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1.
The symmetry, composition, and crystal structure of Cs6.3W11O36 (a=7.2742, c=110.79 Å, Z=6, $R\bar 3c$ , R=0.057), previously considered monoclinic and stoichiometric, are refined. The tungsten-oxygen octahedral units of the structure, which have an AB2O6 defective pyrochlore motif, lie in layers perpendicular to the c axis, with Cs+ ions located in the voids of layer units and between them. An additional interlayer position of cesium, occupied by 31(8)%, has been found. The structures of Cs8.5W11O48 and defective pyrochlore, related to Cs6+xW11O36, form a homologous series with the general formula A2nA 1?yM4n?1X12n (for the above members, n=3,4 and ∞, respectively); the members in the series differ in the number of storeys in pyrochlore-like layers.  相似文献   

2.
Crystals of cesium silicate Cs6Si10O23 were prepared upon the crystallization of glass Cs2O · 4SiO2. The crystal structure of Cs6Si10O23 was determined by single-crystal X-ray diffraction (space group P $\bar 6$ 2m, a = 9.578(5) Å, c = 4.155(5) Å, Z = 0.5, 269 F(hkl), R = 0.0424). The three-dimensional tetrahedral silicate framework in Cs6Si10O23 is similar to that in Rb6Si10O23 (space group P $\bar 6$ 2m, a = 9.475(5) Å, c = 8.200(5) Å) in which layers formed by 12-membered rings of silicon-oxygen tetrahedra may be distinguished. However, while in the rubidium silicate structure the vertices of the tetrahedra neighboring in a layer point to opposite directions, in cesium silicate these tetrahedra are disordered as regards the arrangement of vertices either upward or downward relative to the layer plane. The random disorder results in a smaller unit cell parameter c in Cs6Si10O23 compared to Rb6Si10O23. The compound melts congruently; the melting temperature and the enthalpy of melting of the crystal are 1208 ± 1 K and 156.2 ± 15 kJ/mol, respectively.  相似文献   

3.
In the cocrystal formation of a nonprotic polar (host) molecule (1) with nitromethane (guest) several weak, but directional, intermolecular interactions have vital importance. The endo conformation of the (N)-xylene group of the polycyclic succinimide-based host 1 is stabilized by a Cmethyl $---$ H ??? π interaction [C ??? π /H ??? π distances are 3.554(7)/2.57 Å, the C $---$ H ??? π angle is 159], and the crystal packing is governed by dipole–dipole type interhost (C $ =$ )O ??? C( $ =$ O) connection [C ??? O $ =$ 3.000(5) Å and <C $ =$ O ??? C $ =$ 159.8(3)] in conjunction with possible C $---$ H ??? O interactions [with C ??? O distances ranging between 3.20 and 3.50 Å] involving the polar groups of both host and guest. Crystal data: 1 ??? nitromethane (1:1), C26H21O2 N ? CH3NO2, M w = 440.50, P2 1/n, a = 14.143(1), b = 7.973(1), c = 20.291(2) Å, β = 95.183(9), Z = 4, D c = 1.2840(2) g cm?3, R = 0.055 for 1709 reflections.  相似文献   

4.
The molecular and crystal structure of four acyclic trisiloxane compounds, which differ in substituents at the silicon atoms (Ph-phenyl, mPh-methoxyphenyl, 2mPh-dimethoxyphenyl), was investigated by X-ray diffraction analysis. Due to intermolecular hydrogen bonding between the oxygen atoms of the diol fragments, the crystal structure of 1,1,5,5-tetramethyl-3,3-diphenyl-1,3,5-trisiloxane-1,5-diol (C16H24O4Si3) (I) is a double chain architecture with hydrogen-bonded dimeric motifs of C(8)R 4 4 (12) type in graph set representation. In 1,1,5,5-tetramethyl-3,3-(2-methoxybenzo)-1,3,5-trisiloxane-1,5-diol (C18H28O6Si3) (II) and 1,1,5,5-tetramethyl-3,3-(2,6-dimethoxybenzo)-1,3,5-trisiloxane-1,5-diol (C20H32O8Si3) (III), a double chain structure with a graph set R 3 3 (8)D 3 3 (10) is formed. In contrast to I–III, 1,1,3,3,5,5-hexaphenyl-1,3,5-trisiloxane-1,5-diol (C36H32O4Si3) (IV) has an intramolecular hydrogen bond S(8). The independent molecules are joined by O-H...O intermolecular hydrogen bonds into centrosymmetrical dimers; the system of hydrogen bonds in general may be described as S(8)R 4 4 (8).  相似文献   

