CRYSTAL STRUCTURE INVESTIGATION OF VANADYL COMPLEXES OF TRIDENTATE LIGAND (Ⅰ)——THE CRYSTAL STRUCTURES OF BIS[(1-(2,4-PENTANE- DIONATO(NITROBENZOYL) HYDRAZONE)-2- ETHOXY)OXOVANADIUM] AND BIS-[(1-(2, 4-PENTANEDIONATO-(3-NITROBENZOYL) HYDRAZONE)-2- METHO

The title complexes were obtained by the reactions of bis(2,4-pentanedionato)oxovanadium VO(Acac)_2 and m-nitrophenylhydrazide m-NO_2PhCONHNH_2 in the media EtOH and MeOH respectively. The compound (Ⅰ) crystallizes in the space group PT with unit cell dimensions a=8.123(2), b=10.409(5), c=10.822(4), α=65.78(3)°, β=85.50(3)°,γ=89.04(3)°. The compound (Ⅱ) crystallizes in the space group P2_1/a with unit cell dimensions a=7.745(2), b=19.164(5), c=10.787(4), β=107.87(2)°. The resuhs of structural analyses show that the two compounds have the same characteristics: the tridentate ligand formed by condensation occupies three of the four equatorial positions of vanadium and the rest equatorial position is occupied by alkoxy group RO~-. As RO~-group also bridges the sixth coordinated position of each vanadium atom, it brings about the formation of the new type binuclear complexes of vanadium.     

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     

THE CRYSTAL STRUCTURE OF THE ADDITION COMPOUND OF DECAVANADIC ACID AND 5,7-DIMETHYL-2, 3-DIHYDRO-1, 4-DIAZEPINIUM

The title compound crystallizes in the space group C_(2h)~5-P2_1/n with unit cell constantsa=10.938 A, b=19.189 A, c=13.384 A and β=105.09°. Intensities of 4022 independent reflec-tions were collected with four-circle diffractometer using MoKa radiation. After reduction fordiffractometer data, we derived first the position parameters of all the V atoms by directmethod using SHELXTL program. The coordinates of all the non-hydrogen and hydrogenatoms were obtained from successive Fourier and difference sytheses. The block-diagonalleast-squares refinement for all atoms gave a final discrepancy weighted factor R_w=0.050. The result of structure analysis shows that four protons of each decavanadic acid arecaptured by the nitrogen atoms involved in the azepine molecules which are condensation pro-ducts of ethylenediamine with acetylaceton. In crystal, the isopoly-decavanadate anion, 7-member heterocyclic azepium and the crystal water are linked together by ionic forces andhydrogen bonding and the chemical content within a unit cell has been identified as 2[H_2V_(10)O_(28)]~(-4)·8[C_7N_2H_(13)]~( 1)·12H_2O.     

CRYSTAL AND MOLECULAR STRUCTURE OF DEHYDROCRYDALINE CHLORIDE

The crystals of alkaloid Dehydrocrydaline chloride (C_(22)H_(24)NO_4·HCl) belong to the orthorhombic system. The space group is D_(2k)~(14)-Pbcn with the unit cell parameters of a=8.528,b=23.317 and c=24.798, and eight molecules per unit cell. The coordinates for all the non-hydrogen atoms were found by using direct methods and Fourier syntheses. During the course of refinement of this structure (using least squares and difference Fouriers), it was discovered that there are 4.5 water molecules with different occupancies in one asymmetric volume of the unit cell. The anisotropic refinement of non-hydrogen atoms and the isotropic refinement of non-aqueous hydrogen atoms led to a final R-factor of 0.053. Water molecules formed a relatively complex network around chloride ion.In this paper the small molecule structure and the network of water molecules are described.     

CRYSTAL AND MOLECULAR STRUCTURE OF PALMATINE CHLORIDE PHENOL SOLVATE MONOHYDRATE

<正> The crystal of palnatine chloride phenol solVate monohydrate belongs to the triclinic, space group Cl-P1 with the unit cell parameters of a =14.781, b=11.246, c= 7.505 A,α=95.26(7)°,β=96.87(4)°,γ=94.32(4)°,and Z=2,The coordinates for all the non-hydrogen atoms were found by using direct methods and Sim weighting Fourier synthesis. The anisotropic refinement of non-hydrogen atoms and isotropic refinement of hydrogen atoms led to a final R-factor of 0.055. Solvate molecules form a relatively complex network around chloride ion.In this paper palmatine nolecule structure and the network of solvent molecules are described.     

