Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

A new lanthanumⅢ-ironⅢ complex [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4]·H2O 1 (DMSO=dimethylsulfoxide) has been prepared by a facile approach,ball-milling method,and characterized by X-ray diffraction. The crystal belongs to monoclinic,space group P21/n with a= 9.7125(3),b=21.5336(7),c=14.3804(5),β=93.242(3)o,C16H34FeLaN6O7S5,Mr=777.55,V =3002.8(2)3,Z=4,Dc=1.720 g/cm3,S=1.053,μ(MoKα)=2.278 mm–1,F(000)=1564,R= 0.0490 and wR=0.1270. The crystal structure analysis of 1 reveals a slightly distorted square-antiprism eightfold-coordinated La(Ⅲ) ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4] species are held together via hydrogen bonds to form a three-dimensional framework.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) (A), β = 97.531(4)°V = 4161.0(15)(A)3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O-H…N and O-H…O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N C5H5)3] ions are bound by electrostatic force to form an ionic compound.Keywords: N-benzyl-pyridine, ferricyanic anion, crystal structure, supramolecular, ionic compound.     

Synthesis and Crystal Structure of a New Lanthanum(Ⅲ) 4-Cyanobenzoate Complex

A new dinuclear La(Ⅲ) complex [La2(4-cba)4[H(4-cba)2]2(phen)2(H2O)4] (4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline) 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single- crystal X-ray diffraction. Crystallographic data: C88H58La2N12O20, Mr = 1881.28, triclinic P(1), a = 7.518(3), b = 17.033(6), c = 17.551(6)(A), α = 115.333(4), β = 92.9910(10), γ = 99.366(5)°, V = 1985.3(12) (A)3, Z = 1, Dc = 1.574 g/cm3, F(000) = 944 μ = 1.145 mm-1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ ＞2σ(Ⅰ). In 1, two nine-coordinated La(Ⅲ) ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La(Ⅲ) ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-πstacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln(DMSO)2(H2O)(μ-CN)4Fe(CN)2](Ln= Ce and Eu, DMSO= Dimethylsulfoxide) with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln(DMSO)2(H2O)(μ-CN)4Fe(CN)2] (Ln = Ce 1, Eu 2) have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1: C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852(4), b = 10.729(5), c = 11.181(5) (A), β = 96.992(8)°, V = 935.0(7) A3, Z = 2, Dc = 1.870 g/cm3, μ = 3.421 mm-1, F(000) = 512, R = 0.0363 and wR = 0.0971; and those for 2: C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P2/n, a = 7.739(5), b = 10.668(7), c = 11.008(7) A, β = 96.943(3)°, V = 902.1(11) A3, Z = 2, Dc = 1.981 g/cm3, μ= 4.499 mm-1, F(000) = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe(Ⅲ) ion is in a nearly regular octahedral environment. The title complexes can be described as two-dimensional (2-D) stair-like structures, which are further connected by hydrogen bonds to form three-dimensional (3-D) frameworks.     

Synthesis and Crystal Structure of a Novel Bimetallic Porphyrin Complex Salt {[MnTPP(CH_3OH)_2]_3Fe(CN)_6}·13H_2O

A novel bimetallic porphyrin complex salt, {[MnTPP(CH3OH)2]3Fe(CN)6}13H2O (TPP = tetraphenylporphyrin), has been synthesized and structurally characterized by X-ray diffraction analysis. The crystal is of trigonal, space group R-3 with a = b = 31.0618(10), c = 11.8366(8) A, Z = 3, V = 9890.3(8) A3, C144H134FeMn3N18O19, Mr = 2641.36, Dc = 1.330 g/cm3, μ(MoΚα) = 0.463 mm-1, F(000) = 4131, R = 0.0525 and wR = 0.1382 for 3045 observed reflections (I > 2σ(I)). The title complex is composed of one [Fe(CN)6]3- anion, three [MnTPP(CH3OH)2]+ cations and thirteen water molecules, which are connected by multiform hydrogen bonds leading to a 3D supramolecular network structure.     