5.
Compounds that are formed in the M 2 I O-Ga2O3-TiO2 system and crystallize in three structural types were prepared by solid-phase reactions. The M 2 I Ga2Ti6O16 (MI = Na, K, Rb, Cs) compounds were prepared for the first time. The thermal expansion coefficients of LiGaTiO4, Na2Ga2Ti6O16, K2Ga2Ti6O16, Rb2Ga2Ti6O16, and Cs2Ga2Ti6O16 were determined by high-temperature X-ray diffraction. Some tendencies of thermal distortions in M 2 I A 2 III Ti6O16 and LiAIIITiO4 (MI = Na, K, Rb, Cs; AIII = Al, Cr, Fe, Ga) were disclosed.  相似文献   

6.
An X-ray diffraction study of the single crystals of (C2H7N4O)2[(UO2)2(OH)2(C2O4)(CHO2)2] was carried out. The compound crystallizes in the triclinic system, space group $P\bar 1$ , Z = 2, a = 5.5621(8) Å, b = 8.1489(10) Å, c = 11.8757(16) Å, α = 88.866(7)°, β = 82.204(6)°, γ = 87.378(6)°, V = 532.7(1) Å3, ρcalcd = 2.988 g/cm3. The main structural units in the crystal are the [(UO2)2(OH)2(C2O4)(CHO2)2)]2? chains corresponding to the crystal chemical group A2M 2 2 K02M 2 1 (A = UO 2 2+ , M2 = OH?, K02 = C2O 4 2? , M1 = CHO 2 ? ) of uranyl complexes. The chains are united into a three-dimensional framework through the electrostatic interaction and hydrogen bonds involving uranyl, oxalate, and hydroxyl groups, formate ions, and 1-carbamoylguanidinium cations.  相似文献   

7.
A hydrated crystalline ionized adduct of dibenzo-18-crown-6 and perchloric acid DB18C6 · H3O+ · CiO 4 ? · 3H2O (I) is synthesized and characterized by X-ray diffraction. The crystals of I are monoclinic: a = 17.760 Å, b = 12.922 Å, β = 124.27°, Z = 4, space group Cc. The structure of I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 for 3294 independent reflections (CAD4 automated diffractometer, λMoK α radiation). A DB18C6 molecule has a butterfly conformation with the rough symmetry C 2v . An H3O+ · H2O dimer is situated on one side of the DB18C6 macrocycle, and the ClO 4 ? anion and two other water molecules are on the other side. In the crystal of I, the DB18C6 molecules, H3O+ and ClO 4 ? ions, and water molecules are linked through intermolecular (interionic) hydrogen bonds to form broad infinite chains running along the z axis.  相似文献   

8.
N,N-Dimethylanilinium dicitratoborate monohydrate [C6H5NH(CH3)2][(C6H6O7)2B]·H2O (I) was synthesized for the first time. Single crystals were obtained in an aqueous solution; the crystal structure was studied by X-ray crystallography. Crystals of I are triclinic, space group $P\bar 1$ , a = 9.7017(2) ?, b = 11.0475(2) ?, c = 12.6282(2) ?, ?? = 106.595(2)°, ?? = 106.931(1)°, ?? = 103.568(1)°, V = 1163.97(4) ?3, Z = 2, ??calc = 1.516 g/cm3. The structural units of compound 1 are large complex dicitratoborate anions with a spiran structure, N,N-dimethylanilinium cations, and crystal water molecules. The crystal packing is a three-dimensional framework. A hydrogen-bond system is formed by seven independent contacts O(N)-H??O.  相似文献   

9.
In this paper the technology of producing solid solutions of Csx(NH4)1?xLiSO4 using the slow evaporation method is presented. Appropriate conditions were chosen to grow large samples. The ammonium ion content in the solid solutions was determined using the Kjeldahl method. It was found that the real ammonium ion concentration is twice lower than the one applied in the initial substances. At room temperature, the base crystal, lithium cesium sulfate (CsLiSO4), is paraelastic, whereas lithium ammonium sulfate (NH4LiSO4) is ferroelectric. It is expected that as a result of substituting Cs+ ions with $ N{\text{H}}_{4}^{ + } $ N H 4 + ions, instead of the Cs+ ions, the modification of the ferroic properties of solid solutions of Csx(NH4)1?xLiSO4 will take place. Tests conducted with the use of the differential scanning calorimetry method (DSC) allowed the detection of the ferroelastic phase transition which takes place in these compounds. A gradual increase of temperature transition was observed from 202 K for the pure CsLiSO4 to 203.8 K for Cs0.90(NH4)0.10LiSO4 and 230.1 K for Cs0.85(NH4)0.15LiSO4 with the increase of $ N{\text{H}}_{4}^{ + } $ N H 4 + ions concentration. Using polarized light microscopy, a ferroelastic domain structure was detected in the examined solid solutions, which appeared below the structural phase transition temperature.  相似文献   

