Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

Synthesis and Structural Characterization of Bis(2,2'-bpy)bis(azide)cobalt(III) nitrate dihydrate

The title complex [CoIII(2, 2?-bpy)2(N3)2]@NO3@2H2O was obtained by an auto-oxidization reaction of cobalt nitrate with 2, 2?-bpy and sodium azide in aqueous solution at room temperature, and violet single crystals were prepared in ethanol solution. The structure was determined by X-ray crystallography. The crystal is of triclinic, space group P ī with a = 8.285(4), b = 11.990(8), c = 12.596(7) ?, ( = 86.630(3), ( = 86.280(5), ( = 71.130(10)°, C20H20CoN11O5, Mr = 553.40, Z = 2, V = 1180.6(12) ?3, F(000) = 568, Dc = 1.557 g/cm3, ( = 0.784 mm-1, R = 0.0403 and wR = 0.1008. The title complex consists of a [CoⅢ(2, 2?-bpy)2(N3)2]+ cation, a NO3- anion and two lattice water molecules. The center CoⅢ ion coordinated by two chelating 2, 2?-bpy ligands and two terminal azide groups with a CoN6 coordination environment exhibits a distorted octahedral geometry.     

镧系四元混合配体配合物[Ce(CH2ClCOO)2(NO3)(phen)(H2O)]2的晶体结构、芳环堆积效应和2D氢键网络

The quaternary complex, ［Ce(CH2ClCOO)2(NO3)(phen)(H2O)］2, was synthesized. Interestedly, the title compound is a dimer comparing with the 1D polymer ［La(CH2ClCOO)2(NO3)(phen)*(H2O)］n and powder compound ［Nd(CH2ClCOO)2(NO3)(phen)］. In the title compound there is a monodentate NO-3, which is a first example in the all synthesized quaternary mixed anion complexes, and the NO-3 extended the complex into a 2D network with water from other molecules by inter-molecular hydrogen bonds. The intermolecular hydrogen bonds lead to the weaker Ce—O(COO), Ce—O(NO3) and Ce—N bonds comparing with other quaternary mixed anion complexes of cerium. Also the stacking effect, which makes the compound more stable in the situation of weaker Ce—O and Ce—N bonds, was first found in the series compounds.     

SYNTHESIS AND STRUCTURE OF[Et_4N]_3[FE_3(SPh)_3Br_3Cl_3]

<正> The title compound was synthesized and its structure solved. The formula is [Et4N]3[Fe3(SPh)3Br3Cl3]. M=1231.95, monoclinic, space group C2/c, a=24.569(4), b=13.504(2), c=18.348.(3)A, β=110.78(1)°, V=5691(3)A3, Z=4, Dm= 1.41, Dc=1.44-g/cm3. The flat structure of the anion has. a planar [Fe3S3] ring and three phenyl groups. Statistical distribution of chlorine and bromine atoms on two sides of the [Fe3S3] plane results in a C2 symmetry of the anion.     

Synthesis and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate （phenH）_2[La（NO_3）_5（phen）]·CH_3OH

Lanthanum complex (phenH)2[La(NO3)5(phen)]·CH3OH (1, phen=phenanthroline) was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040(3), b=10.7091(1), c=19.0771(2), β=102.090(1)°, V=4056.07(8)3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F(000)=2056, the final R=0.0346 and wR=0.0793 for 9981 (Rint=0.0358) independent reflections. The mononuclear complex 1 consists of four parts: two phenH+ cations formed by the protonation of phen, one complex anion [La(NO3)5(phen)]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La(III) ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines (phenH+) acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer structure.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

The Molybdenum（0）Complex [Et4N]2[Mo2（CO）6（pys）2]（pys=Pyrindine—2—thiol

The title compound tetraethylammonium hexacarbonylbis(μ-pyridine-2-thiolato-S∶S) dimolybdenum [Et4N]2[Mo2(CO)6(pys)2] crystallizes in the monoclinic, space group, P21/c with a=13.217(2), b=21.648(2), c=27.193(6)(), β=82.52(2)°, V=7714.6()3, Z=8, Mr=840.77, Dc=1.45 g/cm3, μ=7.8 cm-1, R=0.038 and Rw=0.040 for 6082 reflections with I≥3σ(I). X-ray crystal structure study reveals that the asymmetric unit of the title compound is comprised of two independent formulations of the molecular formula. Each dianion has approximate C2 symmetry and the dimetallic Mo2S2 core adopts a "butterfly" conformation with a dihedral angle between the halves of 139.3(1)° for the first independent anion and 142.8(1)° for the second one. The two pyridine rings lie on the same side of the molecule in a cis arrangement and the Mo...Mo separations are 3.76(1) and 3.838(1)().     

