一维链状配位聚合物[(C6H5)3SnO]n的合成和结构研究

在甲醇溶剂中利用(C6H5)3SnCl和三乙胺水解得到一种新型有机锡聚合物[(C6H5)3SnO]n。用元素分析、IR及X-射线衍射法表征配合物。晶体结构用直接法解出,并用全矩阵最小二乘法进行修正。该晶体属于正交晶系,空间群为P212121,晶胞参数为:a=0.8339(15)nm,b=1.040(2)nm,c=1.8067(4)nm,Z=4,V=1.5668(5)nm3,Mr=365.99,Dc=1.552g/cm3,mμ=1.623mm-1,F(000)=724,S=1.065,R=0.0278,wR=0.0511配合物的中心锡原子呈五配位畸变三角双锥构型。     

Synthesis and x-ray crystal structure of [{(C5H4Me)Fe(CO)2}2BiCl]3: A compound containing a planar six-membered Bi3Cl3 ring

The reaction between BiCl₃ and two equivalents of Na[(C₅H₄Me)Fe(CO)₂] affords the title complex, [{(C₅H₄Me)Fe(CO)₂}₂BiCl]₃, containing a planar six-membered Bi₃Cl₃ ring in which each bismuth is bonded to two chlorine atoms and two (C₅H₄Me) Fe(CO)₂ fragments.     

Synthesis, structure, and magnetism of an f element nitrosyl complex, (C5Me4H)3UNO

(C(5)Me(4)H)(3)U, 1, reacts with 1 equiv of NO to form the first f element nitrosyl complex (C(5)Me(4)H)(3)UNO, 2. X-ray crystallography revealed a 180° U-N-O bond angle, typical for (NO)(1+) complexes. However, 2 has a 1.231(5) ? N═O distance in the range for (NO)(1-) complexes and a short 2.013(4) ? U-N bond like the U═N bond of uranium imido complexes. Structural, spectroscopic, and magnetic data as well as DFT calculations suggest that reduction of NO by U(3+) has occurred to form a U(4+) complex of (NO)(1-) that has π interactions between uranium 5f orbitals and NO π* orbitals. These bonding interactions account for the linear geometry and short U-N bond. The complex displays temperature-independent paramagnetism with a magnetic moment of 1.36 μ(B) at room temperature. Complex 2 reacts with Al(2)Me(6) to form the adduct (C(5)Me(4)H)(3)UNO(AlMe(3)), 3.     

Synthesis and crystal structure of a copper(II) 5-sulfosalicylate complex with thiosemicarbazide

The compound [Cu(TSC)₂](H₂SSal)₂ (I) has been synthesized (TSC is thiosemicarbazide, H₃SSal is 5-sulfosalicylic acid) and studied by IR spectroscopy and X-ray crystallography. The crystals of I are triclinic: a = 6.728(2) Å, b = 7.772(1)Å, c = 11.600(6)Å, α = 88.60°, β = 86.68(3)°, γ = 79.22(4)°, V = 594.8(4)ų, Z = 2, space group \(P\bar 1\). The structural units of the crystal are the centrosymmetric [Cu(TSC)₂]²⁺ cation, in which the Cu atom is in a square-planar coordination formed by the bidentate chelating (N,S) TSC ligands, and (H₂SSal)^? anions (Cu(1)-N(3), 2.013(3) Å; Cu(1)-S(1), 2.275(1) Å). The coordination polyhedron of the Cu(1) atom is completed to a prolate tetragonal bipyramid (4 + 2) by Cu-O bonds (2.810(3) Å) of the sulfate moieties of both anions, which form together with hydrogen bonds the [Cu(TSC)₂(H₂SSal)₂] supermolecule. The complex cations are packed in layers and alternate with anion-containing layers. Hydrogen bonding and π?π stacking interactions are responsible for formation of supramolecular layer ensembles.     

