EXAFS and FTIR structural characterization for the crystal of monomeric tetraphenylporphyrinato gadolinium:[Gd(TPP)acac 8H_2O.3TCB]

The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.     

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper(Ⅱ) coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4'-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756(10),b= 1.57756(10),c=2.1438(3)nm,V=5.3352(8) nm3,Dc=1.524 g/cm3,Z=4,F(000)=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper(1) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry;the copper(2) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.     

Synthesis and crystal structure of heteronuclear La(Ⅲ)-Cu(Ⅱ) complex {[LaCu_2(NTA)_2(4,4'-bpy)(H_2O)_3]NO_3·5H_2O}_n

A novel La(Ⅲ)-Cu(Ⅱ)heterometallic coordination polymer {[LaCu2(NTA)2(4,4'-bpy)(H2O)3]NO3 5H2O}n,where H3NTA denotes nitrilotriacetic acid and 4,4'-bpy denotes 4,4'-bipyridine,was synthesized and characterized by IR spectrum,elemental analysis and X-ray diffraction.The complex crystallizes in the triclnic space group PT with cell parameters a=1.33710(10)nm,b=1.44530(10)nm,c=1.0949(2)nm,α=71.905(7),β=74.327(7),γ=64.427(9),V=1.7912(4)nm3 and Z=2.It consists of heterometallic units,in which each La(Ⅲ)ion is coordinated in a distorted mono-capped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA3-ions,and each Cu(Ⅱ)ion is coordinated by one nitrogen atom from 4,4'-bpy and one nitrogen atom,three oxygen atoms from NTA3-.In the title complex,La(Ⅲ)ions and Cu(Ⅱ)ions are connected by the heterometallic bridging of NTA3-,constructing a two-dimensional network structure along the [110].And it is extended into an infinite three-dimensional network struc     

CRYSTAL STRUCTURE OF (NH_4)_(11)[Na(H_2O)_2P_4W_(14)O_(58)] ·12H_2O

<正> (NH4)11[Na(H2O)2P4W14O58)·12H2O, Mr = 4099. 39, triclinic, space group P1, a = 14. 376(2), b = 19.861(9), c=13. 010(3)(?) , α=104. 68(2), β=91. 37(1), γ= 104. 05(2)°, V = 3471. 1 (?)3, Z = 2, Dc=3. 922g/cm3, μ (MoKα) = 238. 274cm-1, F(000) = 3664, R = 0.0510, Rw = 0. 0665 for 9260 observed reflections with I> 3σ(I). The polyanion [Na(H2O)2P4W14O58]11- consists of two PW7O29 subunits anisostructurally, two linkage phosphorous atoms and one sodium ion with two water ligands as well. The geometries of tungsten atoms within these two subunits are almost the same as those in K12P4W14O58· 21H2O[2]. The four phosphorous atoms are in PO4 coordinations. The sodium ion locates nearly at the center of the polyanion, and is coordinated by two water molecules, five oxygen atoms of the anion and one phosphorous atom with Na-P = 3. 053(3) (?). Due to the presence of the sodium atom, the interactions between oxygen and tungsten atoms in the polyanion are somewhat weakened.     

CRYSTAL STRUCTURE OF [Sm(CCl_3COO)_3(H_2O)_2]·2H_2O

<正> Biaqua-trichloroacetate-samarium dihydrate, [Sm(CCl3COO)3(H2O)2]-2H2O, Mr=707.54, orthorhombic, space group Pnne, with a = 19.158(5), b = 22.176(4), c= 9.798(4)A, Z= 8, V= 4162.7A3.F{000)= 2696,λ(MoKα)=0.71069A, Dx = 2.258 g/cm3, final R=0.061. The title compound has non-molecular structural character, and its structural units Sm(μ-CCl3COO)s/2-(H2O>2 constitute 2-dinensional infinite chains of Sm(μ-CCl3COO)4Sm(μ-CCl3-COO)2Sm.The Sa(Ⅲ) atom in each unit is bound to two O atoms from aqua-molecules and six 0 atoms from six bridging CCl3COO groups (four of which are shared with the SB atom of another unit, two shared with the Sm atom of a third unit) forming a square antiprism.     