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound (4,4'-bipyH)4[SiW12O40](4,4'-bipy) (4,4'-bipy = 4,4'-bipyridine) was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767(12), b = 21.1879(11), c = 15.6942(8) , β = 97.068(3)°, V = 7351.3(7) 3, C50H44N10O40SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F(000) = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiW12O40]4- anion, one 4,4'-bipy and four protonated (4,4'-bipyH)+ cations. The [SiW12O40]4- anion and protonated 4,4'-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.     

STUDY ON STRUCTURE OF SULFUR-BRIDGED TRANSITION METAL CLUSTERS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3 [Mo_3(μ_3-S)_2 (μ_2-Cl)_3Cl_6]

The compound (C_5H_7S_2)_3[Mo_3 (μ_3--S)_2 (μ_2--Cl)_3 Cl_6] forms dark black octahedralcrystals with the following crystallographic parameters: a=22.885(10)A, c=25.407(7)A. Thespace group is I4_1/α, Z=16, ρ_(obs.)=2.073g/cm~3, ρ_(calc.)=2.126g/cm~3. The 1621 independentreflections with I≥3σ were collected on a CAD-4 four-circle diffractometer by means of MoK_αradiation. The structure was solved by three-dimensional Patterson synthesis and refined byleast squares technique to a final discrepancy factor of R=0.056. The results of our investiga-tion reveal that the molecule consists of a trinuclear Mo cluster anion and three planar mono-cations.surrounding the cluster anion. As the core of the anion the triad of Mo atoms, possessing anequilateral triangular configuration, is linked by two μ3--S bridging atoms and three μ2--Clatoms. Besides, two terminal Cl atoms are attached to each Mo atom to form an octahedralconfiguration. The diamagnetism and the short Mo-Mo distances (2.556 A, 2.641 A, 2.653 A)clearly indicate the existence of Mo-Mo bonds. The anion as a whole has an idealized D_(3h) localsymmetry.     

The Molybdenum(0) Complex [Et4N]2[Mo2(CO)6(pys)2](pys=Pyridine-2-thiolato)

The title compound tetraethylammonium hexacarbonylbis(μ-pyridine-2-thiolato-S∶S) dimolybdenum [Et4N]2[Mo2(CO)6(pys)2] crystallizes in the monoclinic, space group, P21/c with a=13.217(2), b=21.648(2), c=27.193(6)(), β=82.52(2)°, V=7714.6()3, Z=8, Mr=840.77, Dc=1.45 g/cm3, μ=7.8 cm-1, R=0.038 and Rw=0.040 for 6082 reflections with I≥3σ(I). X-ray crystal structure study reveals that the asymmetric unit of the title compound is comprised of two independent formulations of the molecular formula. Each dianion has approximate C2 symmetry and the dimetallic Mo2S2 core adopts a "butterfly" conformation with a dihedral angle between the halves of 139.3(1)° for the first independent anion and 142.8(1)° for the second one. The two pyridine rings lie on the same side of the molecule in a cis arrangement and the Mo...Mo separations are 3.76(1) and 3.838(1)().     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Synthesis and Crystal Structure of Salicylyl-4-phenyl Thiosemicarbazide Lead with a Two-dimensional Network

A two-dimensional lead complex, [Pb(C14N3O2H12S)(NO3)]n·nH2O, was prepared by the reaction of salicylyl-4-phenyl thiosemicarbazide and lead nitrate. The compound (C14H13N4O6PbS, Mr=572.53) crystallizes in the monoclinic space group P21/c with a=11.2984(2), b=15.6628(7), c=11.1118(2), β= 113.564(2)n, V=1802.43(10)3, Dc=2.110 g/cm3, Z=4, μ(MoKα)= 9.515 mm·1, F(000)=1084, the final R=0.0394 and wR=0.0701 for 2552 observed reflections with I > 2σ(I). The Pb(II) ion displays a distorted octahedron in which the hypothesized stereochemically active lone pair occupies the apex. The compound exhibits a two-dimensional network structure formed by the zigzag one-dimensional chains joined by two μ-O of two nitrate groups in overlapping. A large ring exists in the two-dimensional layers. The TGA of the title compound has been studied.     