One-dimensional Schiff-base-bridged manganese(III) complex: Synthesis,crystal structure and magnetic property

A new one-dimensional Schiff-base ligand bridged manganese(III) complex with the formula [Mn(acacen)(H₂acacen)]ClO₄ (1) (acacen = N, N'-ethylenebis(acetylacetonylideneaminato) has been obtained from the reaction of [Mn(acacen)(H₂O)₂]ClO₄ with K[Fe(bpdBrb)(CN)₂] (bpdBrb^2– = 1,2-bis(pyridine-2-carboxamido)-4,5-dibromobenzenate), which has been characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals it’s onedimensional infinite structure consisting of alternating units of [Mn(acacen)]⁺ and the Schiff-base ligand H₂acacen with a trans conformation, forming a cationic polymeric chain with free ClO₄^- as the balanced anion. The one-dimensional chain structure can be can be further linked into three-dimensional supramolecular network under the help of the intermolecular weak interactions. Investigation over its magnetic property reveals the weak antiferromagnetic coupling between the adjacent Mn(III) ions.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Synthesis, solid-state structure, and bonding analysis of the beryllocenes [Be(C5Me4H)2], [Be(C5Me5)2], and [Be(C5Me5)(C5Me4H)

The beryllocenes [Be(C(5)Me(4)H)(2)] (1), [Be(C(5)Me(5))(2)] (2), and [Be(C(5)Me(5))(C(5)Me(4)H)] (3) have been prepared from BeCl(2) and the appropriate KCp' reagent in toluene/diethyl ether solvent mixtures. The synthesis of 1 is facile (20 degrees C, overnight), but generation of decamethylberyllocene 2 demands high temperatures (ca. 115 degrees C) and extended reaction times (3-4 days). The mixed-ring beryllocene 3 is obtained when the known [(eta(5)-C(5)Me(5))BeCl] is allowed to react with K[C(5)Me(4)H], once more under somewhat forcing conditions (115 degrees C, 36 h). The structures of the three metallocenes have been determined by low-temperature X-ray studies. Both 1 and 3 present eta5/eta1 geometries of the slip-sandwich type, whereas 2 exhibits an almost regular, ferrocene-like, sandwich structure. In the mixed-ring compound 3, C(5)Me(5) is centrally bound to beryllium and the eta(1)-C(5)Me(4)H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the eta(1)-ring of 1. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds 2 and 3, and a comparison with the bonding in [Be(C(5)H(5))(2)] has been made. As for the latter molecule, energy differences between the eta5/eta5 and the eta5/eta1 structures of 2 are very small, being of the order of a few kcal mol(-1). Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C(5)Me(5))(2)] than for [Be(C(5)H(5))(2)] due to larger charge delocalization and to increased polarizability of the C(5)Me(5) fragment.     

Synthesis,crystal structure and magnetic property of an octacyanometalate-bridged complex

An octacyanometalate-bridged complex, [Ni(en)₂(H₂O)W(CN)₈][Ni(en)₃] · 2H₂O, has been prepared and characterized and the magnetic properties studied. The complex was characterized using IR, elemental analysis and UV-Vis. The magnetic susceptibility measured over the range 1.8–300 K shows antiferromagnetic interaction.     

二维网状银(I)配合物的合成及结构表征

用1,10-二(邻氨基苯氧基)癸烷和AgNO3,进行配位反应得到了配合物[Ag2(L)(NO3)2]η(1).并用元素分析,FT-IR和X-射线单晶衍射进行了表征.结果表明,配合物属于单斜晶系,P21/c空间群,晶胞参数为:a=0.5649(l)nm,b=3.3426(7)nm,c=0.9375 (2) nm,β=99...     

Synthesis,crystal structure,and luminescence properties of a novel europium(III) complex

A novel europium(III) complex, [Eu(C₇H₅O₂)₂(C₇H₆O₂)₂(C₁₂H₈N₂)₂Cl], was synthesized and characterized by elemental analysis and single-crystal X-ray determination. It crystallizes in the monoclinic system, space group Cc with a = 17.2814(16), b = 17.9421(17), c = 14.9971(14) Å, β = 101.6510(10)°, Z = 4, ρ _c = 1.508 g/cm³, μ = 1.496 mm^?1, the final R = 0.0516 and wR = 0.1267 for 6435 observed reflections with I > 2σ(I). Structural analysis shows that the Eu(III) atom is nine-coordinated by one chlorine atom, four N atoms of two 1,10-phenanthroline (Phen) ligands, and four O atoms from four carboxybenzene ligands, to form a distorted tricapped trigonal prism. The luminescence spectrum of the complex indicates that the intensity of the emission wavelength at 612 nm is strongest among all emission wavelengths and the second phen ligand shows an enhancement effect on the luminescence of the complex.     