Synthesis,Crystal Structure and Fluorescent and Thermal Stability Properties of the Zinc(Ⅱ) Complex [Zn(C_(15)H_(11)O_3)_2(C_(12)H_8N_2)_2]·5H_2O

A new complex has been synthesized with o-methylbenzoyl-benzoic acid(HL) and 1,10-phenanthroline(phen) in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328(18), b = 17.7876(18), c = 19.998(2), β = 104.720(4)o, C54H48N4O11Zn, Mr = 994.33, V = 4690.2(9)3, Dc = 1.408 g/cm3, Z = 4, F(000) = 2072, μ(MoKα) = 0.59 mm-1, R = 0.0736 and wR = 0.2029. The crystal structure shows that the zinc ions are coordinated with two oxygen atoms from two HL molecules and four nitrogen atoms from two phen molecules, forming distorted octahedral coordination geometry. The fluorescent and thermal stability properties of the complex are studied. The result shows that it has one fluorescent emission band at around 412 nm. In addition, the complex is stable under 210 ℃.     

CRYSTAL AND MOLECULAR STRUCTURE OF MOLYBDENUM COM-PLEX MoO_2Cl_2(C_4H_3OCOOH)_2

<正> The crystal and molecular structure of the title compound was determined by single crystal X-ray diffraction method. The complex crystallizes in the mono-clinic space group P21/n with a = 10. 306 ( 3) , b = 10. 161 (2), c = 14. 798 ( 4) A . β= 108. 52(2)°, V= 1469. 4(6)A3,Z= 4. The structure was solved by direct methods. Least-squares refinement converged to a final value of R = 0. 043 and Rw= 0. 040 for 1237 reflections. The molybdenum (Ⅵ) ion is bonded to two chlorine atoms, two oxo atoms and two oxygen atoms from two monodentately and weakly coordinated carboxyl groups of molecules C4H3OCOOH, forming a octahedron. The Mo-O distances are in the range 1. 66 - 2. 39A ,the Mo-Cl distances fall in the range 2. 33-2. 34A.     

CRYSTAL STRUCTURE OF ORGANOLANTHANIDE [{Li(THF)_2}_2 (μ-Cl)_4(η~5-C_5H_5)Pr(THF)]

<正> The title complex crystallizes in the orthorhombic space group Pna21 with Mr = 570. 8, a = 16. 927(6), b = 18.942(7), c=10. 618(5)(?) and Z = 4. The structure was solved by Patterson and Fourier techniques and refined by block-diagonal least squares techniques to R = 0. 090 and Rw = 0. 093 for 1553 reflections with I>1. 5σ(I). The Pr3+ ion is bonded to five carbon atoms of cyclopentadi-enyl ring, four μ-chlorine atoms and one oxygen atom of THF in an octahedral geometry with the Pr-C distances in the range 2. 6.7 - 2. 79(?)(av. 2. 76(?)) , the Pr-Cl distances in the range 2. 81 - 2. 92(?) (av. 2. 86(?)) and the Pr -O distance of 2. 51 (?). Each Li+ ion is coordinated by two μ-chlorine atoms and two oxygen atoms from THF in a tetrahedral geometry with the Li-Cl distances in the range 2. 24 - 2. 61(?) (av. 2. 43(?)) and the Li -O distances in the range 1. 86-1. 94(?)(av. 1. 91(?)). The Pr atom and the two Li atoms are bridged asymmetrically by the chlorine atoms.     

TRINUCLEAR BASIC CARBOXYLATE COMPOUNDS OF TRANSITION METALS PART 1. SYNTHESIS AND CRYSTAL STRUCTURE OF {Fe_2MnO(EtCO_2)_5(H_2O)_4}·NO_3

<正> The title complex crystallizes in the tetragonal system,space guoup I 4 with α = b=22. 41(1), c=12. 920(3) A. Mr = 682. 06,V = 6488. 5A3,Z=8,Dc= 1. 396g/cm3,F(000) = 2808,final R=0. 098 for 2668 independent reflection with Ⅰ > 3σ( Ⅰ ). This complex was Shown to contain two Fe(Ⅲ ) and one Mn( Ⅱ ) at the apices of an approximately equilateral triangle with a μ3-O bridge. The Mn (Ⅱ)atom and one Fe (Ⅲ )atom are each octahedrally coordinated by six oxygen atoms,while the other Fe atom coordinated by five oxygen atoms to form a square pyramid. The μ3-O is in the centre of the Fe2Mn triangle with the Fe(1)-O, Fe(2)-O and Mn-O distances of 1. 89(1), 1. 90(1) ,and 1. 91(1) A ,respectively. The IR spectrum was also studied.     

