4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Synthesis and properties of tetraalkylammonium chlorides peroxosolvates (CH3)4NCI·H2O2 and (C2H5)4NCl·H2O2

Tetraalkylammonium chlorides peroxosolvates (CH₃)₄NCl·H₂O₂ and (C₂H₅)₄NCl·H₂O₂ were synthesized. The composition of the solvates was proved by chemical analysis; their X-ray patterns, IR spectra, and thermograms were obtained. The solubility of the solvates in water and their stability in aqueous solutions were investigated.     

Syntheses and Structural Researches of Nine-Coordinated (NH4)[EuIII(Edta)(H2O)3] · H2O and (NH4)3[EuIII(Ttha)] · 5H2O1

The crystal and molecular structures of the (NH₄)[Eu^III(Edta)(H₂O)₃] · H₂O (I); Edta^4– is an ethylenediaminetetraacetate anion) and (NH₄)₃[Eu^III(Ttha)] · 5H₂O (II); Ttha^6– is a triethylenetetraminehexaacetate anion) complexes have been determined by single-crystal X-ray structure analysis. The crystal of complex I is orthorhombic with Fdd2 space group. The crystal data are as follows: a = 1.9505(8) nm, b = 3.5445(14) nm, c = 1.2442(5) nm, V = 8.602(6) nm³, Z = 16, M = 531.29, p = 1.579 g cm^–3, = 2.970 mm^–1, and F(OOO) = 3924. The final R and wR values are 0.0378 and 0.1030 for 2799 (I > 2.0(I)) unique reflections, and 0.0495 and 0.1072 for all 6237 reflections, respectively. The nine-coordinated [Eu^III(Edta)(H₂O)₃]^– complex anion has a pseudo-monocapped square antiprismatic structure in which the nine coordinated atoms, two N and four O are from one Edta ligand and three O atoms from water molecules. The crystal of complex II is monoclinic with P2₁/c space group. The crystal data are as follows: a = 1.0387(3) nm, b = 1.2737(4) nm, c = 2.3031(7) nm, = 90.870(5)°, V = 3.047(2) nm³, Z = 4, M = 784.58, C 51.83, H 4.32, N 115.12. = 1.710 g cm^–3, = 2.143 mm^–1 and F(000) = 1608. The final R and wR are 0.0400 and 0.0720 for 5909 (I > 2.0(I)) unique reflections, and 0.0747 and 0.0799 for all 13825 reflections, respectively. The nine-coordinated [Eu^III(Ttha)]^3– complex anion has a pseudo-monocapped square antiprismatic structure in which the Ttha acts as an ninedentate ligand with four N atoms of amino groups and five O atoms of carboxylic groups actually, in addition, there is a non-coordinated free carboxylic group in the structure.     

新型杂多化合物[(CH3CH2)4N]4H3O· {Na[(HMo2O5)3(HPO4)(H2PO4)3]2}·(H2PO4)2·10H2O的水热合成与晶体结构

杂多化合物在催化、医药、材料及光化学等方面具有广泛的应用前景 [1～ 4 ] ,其中钼磷多金属氧酸盐具有优异的氧化催化性能 [5,6 ] .近年来合成的新奇结构的钼磷多金属氧酸盐中已测定结构的有含帽[7,8] 和非帽[9～ 12 ] 系列 .本文利用水热法合成了未见文献报道的结构新颖的夹心型磷钼多金属氧酸盐[( CH3CH2 ) 4N]4 H3O{Na[( HMo2 O5) 3( HPO4 ) ( H2 PO4 ) 3]2 }· ( H2 PO4 ) 2 · 1 0 H2 O,并测定了其晶体结构 .1　实验与晶体结构分析1 .1　仪器与试剂　元素 Na用美国原子吸收分光光度计测定 ;C,H和 N用 Perkin- Elmer 2 4 0…     

Cupro(I)-π-complexes with 1-allyloxybenzotriazole: Synthesis and crystal structure of CuBF4 · 2C6H4N3(OC3H5) · H2O and CuCF3COO · C6H4N3(OC3H5)