Synthesis,identification, crystal structure and theoretical study of a Ce(IV) complex

The compound (dienH₃)₂(pydc)_3, 1; dien: diethyltriamine, pydcH₂: pyridine-2,6-dicarboxylic acid, as a proton transfer ligand was applied to synthesize (dienH₃)₂[Ce(pydc)₃]₃·16.75H₂O, 2. The compounds were examined by elemental analysis, IR, UV and NMR spectroscopy. In addition, the compound 2 was studied by TG analysis, single crystal X-ray diffractometry and computational calculations. Geometry optimizations were carried out using B3PW91 hybrid density functional and quasi-relativistic effective core potentials (ECP46MWB) to represent the atomic core of cerium and 6–311G(d, p) basis set that used to describe the electrons of oxygen, nitrogen, carbon and hydrogen atoms. Also, natural bond orbital (NBO) analysis at the B3 PW91/A level gives the natural electron population and the natural charge for each atom. Cerium atom in 2 is nine-coordinated with three (pydc)^2? groups giving an anionic complex which is balanced by (dienH₃)³⁺ in the crystal structure. Several intermolecular interactions including O–H···O and N–H···O hydrogen bonds, face-to-face and edge-to-face stackings are responsible to stabilize the extended structure.     

Synthesis,crystal structure,spectroscopy, and electrochemistry of a uranium complex

A uranium coordination compound with pyridine-2,6-dicarboxylic acid in deionized water has been synthesized and characterized by IR, UV, XPS, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group C2/c with a?=?1.8427(4)?nm, b?=?0.6886(16)?nm, c?=?1.5442(4)?nm, α?=?90°, β?=?94.082(2)°, γ?=?90°, Z?=?4, and V?=?1.9544(8)?nm³. The structure shows an eight-coordinate uranium forming a hexagonal bi-pyramidal 3-D geometry with pyridine-2,6-dicarboxylate as building units. Fluorescent studies show several strong emissions. Cyclic voltammetric measurement of the compound reveals that uranium(VI) is reduced irreversibly at E _1/2?=?927?mV with ΔE _p?=?77?mV, E _1/2?=??289?mV with ΔE _p?=?113?mV. The electron transfer number (n) involved in reduction processes could be calculated to be approximately two and one, which corresponded to the unusual U(VI)/U(IV) and U(IV)/U(III) couples.     

Synthesis and crystal structure of mononuclear nickel(II) trifloroacetate complex

Russian Journal of General Chemistry -     

Synthesis,crystal structure and magnetic property of a three-dimensional manganese(II) complex

The solvothermal reaction of MnCl₂·4H₂O, H₂asp and CH₃ONa gave rise to a new manganese(II) complex, {[Mn(asp)(H₂O)]·(H₂O)₂} _n (1) (H₂asp?=?5-aminoisophthalic acid). Single-crystal X-ray diffraction analysis reveals that complex 1 is a three-dimensional consisting of two-dimensional layers extended by hydrogen bonding interactions. The two-dimensional layer contains 8-, 14-, and 16-membered rings. A variable temperature magnetic measurement of 1 displays weak antiferromagnetic behavior.     

Zn(Ⅱ)与氯苯基苯并咪唑配合物的合成、表征和晶体结构

带咪唑、苯并咪唑等配位基团的过渡金属配合物是一类很重要的物质[1～ 9] 。本文探讨它与Ｚｎ(Ⅱ )的配位性质及配合物的晶体结构。1　实验部分1 .1　标题配合物的合成及表征将 92ｍｇ 2 (0 氯苯基 )苯并咪唑和 40ｍｇＺｎＣｌ2(ＡＲ)分别溶于无水乙醇(ＡＲ)后混合均匀 ,于室温下静置 3 0天 ,析出长方体形无色晶状物 ,产率为 47%。采用Ｐｅｒｋｉｎ Ｅｌｍｅｒ 2 4 0Ｃ元素分析仪测定配合物中Ｃ、Ｈ、Ｎ含量。用ＤＤＳ 1 1Ｃ数显电导率仪 ,以ＤＭＦ为溶剂测定配合物的摩尔电导。采用Ｎｉｃｏｌｅｔ5ＤＸ Ｂ傅立叶变换红外光谱仪 ,ＫＢｒ压…     

