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1.
Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.  相似文献   

2.
The title complexes, K3[Cd(Dtpa)] (H5Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O (H4Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) Å3, Z = 2, ρ = 1.754 g/cm3, μ = 1.519 mm?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H2O)]2? complex anion the Cd2+ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H2O)4]2+ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P21/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) Å3, Z = 2, ρ = 2.098 g/cm3, μ = 2.086 mm?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd2+ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P21/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) Å3, Z = 2, ρ = 2.015 g/cm3, μ = 1.856 mm?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).  相似文献   

3.
Complexes [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O (I) and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H2Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.  相似文献   

4.
Two novel chiral organic?Cinorganic hybrid materials based on two important heteropolyoxometallate namely Preyssler and Wells?CDawson anions, (Hval)2(Hgly)(H3O)6K5[Na(H2O)P5W30O110]·19.5H2O (1) and (Hpro)6[P2W18O62]·8H2O (2), were prepared and characterized by elemental analysis, X-ray diffraction, and infrared spectroscopy. The mixed amino acid as cations, Preyssler and Wells?CDawson as anions held together into a 3D-network through hydrogen-bonding interactions. The most unique structural features of 1 and 2 are their 3D-inorganic infinite tunnel-like framework. It results a weak van der Waals interlayer interaction. This provides a desirable condition to use its potential as a host in a host?Cguest complex. The chirallity for these two crystal structures, with the space group P21 has been observed. The electrostatic forces and hydrogen bonding, keep these ????adducts???? stable in the solid state.  相似文献   

5.

Reaction of a freshly prepared Ni(OH)2?2 x (CO3) x ·yH2O with maleic acid in H2O at room temperature afforded [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O, which consists of [Ni(H2O)6]2+ cations, [Ni(H2O)2(C4H2O4)]2? anions and lattice H2O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.  相似文献   

6.
7.
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.  相似文献   

8.
9.
Abstract  A novel polyoxotungstate H5[Cu(en)2H2O]{Cu(en)2[P2W19O69(H2O)]} · 2.5H2en · 8H2O (1) has been synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: Triclinic, P-1, a = 12.673(6) ?, b = 20.147(10) ?, c = 20.514(11) ?, α = 110.432(7)°, β = 90.171(5)°, γ = 97.502(6)°, V = 4859(4) ?3, Z = 2. Compound 1 exhibits a 1D linear structure, in which the [Cu(en)2]2+ ions act as the linkages of {P 2 W 19 } lacunary units. Graphical Abstract  A novel polyoxotungstate H5[Cu(en)2H2O]{Cu(en)2[P2W19O69(H2O)]} · 2.5H2en · 8H2O has been made under hydrothermal conditions. Compound 1 exhibits a 1D linear structure based on the {P 2 W 19 } lacunary units linked by the [Cu(en)2]2+ bridging groups.   相似文献   

10.
Calcium titanate (CaTiO3) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO3 materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO3 powders had a surface area of 14.0 m2/g. In addition, the microwave dielectric properties of the resulting CaTiO3 material have been measured.  相似文献   

11.
By controlling the pH of the reaction system, a dilacunary γ-Keggin silicotungstate [Cu(en)2(H2O)][H2en]{γ-SiW10O36[Cu(en)2(H2O)]2}·7.5H2O (1) (en?=?ethylenediamine) has been hydrothermally synthesized by the reaction of CuCl2 with α-H4SiW12O40 and characterized by IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. The product is prepared in the pH range 7.9–8.2, which reveals that pH plays a key role in the assembly of saturated α-H4SiW12O40 to dilacunary [γ-SiW10O36]8? polyoxometalate. The polyoxoanion {γ-SiW10O36[Cu(en)2(H2O)]2]}4? of 1 presents a rare [γ-SiW10O36]8?-retaining structure, in which two lacunary sites of [γ-SiW10O36]8? are unoccupied, meanwhile, two [Cu(en)2(H2O)]2+ groups are grafted on either side of the [γ-SiW10O36]8? unit by Cu–O–W bond.  相似文献   