The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) Å, β = 98.13(1)°, V = 2249(2) ų, Z = 4, R = 0.0705, 577 reflections; I, space group P $ P\bar 1 The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) ?, β = 98.13(1)°, V = 2249(2) ?³, Z = 4, R = 0.0705, 577 reflections; I, space group P , a = 8.8625(7), b = 9.0647(4), c = 9.1650(5) ?, α = 68.37(2)°, β = 85.31(3)°, γ = 69.86(2)°, V = 646(4) ?³, Z = 2, R = 0.1354, 2669 reflections. In compound I, the tetrahedrally distorted trigonal pyramidal environment of the copper atom comprises two nitrogen atoms of two organic molecules (L), the C=C bond of another L molecule, and the O atom of the water molecule. Due to the bridging function of L molecule, infinite chains [Cu · 2C₆H₄N₃(OC₃H₅) · H₂O] _n are formed in the structure along the y axis. The chains are, in turn, assembled into layers through strong O-H…F hydrogen bonds involving both hydrogen atoms of the water molecule and fluorine atoms of the BF₄⁻ anion. In compound II, two bridging oxygen atoms of two trifluoroacetate anions and two copper atoms form a centrosymmetric dimer. The nitrogen atom of the benzotriazole ring of one molecule L and the C=C double bond of the allyl group of the other molecule L complete the distorted coordination tetrahedron of the metal atom. Owing to the bridging function of the L molecule, the [CuCF₃COO · C₆H₄N₃(OC₃H₅)]₂ dimers are connected to form infinite double chains associated in a three-dimensional framework by only weak interactions. The replacement of the covalently bonded trifluoroacetate anion by an outer-sphere tetrafluoroborate ion opens up the possibility for metal atom binding to three L molecules simultaneously. Original Russian Text ? E.A. Goreshnik, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 826–830.     

Molar heat capacity and thermodynamic properties of Lu(C5H9NO4)(C3H4N2)6(ClO4)3·5HClO4·10H2O

A complex of Lutetium perchloric acid coordinated with l-glutaminic acid (C₅H₉NO₄) and imidazole (C₃H₄N₂), Lu(C₅H₉NO₄)(C₃H₄N₂)₆(ClO₄)₃·5HClO₄·10H₂O was synthesized and characterized. Thermodynamic properties of the complex were studied with an adiabatic calorimeter (AC) from 80 to 390 K and differential scanning calorimetry (DSC) from 100 to 300 K. Two thermal abnormalities were discovered at 220.34 and 248.47 K, which were deduced to be phase transitions. One was interpreted as a freezing-in phenomenon of the reorientational motion of ClO₄ ^? ions and the other was attributed to the orientational order/disorder process of ClO₄ ^? ions. The low-temperature molar heat capacities were measured by AC and the thermodynamic functions [H _T  ? H _298.15] and [S _T  ? S _298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex was studied by thermogravimetric analysis and DSC.     

Structure of (C3H5NH3)2H2P2O7·H2O

The bis(cyclopropylammonium)dihydrogenodiphosphate monohydrate is a new diphosphate associated with the organic molecule C₃H₅NH₂. We report the chemical preparation and the crystal structure of this organic cation diphosphate. (C₃H₅NH₃)₂H₂P₂O₇.H₂O is orthorhombic (S.G. : P2₁2₁2₁), with Z = 4 and the following unit-cell parameters : a = 4.828(1) Å, b = 11.011(1) Å, c = 25.645(2) Å. The P₂O₇ groups and H₂O water molecules form a succession of bidimensional layers perpendicular to the c axis. The organic cations ensure the three-dimensional cohesion by NH-O hydrogen bonds.     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

Synthesis,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

Synthesis,Crystal Structure and Vibrational Spectroscopy of NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O

A novel hydrated cobalt tetraborate complex NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O, was synthesized by the reaction of NH₄‐borate aqueous with CoCl₂ and its structure was determined by single crystal X‐ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a=1.2901(2) nm, b=1.6817(3) nm, c=1.1368(2) nm, α=β=γ=90°, V=2.4742(8) nm³, and Z=4. This compound contains infinite borate layers constructed from [B₄O₅(OH)₄]^2? units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co(NH₃)₅(H₂O)]³⁺ groups through hydrogen bonds to form 3D framework. The groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra (4000–400 cm^?1) of NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The middle band observed at 575 cm^?1 in Raman spectrum is the pulse vibration of [B₄O₅(OH)₄]^2?.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(Edta)(H₂O)₃] · 1.5H₂O (I) (H₄Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH₄)₄[Ho ₂ ^III (Dtpa)₂] · 9H₂O (II) (H₅Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH₄)₃[Ho^III(Ttha)] · 5H₂O (III) (H₆ Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) ų, Z = 16, M = 552.26, ρ_calcd = 1.747 g cm^?3 μ = 3.828 mm^?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) ų, Z = 1, M = 1340.80, ρ_calcd = 1.858 g cm^?3, μ = 3.380 mm^?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP2₁/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) ų, Z = 2, M = 797.55, ρ_calcd = 1.734 g cm^?3, μ = 2.674 mm^?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.     