Star hexacarboxylate: Synthesis,crystal structure and luminescent properties of its terbium complex

A new star host, hexakis (carboxylphenyl-2-thiolmethyl)benzene (1H6), has been synthesized by a simple one-step condensation procedure with the high yield. Crystal structure of the DMSO adduct 1H6.6DMSO (2) reveals it to be rhombohedral crystal system, space group R-3, with a =b=2.4129(2), c= 1.1576(3) nm, α=β= 90°γ = 120°?V=5.837(2) nm3,Z=3. The six arms of side benzole acid rings and the H-bonded DMSO molecules are located alternatively above and below the central benzene plane with "1,3,5-up/2,4,6-down" conformation. Terbium complex (Tb21)2Py.9H2O (3) was prepared in hot pyridine, which shows bright characterized Tb(Ⅲ) emission with a longer lifetime and higher luminescent intensity than that of the corresponding terbium benzoate in solid state. These observations suggest that host 1 is a good antenna for sensitizing TbⅢ emission.     

Copper(II) complex with thienyltrifluoroacetylacetone and dimethyl sulfoxide: Synthesis and crystal structure

A new copper(II) complex with thienyltrifluoroacetone (Tfa) and dimethyl sulfoxide (DMSO), Cu(Tfa)₂DMSO, was synthesized, and its X-ray diffraction analysis was carried out. The crystals were triclinic: a = 9.4496(5), b = 10.5075(6), c = 11.9160(6) Å, α = 82.600(1)°, β = 84.116(1)°, γ = 77.904(1)°, V = 1143.8(1) ų, space group P $ \bar 1 $ , Z = 2, ρ_calcd = 1.696 mg/m³, R = 0.0700. The environment of the copper atom was formed by four oxygen atoms of two thienyltrifluoroacetylacetone molecules and one oxygen atom of DMSO.     

N-乙酰皮考林酰肼合铜的合成和晶体结构

N-乙酰皮考林酰肼(HL)与一水乙酸铜在甲醇溶剂中形成配合物Cu(Ⅱ)L2·0 5H2O(C16H17CuN6O4 5,Mr=428 90),晶体属单斜晶系,空间群为C2/c,a=2 8355(2)nm,b=0.90009(4)nm,c=1.49351(9)nm,β=107.974(2)°,V=3 6258(3)nm3,Z=8,F(000)=1760,μ(MoKα)=1 24mm-1,R=0 0338,wR=0 0955.Cu(Ⅱ)原子的配位介于六配位的严重扭曲的八面体和四配位的不规则多面体之间,其中Cu与O(羰基)距离为0 2653(2)和0 2591(7)nm.量子化学从头算方法计算结果表明,铜与羰基氧之间存在弱配键,晶体通过分子间氢键作用形成一维的无限链状结构     

Synthesis, crystal structure of diferrous complex and its reactivity with dioxygen

The dinuclear complex of [Fe2L{O2P(OPh)2}](CIO4)2 ·Et2O(1) (where L represents the dinucleating ligand N-Et-HPTB, anion of N, N, N', N'-tetrakis (N-ethyl-2-benzimidazolyemethyl)-2-hydroxy-1, 3-diamino-propane) has been synthesized and crystallizes in the triclinic space group P T with cell constants α = 1.526(3) nm, b = 1.259 8(3) nm, c = 1.563 0(3) nm , α = 94.41 (3)°, P = 115.31(3)°, β=99.90(3)°, V= 3.267(1) nm3, z=2, R = 0.084 7 and Rw = 0.177 8. The Fe(Ⅱ) sites are bridged by an alkoxide of the dinucleating ligand and a phosphate, affording a diiron core with an Fe-μ-O-Fe angle of 131.20(3)° and an Fe-Fe distance of 0.364 9 nm. Both Fe(II) centers have trigonal bipyramidal geometry. Dioxygen adduct (1/O2) forms upon exposure of the diferrous complex to O2 at low temperature (-60℃). The 1/O2 adduct is stable at -60℃ but decomposes upon warming. The adduct exhibits visible absorption maximum near 606 nm and resonance Raman features at 478 cm-1 (γFe-o) and 897 cm-1 (γo-o), and the latter