12.
Abstract

In an attempt to form new multi-dimensional structures of cyano complexes including cadmium(II) and copper(I), four new complexes were obtained successively from an aqueous solution at intervals of from a few days to a few months. The complex 1 obtained first was unstable in the atmosphere. The crystal structures of the other complexes (2–4) obtained from second to fourth were determined by single crystal X-ray structure determinations. Their crystal data are as follows: 2 Cd(H2O)2 Cu(CN)3·2H2O, monoclinic, C2/m, a = 14.038(1), b = 9.944(1), c = 7.738(1) Å, β = 116.019(7)°, Z = 4; 3 K[Cd(H2O)2Cu2(CN)5]·2H2O, triclinic, PI, a = 17.429(9), b = 16.519(7), c = 10.085(5) Å, α = 128.60(3), β = 137.44(2), γ = 45.82(2)°, Z = 4; 4 K2[Cd(H2O)Cu4(CN)8]·1.5H2O, monoclinic, C2/c, a = 19.387(2), b = 16.056(3), c = 12.663(2)Å, β = 110.419(9)°, Z = 4. The main structural feature found in the complexes is that the whole framework consists of two networks, a Cd-Cu(I)-CN complex network that has an infinite network formed with bridging cyano groups between the metal atoms and a network formed with hydrogen bonding among water molecules. The second network is connected to Cd in the Cd-Cu(I)-CN complex network via a water ligand coordinated to Cd. In 2 a planar network of [CdCu(CN)3] complexes are stacked along the c axis and the second network links the stacked complexes. 3 has a stacked structure of [Cd(H2O)2Cu(CN)5]2? in a bi-layered structure. The second network of 3, which includes K+ ions with an electrostatic interaction, spreads over the crystal, penetrating vacant spaces of the metal complex network. 4 has a double lattice structure with a pair of enantiomeric three-dimensional [Cd(H2O)Cu4(CN)8]2? complexes inter-penetrating each other. There are three structural factors for forming these framwork structures: (1) a non-planar coordination structure for Cd(II) that extends the planar structure of the Cu(I)-CN complex to a three-dimensional structure for the Cd-Cu(I)-CN complex; (2) a trigonal planar coordination structure for Cu(I) that generates vacant space in the metal complex network and makes possible hydrogen bonds to form the second network; (3) structural distortions of bridging cyano groups and a coordination structure of Cu(I) that cause variations of the metal complex network structure.  相似文献   

13.
Two new hybrid Dawson-based polyoxotungstates, [Mn(2,2′-bipy)3]H2[Mn(2,2′-bipy)2][P2W18O62] (1) and [Co(H2biim)3)]2H2[P2W18O62] · 8H2O (2) (2,2′-bipy = 2,2′-bipyridine, H2biim = 2,2′-biimdazole), have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectra. Compound 1 is a 1-D zigzag chain constructed from alternate Dawson-type heteropolyanions [α-P2W18O62]6? and metal coordination cations [Mn(2,2′-bipy)2]2+, in which the 1-D chains are extended into a 3-D framework through C–H ··· π and π–π stacking interactions. Compound 2 is a discrete structure consisting of [α-P2W18O62]6? and two [Co(H2biim)3)]2+ cations, forming a 3-D supramolecular framework via N–H ··· O hydrogen bonds and C–H ··· π interactions. Photoluminescence properties of 1 and 2 have been investigated at room temperature.  相似文献   

14.
H8[P4W14O58Na4(H2O)20]·16H2O的合成、晶体结构与性质   总被引:9,自引:2,他引:7  
用水热法合成了H8[P4W14O58Na4(H2O)20]·16H2O,通过X射线单晶衍射、元素分析和IR进行了结构表征,用TG-DTA研究了热稳定性。晶体属三斜晶系,P1空间群,a=1.1379(2)nm,b=1.3632(3)nm,c=1.6271(3)nm;a=78.20(3)°,β=71.20(3)°,γ=71.62(3)°;V=2.2525(8)nm^3,Z=1,Mr=4374.38,D  相似文献   

15.
After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH2(CH2)4NH2, we report chemical preparation and crystal structure for a new example of such compounds. [NH3(CH2)4NH3]2P4O12.2H2O is monoclinic (S.G. : P21/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P4O12 rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.  相似文献   

16.
Two new decavanadate metal complexes, [Co(H2O)6]2[H2V10O28]·6H2O (1) and (NH4)2[Ca(H2O)7]2[V10O28] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO3 solution with an aqueous solution of CoCl2·6H2O were used for generating 1 and aqueous CaCl2·2H2O and NH4VO3 solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H2O)6]2+ cations, [H2V10O28]4− anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H2O)7]2+ cations, ammonium NH4 + and [V10O28]6− anion. For compound 2, the distorted pentagonal bipyramid [Ca(H2O)7]2+ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.  相似文献   