Solvothermal Synthesis,Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)_2(2,2′-bipy)(H_2O)]·(H_2O)

One novel complex [Co(p-MBA)2(2,2′-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2′-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic,space group P1 with a=0.70479(14),b=1.1211(2),c=1.6718(3) nm,α=103.806(3),β=90.795(3),γ=104.207(3)o,V=1.2399(4) nm3,Mr=512.41,Dc=1.373 g/cm3,Z=2,F(000)=532,μ=0.733 mm-1,R= 0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2′-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Complex Cu(o-Methylbenzoic acid)_2(2,2′-bipy)·(H_2O)

The title complex (C26H24CuN2O5, Mr = 508.01) has been synthesized by o-me- thylbenzoic acid, 2,2′-bipyridine (bipy) and copper perchlorate in the mixed solvent of water and methanol. It crystallizes in orthorhombic, space group P212121 with a = 0.70814(10), b = 1.6953(3), c = 1.9539(3) nm, V = 2.3457(6) nm3, Dc = 1.439 g/cm3, Z = 4, μ = 0.971 mm-1, F(000) = 1052, R = 0.0432 and wR = 0.0860. The structural determination shows that the copper atom is coordinated by three oxygen atoms from two o-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The cyclic voltammetric behavior of the complex is also discussed.     

CRYSTAL STRUCTURE OF ERBIUM (HI) COMPLEX WITH 5-SUL-FOSALICYLIC ACID[Er (SO_3C_8H_3(OH)CO_2) (H_2O)_7] [Er (SO_3C_6H_3-(OH)CO_2)_2(H_2O)_6]·8H_2O

<正> [Er(SSA)(H2O)7][Er(SSA)2(H2O)6]·8H2O (H2SSA = 5-sul-fosalicylic acid), Mr=1361.3, monoclinic,P21/c, a = 21.459(7), b = 10.125(2), c = 22. 033(5)(?), β=109. 07(2)°, V = 4524(2)(?)3, Z = 4, D,= 1. 998g/cm3, μ (MoKa) = 40. 6cm-1, F(000)=2704, R = 0. 038 for 5805 observed reflections. The Er(Ⅲ) ions in-both complex cation and anion are coordinated by unidentate SSA ligand(s) and water molecules in a trigondodecahedral geometry. The coordination polyhedra are connected with each other by hydrogen bonds involving the uncoordinated carboxylato oxygen atoms and the coordinated water molecules. Stacking interactions between the phenyl rings further stabilize the structure.     

STRUCTURE OF PENTAAQUO PYROMEL DIZINE (Ⅱ)-DIHYDROUS [C_6H_2(COO)_4Zn_2(H_2O)_5]·2H_2O

Crystal and molecular structure of [C6H2(COO)4Zn2(H2O)5]·2H2O has been determined by X-ray diffraction technique, Mr = 507. 0,monoclinic,space group P21/n,a = 5. 925(1), 6 = 23. 613(9) ,c= 11. 790(5) A ,β= 96. 36 (3)°, V=1639. 3 (1. 0) A3,Z=4,DC = 2. 05g/cm3,λ=0. 71069 A,μ(MoKa) = 30. 9/cm-1,F(000) = 1024e. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R value of 0. 055(Re = 0. 059)for 1557(I>3σ(I))reflections. Both atoms Zn(1) and Zn(2) are bridged by the Z,E-type of the car-boxyl group, in addition, Zn (1) is monodentate-bonded to the three remaining carboxyl and Zn(2) is bonded to five water molecules. The crystal structure shows a 2-dimensional polymeric network along(010)face. The Zn(l) -O distances are in the range of 1. 94~ 2. 01 A (average 1. 98 A ). The Zn(2) -O distances are in the range of 2. 06~2. 21 A (average 2. 12A).     