Synthesis and Crystal Structure of a Bimetallic Cyanide-bridged Complex Derived from Manganese(Ⅲ) Schiff-base Complex and Pentacyanidonitrosylferrate(Ⅱ) Building Blocks

A new cyanide-bridged bimetallic assembly [Mn(3-meosalpn)(H2O)]2[Fe(CN)5NO](1) was obtained by the reaction of [Fe(CN)5NO]2-with [Mn(3-meosalpn)]+,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992(5),b = 13.274(6),c = 14.644(6) ,β = 115.198(4)o,V = 2285.2(16)3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F(000) = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections(Ⅰ 2σ(Ⅰ)).X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn(3-meosalpn)(H2O)]+ cations are linked by the central [Fe(CN)5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn(3-meo-salpn)(H2O)]+ cations and [Fe(CN)5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6(phCH_2NC_5H_5)3]·(H_2O)_4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) , β = 97.531(4)o, V = 4161.0(15) A3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N+C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O–H···N and O–H···O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N+C5H5)3] ions are bound by electrostatic force to form an ionic compound.     

Crystal Structure and Binding Properties of a New Molecular Clip Based on Diethoxycarbonyl Glycoluril： C42H36N6O6

A new molecular clip based on diethoxycarbonyl glycoluril 5: C42H36N6O6 , has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbca with a=12.7639(5), b=16.9727(7),c=34.2069(14) , V=7410.5(5)3 , Z=8, Dc=1.292 g/cm3 , μ(MoKα)=0.088 mm-1 , F(000)=3024, the final R=0.0655 and wR=0.1566 for 5123 observed reflections with I>2σ(I). The crystal structural analysis shows that intermolecular c-H…O and C-H…N hydrogen bonds stabilized the whole crystal structure. The binding study by fluorescence spectroscope titration showed that the title molecule can selectively recognize Fe3+ with fluorescence quenching.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Synethesis and Crystal Structure of Bi(ethylenediamine)copper Tetracyanonickelate(Ⅱ)

The crystal structure of the title compound C8H16CuN8Ni has been determined by single crystal X-ray diffraction. The crystal is triclinic with space group P1, a=6.494(3), b=7.270(4), c=7.936(5) .A, α=106.67(3), β=91.33(4), γ=106. 80(6)°, V=341. 3(3) A3, Z==1, Mr=346. 54, F(000)=177, μ=2. 933mm-1, Dc= 1. 686 Mg/m3. The final R factor is 0. 0603 for 1214 unique ob24- served reflections [I≥2σ(I)]. The structure consists of [Cu(en)2]2+ (eh=ethylenedi amine) cations and [Ni(CN)4]2- anions linked together by two of the CN groups (the remaining two act as unidentate ligands) to form infinite chains, in the chain, the hy between the interchains also exist, with distances of 3. 160 and 3. 124 A , so it forms a three-dimensional structure of the title compound.     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