10.
The solubilities and the relevant physicochemical properties of the systems MgCl2 + MgB6O10 + H2O and MgSO4 + MgB6O10 + H2O at 323.15 K were determined by the method of isothermal dissolution, and the phase diagrams and the diagrams of physicochemical properties versus composition were plotted. Both of the systems belong to a simple eutectic type, and neither double salts nor solid solution were found. Based on the extended Harvie-Weare (HW) model and its temperature-dependent equations, the value of the singlesalt Pitzer parameters ??(0), ??(1), ??(2), and C ? for MgCl2, MgSO4, and Mg(B6O7)(OH)6, the mixed ion-interaction parameters $\theta _{Cl, B_6 O_{10} }$ , $\theta _{SO_4 , B_6 O_{10} }$ , $\Psi _{Mg, Cl, B_6 O_{10} }$ , $\Psi _{Mg, SO_4 , B_6 O_{10} }$ , the average equilibrium constants (lnK aver) of solids in the systems and the Debye-Hückel parameter A ? were fitted. Using the Pitzer parameters and the average equilibrium constants of solids at equilibrium, the solubilities of the two systems at 323.15 K have been calculated. Comparisons between the calculated and experimental results show that the predicted solubilities agree well with experimental data.  相似文献   

11.
Complex formation in the Nb6O 19 8? -WO 4 2? -H+-H2O system with c Nb : c W = 1 : 5 and varied c Nb + W 0 = 10?2, 5 × 10?3, 2.5 × 10?3, and 10?3 mol/L) has been studied. Distribution diagrams were simulated for individual niobium(V) and tungsten(VI) isopolyanions and mixed isopolyniobotungstates for $Z = \frac{{c_{H^ + }^0 }}{{c_{Nb + W}^0 }} = 0 - 3.0$ in an NaCl background electrolyte. We have shown that isopolyniobotungstates-6 of composition H x NbW5O 19 (3 ? x)? are formed via H x Nb n W6?n O 19 (2 + n ? x)? (n=2, 3, 5) ions. The concentration formation constants and thermodynamic formation constants of isopolyniobotungstate anions (IPNTAs) in aqueous solution have been calculated. Salt Tl3NbW5O19·9H2O has been synthesized and identified by chemical analysis and IR spectroscopy.  相似文献   

12.
Suprapolyhedral cluster precursors Kn with a hierarchical structure (with the number of polyhedra n = 4, 6, 8) have been derived and their topological representation as bichromatic graphs has been performed. With the use of computer methods (the TOPOS program package), combinatorial-topological analysis of icosahedral monster structures of close compositions Ir8Mg58 (cF396, F $ \bar 4 $ 3m, V = 8139 Å3) and Ir7Mg44 (cF408, F $ \bar 4 $ 3m, V = 8117 Å3) has been performed. Suprapolyhedral nanoclusters consisting of eight and six Ir icosahedra (nanoclusters i-K8 and i-K6 comprising 86 and 50 atoms) have been identified by the method of complete decomposition of the 3D factor graph of crystal structures into cluster substructures in Ir7Mg44. In Ir8Mg58, the i-K8 nanocluster is retained, whereas the i-K6 cluster is substituted by the K4 nanocluster composed of four Ir polyhedra with CN = 9 comprising 34 atoms. Complete 3D reconstruction of the self-assembly mechanism of crystal structure has been carried out by the scheme nanocluster precursor-primary chain-microlayer-microframework. It has been demonstrated that the voids in the Ir8Mg58 and Ir7Mg44 frameworks accommodate tetrahedral cluster spacers T-Mg(Mg4) and T-Mg4, respectively. The Ir6Mg26 structure (hR96, R $ \bar 3 $ c, V = 1890 Å3) is made of the suprapolyhedral cluster K6 formed by six Ir polyhedra with CN = 11 and comprising 50 atoms; in this case, the structure contains no cluster spacers. In all structures, nanoclusters retain their own symmetry ( $ \bar 4 $ 3m for i-K8, i-K6, and K4 and $ \bar 3 $ for K6).  相似文献   