CRYSTAL STRUCTURE OF GdCl_3(DIMETHOXYETHANK)_2

<正> C8H2oCl3GdO4,Mr=443.80,monoclinic, space group P21/c, a=11.442 (3),b= 8.849(2), c= 15.575(5)A,β=104.8l(2)° ,V=1521.9(7)A3,Z= 4, DC = 1.94 g/cm3,λ(MoKα) =0.71069A,F(000)=860. The structure was solved by Patterson and Fourier techniques and refined by least-squares nethod to a final conventional lvalue of 0.051 (Rw=0.054). The central ion Gd(III) is bonded to three chlorine atoms and four oxygen atoms froa two dimethoxye-thane molecules to form a distorted pentagonal bipyramid. The Qd-Cl distances are in the range of 2.460-2.628A (average 2.571A). The Gd-O distances are in the range of 2.408-2.493A (average 2.458A).     

Synthesis,Crystal Structure and Thermal Stability of Complex [Cu（C_（14）H_（10）O_4）（C_（12）H_8N_2）_2]·2H_2O

The title complex has been synthesized with 2,2'-biphenyl dicarboxylic acid and 1,10-phenanthroline(phen)in the solvent mixture of water and methanol.It crystallizes(C38H28CuN4O6,Mr = 700.1)in triclinic,space group P1 with a = 1.0868(2),b = 1.2175(2),c = 1.6206(3)nm,α = 110.161(2),β = 102.605(3),γ = 93.667(2)o,V = 1941.6(6)nm3,Dc = 1.198 g/cm3,Z = 2,F(000)= 722,R = 0.0558 and wR = 0.1208.The crystal structure shows that the copper atom is coordinated with one oxygen atom from 2,2'-bphenyl dicarboxylic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules,forming a distorted square-pyramidal coordination.The TG analysis shows that the title complex is stable under 160.0 ℃.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_3 (μ-C_2H_5COO)(dtp)_3Py

<正> C20H40Mo3NO8P3S10, Mr=1123.93, triclinic, P1,a=12.972(3), b=13.763(2), c= 14.515(7)A,α=66.22(3),β=101.72(3),γ=118.90(1)° , V= 2076(2) A3, Z=2,Dc=1.798 g.cm-3, MoKa radiation, final R= 0.040 and Rw=0.056 for 5645 observed reflections. The molecule contains three Mo atoms arranged in a triangle with one capping-S atom, three (μ-S) atoms, one (μ-EtCOO) ligand, one chelate ligand dtp on each Mo atom, and one terminal Py on atom Mo(1). The coordination of Mo atoms is of distorted octahedron.     

STUDY ON SYNTHESIS, STRUCTURE AND COMPLEXATION CHARACTERISTIC OF UO_2Cl_4(DCH 18C6·H_3O)_2*

The title compound was synthesized by extracting nranylchloride in HC1 system using dicyclohexyl-18-crown-6 as extraction agent. The absorption peaks 1090 cm~(-1) and 912 cm~(-1) in IR spectrum result from frequence red-shift of anti-symmetric stretch vibration of C—O—C of crown ring and [OUO] group, respectively.X-ray diffraction analysis results in its crystallographic parameters: triclinic system, space group P; a=10.183(3), b=10.606(3), c=12.850(6), α=72.09(3), β=85.97(4), γ=86.14(2)°, V=1315.7, z=1. The structure was solved by heavy atom method. Structure refinements converged to final R=0.062, R_w=0.061. U atom is situated on the symmetry center and coordinated by four chlorine atoms and two oxygen atoms to form a square bipyramid coordination polyhedron. The H_3O~+ group is embedded in the crown ring and connected with three crown oxygen atoms via hydrogen bonds.     

Synthesis and Crystal Structure of [Zn(FcCOO)_2(2,2'-bipy)(H_2O)]_2·H_2O

A novel complex [Zn(FcCOO)2(2,2'-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) A, α = 90, β = 97.7420(10), γ = 90o, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) A3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I > 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

CRYSTAL AND MOLECULAR STRUCTURE OF [K(C_(14)H_(20)O_5)_2]_2[Co(NCS)_4]

<正> The title complex (Mr= 1442.6) crystallizes in the monoclinic, space group PC, with a =14.515(7),b =15.773(5), c =16.287(11)51,β=95.13(5)°,Z=2,V=3713.8A3,Dc=1.29 g·cm-3. The structure was solved by Patterson method and the final R=0.068. The potassium atom in the cation lies between the two planes of the oxygen atoms from two benzo-15-crown-5 molecules.     

Synthesis and Structure Study of Molybdenum Complex Mo[o-NHCOCH_3-m-NO_2C_6H_3COOH]_2_O2Cl_2·PhCl

The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.