Synthesis and Structure of Dibenzoyl-bissemicarbazone Neodymium(Ⅲ) Perchlorate

A new Schiff base Dibenzoyl-bissemicarbazone C15H16N6O2(L) and its complex with neodymium(Ⅲ ) perchlorate [NdL2(H2O)2](ClO4)3 were synthesized. The crystal and molecular structure of the title complex were determined by single crystal X-ray diffraction. The crystal is monoclinic and conforms to space group P. with cell constants a=10. 893(2) A, b= 12. 118(3) A , c=22. 494(5) A , β=89. 86(3)% V = 2969.19A3. The final standard deviation R=0. 0919. In the complex Nd is coordinated by four nitrogen and six oxygen atoms, of which four nitrogen and four oxygen atoms are provided by two neutral ligands L, and the other two oxygen atoms are provided by two water molecules, forming a ten-coordinated complex cation, which the perchlorate groups exist in the outer sphere. The coordination polyhedron takes a bicapped anti-square prism arrangement. That the average bond length of Nd-N is 2. 735 A indicates that the coordination of N in groups to Nd( Ⅲ ) is very weak.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions:[NH3(CH2)4NH3]6[Co4(HzO)2(B-α-GeW9034)2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate,[NH3(CH2)4NH3]6 [Co4(H2O)2(B-α-GeW9O34)2]·7H2O 1,was hydrothermally synthesized and characterized by IR spectra and single-crystal X-ray diffraction.The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system,space group P21/c with a=16.6073(6),b=15.3333(5),C=19.9869(7)(A),β=103.41(1)°,Mr=5481.38,V=4950.8(3)(A)3,Z=2,Dc=3.677 g/cm3,F(000)=4900,μ(MoKα)=22.165 mm-1,GOOF=1.005,the final R=0.0228 and wR=0.0527.The crystal structure indicates that the[Co4(H2O)2(B-α-GeW9O34)2]12-polyoxoanion contains two trivacant Keggin[B-α-GeW9O34]10-fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement(C2h symmetry)leading to a sandwich-type structure.     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound [Et4N ] 2 [Mo2 (CO) 8 (SC6H4-OCH3-p) 2]

Reaction of Mo(CO)6 with p-H3CO-C6H4SNa and Et4NCl · H2O in CH3CN afforded a dinuclear molybdenum(0) compound [Et4N]2[Mo2 (CO)8 (SC6H4-OCH3-p)2] (1). The crystal structure was determined by X-ray diffraction. The crystallographic data: C38H54Mo2N2O10S2, Mr = 954.87, triclinic, P-1, a = 11.348 (7), b =11.616(5), c=10.065(7) A, a=113.86(4), β=111.39(5), γ=91.92(5)°, V=1104.0(1) A3, Z=1, Dc=1.44 g/cm3, F(000)=492, μ=7.0cm-1, Final R=0. 046 and Rw=0. 049 for 2657 reflections with I＞3. Oσ(I). The X-ray structure analysis revealed that the Mo2S2 core of 1 is planar. The geometry around each Mo atom is a distorted octahedron, the two octahedrons form an edge-sharing bioctahedron. The bond. In addition, the 95Mo NMR chemical shift of 1 is discussed.     

Synthesis and Structure Characterization of Aqua-（μ2-carbonato-O,O′）-（2,2′-bipyridyl）-copper（Ⅱ） Dihydrate

Under hydrothermal conditions the reaction of cis-aconitic acid with Cu2(OH)2CO3 and bipy (bipy = 2,2'-bipy) in H2O/DMF (3:2) afforded a neutral mononuclear compound [Cu- (bipy)((2-CO3)(H2O)](2H2O, which has been structurally characterized by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group Pī with a = 8.3950(5), b = 8.7974(5), c = 9.4496(3)（A。）, α = 98.270(3), β = 93.014(3), γ = 100.068(3)°, V = 677.83(6) （A。）3, Dc = 1.635 g/cm3, Z = 2, C11H14CuN2O6, Mr = 333.78, μ = 1.637 mm－1, λ(MoKα) = 0.71073 （A。）, F(000) = 342, the final R = 0.0616 and wR = 0.1273 for 1621 observed reflections with I > 2σ(I). The structure of the complex contains a distorted square pyramidal core with a bipy, a carbonate anion and a water molecule coordinating to a CuⅡ atom. The dihedral angle between the two planes composed of N(1)N(2)Cu(1) and O(1)O(3)Cu(1) is 21.73(8)°. The intermolecular hydrogen bonds (O…O) are observed in the crystal structure.     