新型电荷转移复合物(BEDT-TTF)4·H2O·Fe(C2O3)3·C6H5NO2的合成、结构与物理性质

导电性的电荷转移复合物（盐）由于其特殊的物理性质和潜在的应用前景，近年来得到广泛研究［１，２］．导电电荷转移复合物主要包括基于Ｍ（ｄｍｉｔ）２（ｄｍｉｔ＝１，３－二硫－２－硫酮－４，５－二硫醇盐）阴离子自由基［３～５］和ＢＥＤＴ－ＴＴＦ（乙二硫撑四硫...     

纳米晶MgSO4·5Mg(OH)2·3H2O合成与表征

纳米材料由于具有表面、体积和量子尺寸效应的特殊性而受到广泛重视[1～3]. 微米级硫氧镁晶须作为塑料添加增强和阻燃剂已有报道[4～7]. 纳米晶MgSO4*5Mg(OH)2*3H2O不仅对塑料起补强作用, 而且其粒度小, 使塑料变得更致密, 强度、韧性与防水性能大大提高. 目前纳米材料的合成方法多种多样[8～10], 本文采用水热法制得纳米硫氧镁晶粒, 产物纯度高、分散性好且粒度易控制.     

Thermochemical study of [Sm(C7H5O3)2·(C4H6NO2S)]·2H2O

The product from reaction of samarium chloride hexahydrate with salicylic acid and Thioproline, [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O, was synthesized and characterized by IR, elemental analysis, molar conductance, and thermogravimetric analysis. The standard molar enthalpies of solution of [SmCl₃·6H₂O(s)], [2C₇H₆O₃(s)], [C₄H₇NO₂S(s)] and [Sm(C₇H₅O₃)₂·(C₄H₇NO₂S)·H₂O(s)] in a mixed solvent of absolute ethyl alcohol, dimethyl sulfoxide(DMSO) and 3 mol L^?1 HCl were determined by calorimetry to be Δ_s H _m ^Φ [SmCl₃ δ6H₂O (s), 298.15 K]= ?46.68±0.15 kJ mol^?1 Δ_s H _m ^Φ [2C₇H₆O₃ (s), 298.15 K]= 25.19±0.02 kJ mol^?1, Δ_s H _m ^Φ [C₄H₇NO₂S (s), 298.15 K]=16.20±0.17 kJ mol^?1 and Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O (s), 298.15 K]= ?81.24±0.67 kJ mol^?1. The enthalpy change of the reaction (1) $$ SmCl_3 \cdot 6H_2 O(s) + 2C_7 H_6 O_3 (s) + C_4 H_7 NO_2 S(s) = Sm(C_7 H_5 O_3 )_2 \cdot (C_4 H_6 NO_2 S) \cdot 2H_2 O(s) + 3HCl(g) + 4H_2 O(1) $$ was determined to be Δ_s H _m ^Φ =123.45±0.71 kJ mol^?1. From date in the literature, through Hess’ law, the standard molar enthalpy of formation of Sm(C₇H₅O₃)₂(C₄H₆NO₂S)δ2H₂O(s) was estimated to be Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O(s), 298.15 K]= ?2912.03±3.10 kJ mol^?1.     

K3[GdⅢ(nta)2(H2O)]·6H2O和(NH4)·[GdⅢ(Cydta)(H2O)2]·5H2O的合成及晶体结构

GdⅢ的配合物常被用作MRI造影剂[1,2]. GdⅢ的离子半径和电子结构分别为0.107 8 nm和高自旋f 7, 理论预测应与氨基多羧酸类配体形成稳定的九配位配合物[3～5]. 为证实理论预测并在此基础上寻找合适的可用于定向修饰的配体以及为提高GdⅢ配合物的脂溶性使其具有更好的细胞渗透性, 选择四齿配体nta和含有脂环烃的六齿配体Cydta分别合成了GdⅢ的配合物, 并测定了它们的分子结构. 结果显示, GdⅢ与nta形成九配位配合物, GdⅢ与Cydta形成八配位配合物.