CRYSTAL AND MOLECULAR STRUCTURE OF A DIPHENYL SULFOXIDE COMPLEX WITH CERIUM NITRATE, Ce(N0_3)_3[(C_6H_5)_2SO]_4

<正> The title complex crystallises in the triclinic, space group PT with two formula units in a unit cell of dimensions a=11.182(4), b=14.357(5), c=17.362(6) A and α= 84.08(3)°, β=72.79(3)°, r= 69.27(2)°, Dx=1.51 g.cm-3, V=2489.6(15) A3. The final index for 6319 observed reflections is 0.0274. The Ce3+ ion is coordinated by ten oxygen atoms with Ce-O distances varying from 2.469 to 2.706 A. The three nitrate groups are all bidentate ligands.     

THE CRYSTAL STRUCTURE AND SPECTROSCOPIC PROPERTIES OF THE COMPLEXES FORMED BY TiCl_4 AND MgCl_2 WITH ESTERS——A RESEARCH ON THE STRUCTURE OF HIGHLY EFFICIENT CATALYSTS FOR POLYPROPYLENE

The complexes of TiCl_4, MgCl_2 and esters which are significant in industry have beenstudied by X-ray diffraction, IR and uv spectra. Their single crystal structures have also beendetermined. TiCl_4 and PhCOOEt can form two complexes, TiCl_4·L and TiCl_4·2L·MgGl_2, CH_3COOEtand H_2O form complex MgCl_2·2CH_3COOEt·2H_2O. All of them are molecular crystals. Theirspacial groups are C_(2h)~5-P2_1/c, C_(2h)~5-P2_1/n and C_(2h)~6-C_2/c respectively. From the XRD powderpattern, it has been ascertained that TiCl_4·L is formed in the process of the catalyst prepara-tion with milling-soaking method. Comparison between the IR spectra of the catalyst and Mgcomplex indicates that the coordinative bonds of the surface complex of the catalyst are verysimilar to that of the complex.     

CRYSTAL AND MOLECULAR STRUCTURE OF N-CYANOMETHYL PH-THALIMIDE AND N-CYANOMETHYL SUCCIMIDE

<正> Diethylaminoacetonitrile (1) reacts with phthalimide (2) or succirnide (3) to produce N-cyanomethyl phthalimide (4) C10H6O2N2 (Mr = 186. 168) or N-cyanomethyl succirnide (5) C6H6O2N2(Mr= 138. 128),respectively. Their molecular and crystal structures were determined by IR, 1H NMR, MS and X-ray diffraction analysis, compound (4) crystallizes in monoclinic space group P21/a(P21/c) ,with cell dimensions 0=8. 225(4) ,6= 10. 956(4),c= 10. 041(5) A .β=102. 43(4)°,V=883. 1A3, μ= 0. 90cm-1, F (000) = 384, Z = 4; compound (5) crystallizes in monoclinic space group P1,with a=8. 404(2),b = 9. 710(2),c= 10. 093(2) A ,α= 104. 73(2)°,β = 108. 55(2)°, γ= 112. 03(2)°,V= 655. 2 A3,μ= 1.0cm-1 ,F(000) = 288,Z= 4. The average inner angles of the five-membered ring of (4) and (5) are about 108°. The imide and the carbon atom of the methylene radical of N-cyanomethyl and phenyl ring are all in one plane . so the bonds are delocalized and the α-hydrogen atoms of N-cyanomethyl are activated. The syntheses and crysta     

THE CRYSTAL AND MOLECULAR STRUCTURE OF CHLORO(BIS-2,2''''-DIPYRIDYL) COPPER7,7'''',8,8''''-TETRACYANOQUINODIMETHANE [Cu(bipy)_2Cl]·TCNQ_2

The crystals of title compound are prepared by the electrochemical method and its structure has been determined by X-ray diffractions method. The crystals are triclinic with space group P(?). a=7.920, b=13.140, c=19.126; a=100.77°, β=94.45° and γ=101.08° ; Z=2, Calculating of electronic structure of TCNQ and its packing mode are discussed.     

TRINUCLEAR BASIC CARBOXYLATE COMPOUNDS OF TRANSITION METALS PART 2. SYNTHESIS AND CRYSTAL STRUCTURE OF [Fe_3O (EtCO_2)_3(MeCO_2)_3(H_2O)_3]NO3·H_2O

<正> The title complex crystallizes in monoclinic system,space group C 2/m with α=19. 870(5),b=13. 070(2),c=18. 246(4)A ,β=134. 32(1)°,Mr = 707. 88, V=3390. 0A3.Z = 4,DC=1. 387g/cm3,F(000) = 1468,final R=0. 066 for 2244 independent reflections with Ⅰ >3σ(Ⅰ). The cation was shown to contain three Fe (Ⅲ) atoms at the apices of an equilateral triangle with a 3-O bridge.The Fe (1)-(μ3-O)and Fe(2)-(μ3-O) distances are 1. 907(6) and 1. 87(1) A , respectively. And mixed ligands of acetato and propionyloxy lato are bridged to each pair of the Fe(Ⅲ) atoms.     