Synthesis and Crystal Structure of a Three-dimensional Manganese(II) Complex (tataH)_2[Mn(pydc)_2]·4H_2O (tata = 2,4,6-Triamino-1,3,5-triazine, pydcH_2 = Pyridine-2,6-dicarboxylic Acid)

A manganese(II) complex (tataH)2[Mn(pydc)2]·4H2O (C20H28MnN14O12, Mr = 711.50, tata = 2,4,6-triamino-1,3,5-triazine, pydcH2 = pyridine-2,6-dicarboxylic acid) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1, with a = 9.9847(3), b = 10.9813(3), c = 15.2616(5) , α = 101.5310(10), β = 90.2610(10), γ = 116.4600(10)°, V = 1459.44(8) 3, Z = 2, Dc = 1.619 g/cm3, μ = 0.539 mm–1, F(000) = 734, the final R = 0.0292 and wR = 0.0745. In the crystal the MnII atom is six-coordinated by four carbonyl oxygen atoms and two pyridine nitrogen atoms from two tridentate pydc ligands to furnish a distorted octahedral geometry. The complex shows the A…D…D’…A’ H-bonded tetramer. The molecules are packed in a three-dimensional framework structure by the combination of O–H…O, N–H…O and N–H…N hydrogen bonds between (tataH)+, [Mn(pydc)2]2– and crystal water.     

Synthesis and Crystal Structure of a 2D Cu Framework Constructed from Dinuclear Building Units

A novel 2D Cu coordination polymer [Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O]n(2, H2 pca = pyrazole-3-carboxylic acid) has been prepared by dissolving a dinuclear Cu complex Cu2(py)3(pca)2(H2O)·(H2O)(1) in DMSO solution and structurally characterized by X-ray diffraction. The polymer crystallizes in space group P1 with a = 9.538(3), b = 9.714(3), c = 10.765(3) A, α = 86.492(6), β = 84.007(7), γ = 82.592(6)o, Mr = 1079.04, V = 982.4(5) A3, Z = 1, Dc = 1.824 g/cm3, μ = 2.425 mm-1 and F(000) = 548. The final refinement gave R = 0.0785 and w R = 0.1940 for 2787 reflections with I 2σ(I). The structure of 2 consists of Cu4(pca)4(H2O)2(DMSO)2·2DMSO·2H2O units, which can be viewed as two dinuclear subunits of Cu2(pca)2(H2O)2 and Cu2(pca)2(DMSO)2 connected to each other alternately, with solvent DMSO and H2 O molecules around. The framework features a grid-like topology, with the walls of the grids composed of Cu4(pca)4 units, and the coordinated solvent molecules trapped in the grids.     

Syntheses,Crystal Structures and Magnetic Studies of Heterobimetallates Based on Paramagnetic Ruthenium(Ⅲ) Building Block [Ru~Ⅲ(salchda)(CN)_2]

The syntheses, crystal structures and magnetic properties of two cyano-bridged heterobimetallic compounds prepared from a paramagnetic Ru Ⅲ building block, transK[RuI II(salchda)(CN)_2](1, salchda = N,N?-bis(salicylidene)-o-cyclohexylenediamine), are described.1 reacts with hydrated CoCl_2 and [Mn Ⅲ(salchda)(Cl)(H_2O)] in MeOH to produce a trinuclear compound {[Ru~Ⅲ(salchda)(CN)]_2(μ-CN)_2[Co(MeOH)_4]?4MeOH}_n(2) and a dinuclear{[Ru~Ⅲ(salchda)(CN)](μ-CN)[Mn~Ⅲ(salchda)(MeOH)]?2MeOH}n(3), respectively. Both compounds exhibit intramolecular ferromagnetic coupling between Ru~Ⅲ and 3-d metal centers via the cyano bridge and intermolecular antiferromagnetic coupling. Moreover, 2 exhibits antiferromagnetic ordering below 3.4 K.     

The preparation, structure and spectra properties of dual μ3-oxo bridged tetranuclear complexes containing the [CrnFe4-nO2]8+ core(n=0,2,4)

The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on different     

A Novel Dimer--Heteropolytungstate with a Vanadium Atom as the Centre--Synthesis and Structural Characterization of (H3O)4[VW12O40Na(H2O)4]2

A novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,βA novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,β=93.17(3)°,γ=117.47(3)°,V=2.2106(8) nm3,Z=1,Dc=4.552 g.cm-3,λ(Mo Kα)=0.071073 nm,μ=31.402 mm-1,F(000)=2648,R=0.0780.The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm×0.7785 nm.