13.
Cs2[(UO2)2(C2O4)3] (I) and Cs2[UO2(C3H2O4)2] · H2O (II) have been synthesized and studied by X-ray diffraction. The crystals of complexes I and II are monoclinic: a = 8.1453(2) Å, b = 8.9831(2) Å, c = 11.3897(4) Å, β = 104.0950(10)°, V = 808.29(4) Å3, space group P21/n, Z = 2, and R 1 = 0.0255 for I and a = 9.6998(2) Å, b = 17.8686(3) Å, c = 8.2074(2) Å, β = 97.5780(10)°, V = 1410.10(5) Å3, space group P21/c, Z = 4, and R 1 = 0.0287 for II. The uranium-containing structural units of complexes I and II are [(UO2)2(C2O4)3]2? chains and [UO2(C3H2O4)2] 2 4? dimers, which belong to the AK 0.5 02 T11 and AT11B01 crystallochemical groups (A = UO 2 2+ , K02 and T11 = C2O 4 2? , T11 and B01 = C3H2O 4 2? ) of uranyl complexes.  相似文献   

14.
The crystal structure of Cr3AsN has been determined by single crystal methods: Space group I4/mcm-D 4h 18 $$a = 5,360 {\AA}, c = 8,066{\AA}; c/a = 1,505$$ The crystal structure can be described by filling of the octahedral voids of the U3Si-type. The phases Mn3GeC, Mn3GeN1-x, and Fe3GeN1-x are isotypic to Cr3AsN.  相似文献   

15.
Modified wheat straw (MWS) was prepared by the grafting of epichlorohydrin, triethylamine and ethylenediamine onto WS. The characteristics of MWS and its adsorption capacity for NO 3 ? , PO 4 3? and Cr2O 7 2? were investigated. The results indicate that amine groups with positive charge have been introduced into the structure of MWS, and significantly increased its anion adsorption property. The functions of MWS dosage, the solution pH, the contact time and temperature have significant influence on the adsorption process, and the adsorption is well fitted with the Langmuir equation and pseudo second-order model. The maximum adsorption capacity of MWS for NO 3 ? , PO 4 (P) and Cr2O 7 2? (Cr) is 53.5, 62.4 and 386.2 mg g?1, respectively.  相似文献   

16.
The crystal structure of α-d-mannosido-benzo-18-crown-6·KSCN (1) was solved by X-ray single crystal diffractometry. C28H36O10·KSCN is orthorhombic, space groupP212121 withZ=4,a=8.035(4),b=9.960(2),c=38.83(2) Å,M r =629.8,V=3103.6 Å3,D x =1.347 g cm?3, μ(CuKα)=2.53 mm?1, λ=1.54178 Å,F(000)=1324. FinalR=0.043 for 1139 unique observed reflections measured at room temperature. The potassium ion is surrounded by a nearly planar hexagon of oxygen atoms of the macrocyclic ring and lies on the plane formed by those atoms. Hexagonal pyramidal coordination is completed by the nitrogen atom of the thiocyanate anion. The SCN ion was found on the face of the macrocyclic ring opposite that for the chiral mannopyranoside moiety. The molecular structure of α-d-mannosido-18-crown-6 (2) and the structure of molecular complexes of2 and α-d-glucosido-benzo-18-crown-6 (3) were studied by molecular mechanics methods. The results suggest enthalpy driven selectivity of complexation of the phenylalanine methyl ester (4) by2 and both enthalpy and entropy effects in selective complexation of4 by3.  相似文献   

17.
The gas-phase niobium oxochloride anions that result by the interaction between the finely dispersed stereoselective acetylene cyclotrimerization catalyst NbCl2(C n H n ) (n = 10–12) and atmospheric oxygen and moisture have been characterized by matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry. From the relative intensities of mass spectrometric lines, it has been deduced that, among the various niobium oxochloride species passing into the gas phase under the action of laser radiation, the most abundant monomer ion is NbO2Cl 2 ? , the most abundant dimers are Nb2O4Cl 3 ? and Nb2O3Cl 5 ? , the most abundant trimer is Nb3O6Cl 5 ? , and the most abundant tetramer is Nb4O8Cl 5 ? . The gas phase also contains low concentrations of fragments corresponding to the pentanuclear anion Nb3O11Cl 4 ? and the hexanuclear anion Nb6O15Cl 2 ? . The geometric parameters and total energy of the stable isomers of the dinuclear and polynuclear niobium oxochloride anions existing in the gas phase has been calculated by quantum chemical methods, and their relative thermodynamic stabilities have been determined for different metal core configurations and different arrangements of oxygen and chlorine ions. The stereochemistry of the niobium oxochlorides is discussed.  相似文献   