Synthesis and Crystal Structure of a One-dimensional Azido-bridged Manganese (II) Compound [Mn(N_3)_2(H_2O)_3·C_6H_(12)N_4]_n

1 INTRODUCTION The azide anion is a good bridging ligand for di- valent metal ions to form discrete, one-dimensional, two-dimensional or three-dimensional complexes. In recent years, these complexes have drawn consider- able attentions for their interesting magnetic charace- ristics which attribute to the efficient magnetic coup- ling ability of the azido bridges[1]. When the azide anion acts as a bridging ligand, two typical modes are adopted: end-to-end (EE, μ1, 3) or end-on (EO, μ1…     

Solvothermal Synthesis and Structure Studies of a Mixed-valence Oxochloromolybdenum Complex

Emerald green crystals of a new mixed-valence oxochloromolybdenum complex,Mo(OH)2(2,2′-bipy)Cl2.[MoO(2,2′-bipy)Cl3]2, were obtained in an attempt to synthesize the Mo-S cluster compounds under solvothermal conditions. The title compound was characterized by EPR and X-ray single-crystal diffraction techniques. Crystallographic data: orthorhombic, space group Fdd2, a = 12.684(1), b = 21.518(2), c = 29.096(3)A, Mr = 1103.97, V= 7941(1)A^3, Z= 8, Dc =1.843 g/cm^3,μ= 1.514 mm^-1, F(000) = 4304, R = 0.0654 and wR = 0.1544 for 1944 observed reflections with 1 ≥/ 2σ(I). The compound consists of two different neutral molecules, Mo^IV-(OH)2(2,2′-bipy)Cl2 and MoVO(2,2′-bipy)Cl3. Both Mo^IV and Mo^V ions are in a distorted octahedral environment. The Mo(1)^IV atom is surrounded by two Cl^- ions and two O atoms from OH^- and two N atoms from a 2,2′-bipy ligand. The Mo(2) atom is surrounded by three Cl^- ions, one O^2- anion and two N atoms from another 2,2“-bipy ligand. The bipyridine occupies two cis-equatorial sites, while the Cl^- ions are located at the axial and equatorial positions.     

Synthesis, Crystal Structure and Characterization of α-（1-Benzimidazolyl） -hypnone Cobalt（Ⅱ） Complex： [CoCl （ C7H5N2CH2COPh）4] Br

The crystal structure of [CoCl ( C7H5N2CH2COPh)4] Br has been determined by means of X-ray crystallography. The molecular structure consists of a discrete [CoCl ( C7H5N2CH2COPh)4] ^ cation and one Br^- anion, in the [CoCl ( C7H5N2CH2COPh)4]^ cation, the coordination geometry of the central Co atom is square-pyramidal with four tertiary N atoms of benzimidazole from four α-( benzimidazol-1-yl) -hypnone ligands in the basal position and one chloride anion in the apical position. In the solid state, [CoCl ( C7H5N2CH2COPh)4]^ and Br^- anion possess intermolecular and intramolecular interactions, which stabilize the crystal structure. The characterization of the title compound were also carried out by using elemeutal analysis, FTIR, UV spectrometries and TG-DSC.     

Synthesis, crystal structure and thermal analysis of tetraiodo-4, 4’-bi-1, 2, 4-triazole

Tetraiodo-4,4’-bi-1,2,4-triazole(1)was synthesized from a reaction of iodine monochloride with 4,4’-bi-1,2,4-triazole(2),which was prepared by a transamination reaction between 4-amine-1,2,4-triazole and N,N-dimethylformamide azine dihydrochloride(3)obtained via a Vilsmeier reaction.The title compound was extensively characterized by melting point,elemental analysis,IR,HRMS and single crystal X-ray diffraction.The single crystal X-ray structural analysis reveals that compound 1 exhibits a stable conformation with the two triazole rings being perpendicular to minimize three-dimensional steric hindrance and stacking through aromatic π...π packing interactions between molecules.The thermal analysis from TGA and DSC indicates that compound 1 decomposes at 275.40℃ and 338.35℃,respectively.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A MOLYBDENUM-COPPER-SULFUR CLUSTER COMPLEX WITH DITHIOBENZOATE LIGAND [Bu_4N]_2[MoCu_2S_4(C_6H_5CS_2)_2]

<正> The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021 (6), b = 17.045(8), c=17. 136(7)(?) , α=110.05(3), β=108.64(4), γ=103.87 (4)°, V = 2873(3)(?)3, Dc=1. 321gcm-3, Z = 2. The structure was refined to R = 0. 065 for .4783 reflections. The anion of the title compound can be described as a MoS42- tetrahedron coordinated by two [Cu(C6H5CS2)] units with the three metal atoms lying on a line. The coordination number of each Cu atom is three.     