THE CRYSTAL STRUCTURE OF BAYLEYITE

The bayleyite crystallizes in monoclinic space group C_2~5h-P2_1/c with a=6.499(1), b=15.235(5), c=26.513(6), β= 92.92(2)°, Z=4. Intensities of 3430 independent reflections are collected with diffractometer using MoKα radiation. The crystal structure has been solved by the Patterson method and refined by block least square refinement for positional parameters and isotropic temperature factor of non-hydrogen atoms. The final R factor is 0.038.The result of crystal structure analysis shows that the structure consists of discrete [UO_2(CO_3)_3]~(4-) ions and Mg~(2 ) cations are between slab-like units, but they are not in a slablike unit. Its crystal struture is different from that of liebigite which was determined by Appleman. Complexes and cations between slab-like units and in a slab-like unit are connected by hydrogen bonds formed by water molecules.     

SYNTHESIS AND STRUCTURE OF A TRITHIOCARBONATO Mo(Et_4 N)_2 [(S_2)Mo_2O_2(μ-S)_2(CS_3)]

A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from asystem containing MoO_4~(2-),S_x~(2-),and CS_2 and characterized by IR and X-ray structural analysis.The complex crystallizes in the (?)onoclinic space group P2_1/c with a=9.539(3)(?),b=20.745(2)(?),c=15.452(2)(?),β=94.58(2)°,and Z=4.The structure was solved by direct anddifference Fourier synthesis methods.Least squares refinement using 2910 reflections withI>3σ(I)converged to R=0.054.The CS_3~(2-) iigand in the complex chelates to Mo atom andvalues of the C-S bond distances in the CS_3~(2-) ligend indicate a substantial contribution ofthree resonance forms.     

SYNTHESIS, CHARACTERIZATION AND STRUCTURE OF [Co(DBP)_2·3Py]_2·2CHCl_3

The mixed ligand complex of cobalt with dibutylphosphate (HDBP) and pyridine has been synthesized. Elemental analysis yields the result that the formula of this compound is Co(DBP)_2·3Py·CHCl_3 (Py=pyridine). The thermal analsyis, visible spectra and magnetic properties of it have been studied as well. Single crystal structural analysis shows that the crystal is triclinic with space group P and the unit cell parameters are as follows:a=14.490(10), α=90.37(4)°,b=15.721(7), β=96.04(5)°,c=20.109(12), γ=105.63(4)°.The final R factor is 0.0773. Two Co atoms are connected by two bridging DBP groups to form a dinuclear molecule [Co(DBP)_2·3Py]_2 which has a C_s, symmetry. Each cell contains two dinuclear molecules and four chloroform molecules. The cobalt is coordinated in an octahedral arrangement by three oxygen atoms and three nitrogen atoms, of which one oxygen atom comes from a monodentate DBP group, two oxygen atoms from two bridging DBP groups, and the three nitrogen atoms from the three pyridi     

SYNTHESIS AND STRUCTURE OF Ni_2(PBu_3~n)_2(SC_7H_6S)_2

<正> The nickel(Ⅱ) complex Ni2(PBu3n)2(tdt)2(tdt = SC7H6S2-) containing dithiolato and phosphino ligands has been prepared and characterized by X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a = 14. 423(4), b = 15. 053(3), c=10. 648(3)(?), α=93.,95(2), β=100. 31(3), γ = 84. 16(2)°; V =2259.6 (?)3; Z = 2, Dc= 1. 22 gem-3, Mr = 830. 57; μ = 11. 076cm-1, F (000) = 888. In the complex, the Nickel atoms are linked by two bridging sulfur atoms from the two tdt ligands with the Ni-Ni distance of 2. 679 (?) . and each nickel atom is four coordinated by one phosphorus and three sulfur atoms with a square-planar geometry, the average length of Ni -S bond is 2. 193(?) and that of Ni-P bond 2.186(?).     

HETERONUCLEAR COMPLEX CONTAINING COPPER-LANTHANIDE ARRAYS: THE SYNTHESIS AND CRYSTAL STRUCTURE OF Ln_2Cu_4L_8 (HL)_4(OH)_2(CIO_4)_4(H_2O)_(10)·2CH_3COCH_3 (Ln = Tb (1), Y (2); HL = 2-Pyridone C_5H_5NO)

Reaction of 2-pyridone, copper acetate and terbium(or yttrium) perchlorate in acetone with the moleratio 6: 2: 1 results in the formation of heteronuclear complex Ln_2Cu_4L_8 (HL)_4 (OH)_2 (ClO_4)_4 (H_20)_(10)2CH_3COCH_3(Ln = Tb (1), Y (2)). By recrystallizing (1) in CHCl_3 single crystals were obtained and thestructure was determined by four-circle diffractometer. Data showed that the crystal is in space groupC2/m with a=27. 454(9)A, b=13, 608A, c=30. 556(11)A, β=99. 89(3)°, v=11245. 7(7. 5)A~3. Thestructure was solved by a combination of Patterson method and Fourier technique. The final R value is0. 103. In the structure, four copper and two terbium ions are bridged by 2-pyridone anions to form anessentially octahedral Cu_4Tb_2 core. The terbium atoms are each eight-coordinate and the copper atomsare five-coordinate.     

