors of 0.028 and 0.034 for 2853 observed unique reflections.     

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 BEDT-TTF[Pd(dmit)_2] (H_2dmit=4,5-dimercapto-1,3-dithiole-2-thione)

<正> C16H8PdS18, Mr=984.6, triclinic, Pl, a=6.6889(20), b=7.3824(21), c=15.0945(38)A; α=92.098(23)°,β=97.958(22)°, r=109.269(22)°, V=694.14(33)A3, Z=1; μ(MoKα)=19.68 cm-1. F(000)=437.98, room temperature, R=0.042, Rw=0.041 for 1865 independent diffractions. Planar BEDT-TTF and Pd(dmit)a stack along b axis separately. The separation between BEDT-TTFs is 6.74A, that between Pd(dimt)a planes 6.53A. This feature of BEDT-TTF[Pd(dimt)2] stacking may be used to explain the semiconducting character of the title compound.     

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 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.     

CRYSTAL STRUCTURE OF (μ-PYRAZINE)-BIS[DIAQUA(IMINODIACETATO) COPPBR(Ⅱ)] DIHYDRATE

<正> PRELIMINARY INFORMATION. Recently multinuclear complexes with bridging ligand have been found possibly to possess special catalytical and special electric properties. Therefore more attention has been paid to such complexes. This study is a part of systimatic investigations on structures and properties of the kind of complexes, which have been carred out previously.     

REPLACED SITE OF Eu~(2+) ION IN THE COMPLEX FLUORIDES WITH THE PEROVSKITE CRYSTAL STRUCTURE

The replaced site of Eu~(2+) ion is dependent on the electronegativitydifference of the cations in complex fluorides.In the mixed fluorideKMgF_3:Eu~(2+),Eu~(2+) ion occupies K~+ site,its emission spectrum is a sharpline and its valence-state is stable.     

CRYSTAL AND MOLECULAR STRUCTURE OF GUANIDINIUM BIS (o-AMINOPHENYLARSENIC) HEXAMOLYBDATE (CN_3H_6)_4[(o NH_2C_6H_4 As)_2Mo_6O_(24)]

<正> Guanidinium bis (o - aminophenylarsenic) hexamolybdate belongs to monoclinic space group P21/c,with a=10. 217(2),b= 18. 870(2),c= 10. 939(2)A,β = 102. 82(3)°,Z = 2,V=2056. 4A3,and Dc=2. 477 g·cm-3. Each molecule contains one [(o-NH2C6H4As)2Mo6O24]4- anion and four CN3H6+ cations. In the anion,six distorted MoO6 octahedra are connected with edges-sharing to form a six-membered Mo ring which is capped above and below by two o - aminophenylarsenic groups. There is half a molecule in an asymmetric unit. It is interesting that both phenyl planes are almost perpendicular to the plane of the Mo atoms. The structure of the anion is similar to that of [ (CH3 As)2Mo6O24]4-,[(n-C3H7As)2Mo6O24]4- or [(C6H5CH2As)2Mo6O24]4-. This is the first example of this type of compounds in which the As atom is directly connected to a substituted phenyl group.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-PhS) (μ-σ,π-CH_3CH = CH)Fe_2(CO)_6

<正> The crystal and molecular structure of (μ-PhS) (μ-σ, n-CH3CH = CH)-Fe2(CO)6 has been determined by X - ray diffraction technique. The complex has chemical formula of C15H10O6SFe2 and Mr=129. 99. The crystals are monoclinic,space group P21/c,with α=11. 789(2),b= 7. 159(1),c = 20. 890(4) A ;β = 100. 89(2);V = 1731. 32 A3;Z=4,Dc=1. 65g·cm-3;F(000) = 863. 86. The final R and Rw equal 0. 0315 and 0. 0405 respectively for 2527 observed unique reflections.     

MOLECULAR AND CRYSTAL STRUCTURE OF TETRAHYDROFURAN COORDINATED YTTERBIUM TRICHLORIDES YbCl_3(C_4H_8O)_3

<正> YbCl3(C4H8O)3, Mr = 495. 73, monoclinic, space group P21/c, a = 9.024(2), b=12.863(2), c=15. 762(7) A ,β=92. 21(2)°. V = 1828. 7(9) A3, Z = 4, DC=1. 801gcm-3, A(MoKa) = 0. 71073A, μ= 64. 44cm-1, F (000) = 964, R = 0. 075 for 2259 unique observed reflections. The Yb3+ ion is in a distorted octahedral coordination with three Cl ions and three O atoms from three tetrahydrofuran (THF) molecules. The average Yb -Cl distance is 2. 525A and Yb -O is 2. 303A.