STUDY ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF THE TWO TRINUCLEAR MOLYBDENUM CLUSTERS(C_5H_7S_2)[Mo_3(μ_3-O )(μ-X)_3(μ-OAc)_3Cl_3](X=Cl,Br)

The crystal structure of two isomorphic cluster compounds with formula (C_5H_7S_2)-[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (X=Cl for compound (Ⅰ) and compound (Ⅱ)) has been investigated by X-ray diffraction method. The parameters of two crystals are: a=10.423(1),b=17.095(4), c=14.062(7), β=97.54(4)(°); Dc=2.20gcm~(-3), D_o=2.17g cm~(-3) for compound (Ⅰ). and a=10.511(3), b=11.213(2), c=14.053(3), β=96.12(2)(°); D_c=2.52g cm~(-3), D_o=2.53gcm~(-3) for compound (Ⅱ). The space groups are P2_1/C. Z=4. The 2621 and 2548 independent reflections with I>3σ(I) were collected on a CAD-4 four-circle diffractometer by means of MoKα radiation. The crystal structures were solved by heavy atom method and refined by full-matrix least-squares technique to a final discrepancy factors of R=0.061 and 0.051 respectively. The results of investigation show that the molecule consists of the cation (C_5H_7S_2)+ and the trinuclear Mo cluster anion, the configuration of which is similar to that of (Et_4N)_2[Mo_3(μ_3-O)(μ     

CRYSTAL STRUCTURE OF 2, 4-DITHIONE-3-AMINO-1, 3, 2-OX-AZAPHOSPHORINEBENZO-2-THIONO PYRIDINIUM

<正> The structure of title compound [C7H6N2OPS3]-·[HNC5H5]+ was determined by x-ray diffraction. It belongs to monoclinic system with space group P21/a, a = 16.745(2), b= 8.563(2), c=21. 050(5)(?), β=93.32(1)°, V= 3013. 6(?)3, Z = 8, Mr = 341. 4, F (000) = 1536, Dc=1. 504 g. cm-3,μ= 53. 0 cm-1. The crystal is composed of discrete cations C5H5NH+ and anions CrH6N2OPS3-. There are two pairs of the cations and the anions in each asymmetric unit. The stability of the anion is increased by the formation of (d-p)π bonding involving the 3d orbital of the P atom and the lone electron pairs of the S atoms.     

Synthesis and Crystal Structure of 1D Cd-amine Coordination Polymer and Its Luminescent Properties

A novel one dimension（1D） cadmium coordination polymer {[Cd（mpda）3]·2（NO3）}n（1） was synthesized via refluxing a mixture of tetradentate Schiff base ligand N,N＇-bis（2-pyridinylethylidene）phenylene-1,3-diamine（L） and Cd（NO3）2 in acetonitrile, whose structure was characterized by means of single crystal X-ray diffraction, FTIR spectroscopy, elemental analysis and proton nuclear magnetic resonance（1H NMR）. Center metal Cd（II） ion is six-coordinated by six nitrogen atoms from six different m-phenylenediamine（mpda）, giving rise to a [CdN6] octahe- dral coordination environment. The two adjacent cadmium centers are linked by three mpda molecules leading to the construction of 1D chain structure. The crystal structure is stabilized by N-H…O hydrogen bonds to form three-dimension supramolecule. Compound 1 exhibits intense yellow luminescence in solid state at 298 K（λem=554 nm）, which shows a blue shift at 77 K（ca. 147 nm）. Additionally, fluorescence characteristics of compound 1 were investigated in different solvents（polarity： DMSO〉CH3CN〉CH3OH〉CHC13〉toluene） at 298 and 77 K. The results show that the emission peak of compound 1 in solvent exhibits a slight bathochromic shift. However, the emission peaks of compound 1 in CH3OH and CHC13 are red shift compared with that in CH3CN. It is revealed that the lumi- nescence behavior of compound 1 depends on not only the polarity of solvent but also the hydrogen bonding proper- ties between solvent and solute. In addition, the emission peak of compound 1 in solution shows a red shift obviously at 77 K than that at 298 K（ca. 144-159 nm）, with the fluorescence lifetime increased at 77 K. The lifetime in DMSO at 77 K（r=12.470μs） was the longest one. The quantum yield of compoud 1 increases with increasing the polarity of solvent within a range of 1.8%-8.3 %.