18.
The structure of premixisterone (I) — a new ecdysteroid fromS. praemixta M. Pop. (Caryophyllaceae) — has been established. Compound (I) has the composition C27H44O5, mp 110–112°C (from C2H5OH + H2O), [α] D 24 0 ± 4° (c 0.85; MeOH), \(\lambda _{\max }^{{\text{C}}_{\text{2}} {\text{H}}_{\text{5}} {\text{OH}}}\) 202 nm (log ? 3.35), ν max KBr 3415 cm?1 (OH), 1710 cm?1 (C=0), and does not contain the δ7-6-keto grouping that is characteristic of natural ecdysteroids. The acetylation of (I) with (CH3CO)2 in Py gave the amorphous 3,22-diacetylpremixisterone (II), C21H48O7. Compound (I) has the structure of 3β,14α,22R,25-tetrahydroxy-5β-cholest-8-en-6-one. The IR, PMR, and mass spectra of (I) and (II) are given.  相似文献   

19.
New (C17H20FN3O3)2[CoCl4]2·3H2O (I) and C17H20FN3O3[CoCl4]·H2O (II) compounds, where C17H18FN3O3 is ciprofloxacin (CfH), are synthesized and their crystal structures are determined. Crystallographic data for I: a = 18.441(5) Å, b = 9.030(3) Å, c = 27.551(8) Å, V = 4588(4) Å3, space group Pca21, Z = 4; for II: a = 9.305(3) Å, b = 9.885(3) Å, c = 12.999(4) Å, α = 82.782(4)°, β = 72.954(4)°, γ = 89.736(4)°, V = 1133(1) Å3, P-1 space group, Z = 2. Both structures contain CfH 3 2+ ion pairs bonded by the π-π interaction. Additionally, in the crystal of I there is a stacking interaction between the π clouds of aromatic rings and hydrogen atoms of the cyclopropyl group linking the pairs of molecules with each other. The structure of the centrosymmetric crystal of triclinic phase II is also formed from CfH 3 2+ ion pairs bonded by the π-π interaction, which, in this case, are not independent because they are related by the symmetry center. Hydrogen bonds form a branched three-dimensional network linking the CfH 3 2+ and CoCl 4 2? ions and water molecules.  相似文献   

20.
[[UO2(L)(OH)] (I), (CN3H6)2[(UO2)2CrO4(L)4] · 2H2O (II), and [UO2(H2O)5][(UO2)2Cr2O7(L)4] (III) crystals, where L is picolinate ion C5H4NCOO?, have been synthesized and studied by X-ray diffraction and IR spectroscopy. Complex I crystallizes in triclinic system with the unit cell parameters a = 6.2858(5) Å, b = 7.9522(5) Å, c = 8.3598(6) Å, α = 79.527(6)°, β = 87.760(6)°, γ = 79.126(6)°, space group P $\bar 1$ , Z = 2, R = 0.0306, and complexes II and III crystalize in monoclinic system with a = 8.8630(9) Å, b = 13.4540(13) Å, c = 31.266(3) Å, β = 93.118(3)°, space group C2/c, Z = 4, R = 0.0187 (II), and a = 7.3172(4) Å, b = 15.4719(8) Å, c = 16.6534(10) Å, β = 98.943(4)°, space group P21/m, Z = 2, R = 0.0588 (III). The structure of complex I is built of electronegative [UO2(L)(OH)] chains, which belong to the AT11M2 crystallochemical group (A = UO 2 2+ , T11 = L, M2 = OH?) of uranyl complexes. The structure of complexes II and III contains [(UO2)2(L′)(L)4]2? dimers (L′ = CrO 4 2? or Cr2O 7 2? ), which belong to the A2B2B 4 01 group (A = UO 2 2+ ,B2 = L′, B01 = L). The specifics of intermolecular interactions in the structures of complexes I–III and some their analogues have been considered using molecular Voronoi-Dirichlet polyhedra.  相似文献   

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