17.
Saturation molalities m(sat) in H2O(l) have been measured for the substances adenosine(cr), guanosine · 2H2O(cr), inosine(cr), and xanthosine · 2H2O(cr) over the temperature range T=287.91 K to T=308.18 K by using h.p.l.c. The indicated states of hydration of these substances were established by performing Karl–Fischer analyses of samples of these substances which had been equilibrated over H2O(l) and of samples obtained by passing air over the wet crystals (air dried samples). The crystalline phases of these substances were identified by comparison of the results of X-ray diffraction measurements with results from the literature. Molar enthalpies of solution ΔsolHm for adenosine(cr) and inosine(cr) were measured by using an isoperibol solution calorimeter. A “stacking” or “self-association” model was used to estimate values of the activity coefficients γ and relative apparent molar enthalpies Lφ for these substances. These γ and Lφ values were used to adjust the measured values of m(sat) and ΔsolHm to the standard state and obtain values of the standard molar Gibbs free energy and enthalpy changes ΔsolGm and ΔsolHm, respectively, for the dissolution reactions of these substances. Values of ΔsolHm calculated from the temperature dependence of values of ΔsolGm were in good agreement with the values of ΔsolHm obtained by using calorimetry.  相似文献   

18.
Three complexes, Na4[DyIII(dtpa)(H2O)]2?·?16H2O, Na[DyIII(edta)(H2O)3]?·?3.25H2O and Na3[DyIII (nta)2(H2O)]?·?5.5H2O, have been synthesized in aqueous solution and characterized by FT–IR, elemental analyses, TG–DTA and single-crystal X-ray diffraction. Na4[DyIII(dtpa)(H2O)]2?·?16H2O crystallizes in the monoclinic system with P21/n space group, a?=?18.158(10)?Å, b?=?14.968(9)?Å, c?=?20.769(12)?Å, β?=?108.552(9)°, V?=?5351(5)?Å3, Z?=?4, M?=?1517.87?g?mol?1, D c?=?1.879?g?cm?3, μ?=?2.914?mm?1, F(000)?=?3032, and its structure is refined to R 1(F)?=?0.0500 for 9384 observed reflections [I?>?2σ(I)]. Na[DyIII(edta)(H2O)3]?·?3.25H2O crystallizes in the orthorhombic system with Fdd2 space group, a?=?19.338(7)?Å, b?=?35.378(13)?Å, c?=?12.137(5)?Å, β?=?90°, V?=?8303(5)?Å3, Z?=?16, M?=?586.31?g?mol?1, D c?=?1.876?g?cm?3, μ?=?3.690?mm?1, F(000)?=?4632, and its structure is refined to R 1(F)?=?0.0307 for 4027 observed reflections [I?>?2σ(I)]. Na3[DyIII(nta)2(H2O)]?·?5.5H2O crystallizes in the orthorhombic system with Pccn space group, a?=?15.964(12)?Å, b?=?19.665(15)?Å, c?=?14.552(11)?Å, β?=?90°, V?=?4568(6)?Å3, Z?=?8, M?=?724.81?g?mol?1, D c?=?2.102?g?cm?3, μ?=?3.422?mm?1, F(000)?=?2848, and its structure is refined to R 1(F)?=?0.0449 for 4033 observed reflections [I?>?2?σ(I)]. The coordination polyhedra are tricapped trigonal prism for Na4[DyIII(dtpa)(H2O)]2?·?16H2O and Na3[DyIII(nta)2(H2O)]?·?5.5H2O, but monocapped square antiprism for Na[DyIII(edta)(H2O)3]?·?3.25H2O. The crystal structures of these three complexes are completely different from one another. The three-dimensional geometries of three polymers are 3-D layer-shaped structure for Na4[DyIII(dtpa)(H2O)]2?·?16H2O, 1-D zigzag type structure for Na[DyIII(edta)(H2O)3]?·?3.25H2O and a 2-D parallelogram for Na3[DyIII(nta)2(H2O)]?·?5.5H2O. According to thermal analyses, the collapsing temperatures are 356°C for Na4[DyIII(dtpa)(H2O)]2?·?16H2O, 371°C for Na[DyIII(edta)(H2O)3]?·?3.25H2O and 387°C for Na3[DyIII(nta)2(H2O)]?·?5.5H2O, which indicates that their crystal structures are very stable.  相似文献   

19.
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.  相似文献   

20.
Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H2O)6]H3[V10O28] · 2H2O (I) was obtained and examined by mass spectrometry, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The crystals are monoclinic, space group $P\bar 1$ a = 7.862(3), b = 8.427(5), c = 5.000(2) Å, β = 96.46(4)°, V = 867.0(3) Å3, ρcalcd = 5.83 g/cm3, Z = 1.  相似文献   

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