A CLUSTER COMPOUND WITH DI-ENDOXYGEN LIGANDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF [Fe(MOS_4O)_2][N(C_2H_5)_4]3

[Fe(MoS_4O)_2] [N(C_2H_3)_4]_3 cluster compound with di-end-oxygen ligands has been prepared and characterized by the X-ray diffraction method. The compound crystallizes in a monoclinic space group P2_1/n with lattice parameters a=13.019(4), b=16.959(5), c=18.234(5), β=97.34(2)(°), Z=4. The final agreement factors are R=0.0740, Rw=0.0598. The terminal bond length, Mo-S_t and bridged one, MO-S_b for the compound are much longer than the counterpart without end-oxygen ligand. It possibly suggests that low valence of molybdenum and smaller electronegativity of sulphur than oxygen lead to the charge transfer as S→Mo→O.     

THE CRYSTAL STRUCTURE OF THE ADDITION COMPOUND OF SODIUM TETRAHYDROGEN DECAVANADATE AND HEXAMETHYLENETETRAMINE

The title compound crystallizes in the space group C_i~1-Pī with cell constants a=9.589, b=10.486, c=11.139, α=103.27° β=98.20° and γ=103.16°. After deriving the position parameters of all V atoms by Patterson method, the coordiuates of all the non-hydrogen and hydrogen atoms were obtained from successive Fourier and difference syntheses, and the leastsquares refinement for all atoms gave a final discrepancy factor R=0.0279. The chemical content within a unit cell has been identified definitely as (Na~+)_2·(H_2V_(10)O_(28)~(4-))·2((CH_2)_6N_3N-H~+)·8H_2O.     

CRYSTAL AND MOLECULAR STRUCTURE OF [K(18-CROWN-6)][Bi(SCN)Cl_3]

<正> The crystal and Molecular structure of [K(18-crown-6)](Bi(SCN)Cl3] has been deterained by X-ray diffraction Method. Its crystal is triclinic, space group Pl,with a = 9.233(4), b = 11.661(5), c=11.738(5)A,a= 81.82(4)° ,β=71.47(4)°,γ=75.55(4)°, and Z = 2. The final structural refine-ment converged with unweighted and weighted R factors of 0.051 and 0.047 for 2924 observed reflections. Results of the structure analysis indicate that the K+ ion enters the cavity of the 18-crown-6 to form the complex cation and one Bi(Ⅲ) atom, one SCN ligand and three Cl atoms fora the anion. Each Bi(Ⅲ) atoa is coordinated by four Cl atoas, of which two are shared with other Bi(Ⅲ) atom, one N atom and one S atoa from two SCN ligands respectively shared with a third Bi(Ⅲ) atoa, forming octahedral geometry.     

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.     

CRYSTAL STRUCTURE OF THE ADDUCT OF DECAVANADATE AND HEXAMETHYLENE-TETRAMINE {[HMT· H~+(V_(10)O_(28))~(6-)·H~+·HMT]· 2[HMT· CH_2NH_2]~+·2(H_3~+O)·12H~2O}

The title compound crystal belongs to the trilinic space group C_i~1—P(?) with unit cell parameters: a=11.208 (4), b=13.166 (4), c=13.239 (3),α=118.15 (2)°,β=94.78(2)°,γ=109.19 (2)°, and Z=1. The crystal structure was solved by direct method and difference Fourier techniques using the SHELXTL program, and was refined finally to R=R_W=0.0462 for 4702 reflections. Structural analysis shows that the four protons in the cluster of the decavanadate group are separated into two types. For one of them, the two protons are captured by two O7 in the cluster of the decavanadate and two nitrogen atoms of the hexamethylenetetramine, to form hydrogen bonds; moreover, we have verified that the N-aminomethylhexamethylenetetraminium which was produced during the reaction existed in the title compound crystal. We infer that the N-aminomethylhexamethylenetetraminium [(CH_2)_6N_4CH_2NH_2]~+ could be produced by the heterogeneous catalysis reaction from the surface of the vanadium pentoxide [V_2O_5].