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1.
[TMPA]4[Si8O20] · 34 H2O ( 1 ) and [DDBO]4[Si8O20] · 32 H2O ( 2 ) have been prepared by crystallization from aqueous solutions of the respective quaternary alkylammonium hydroxide and SiO2. The crystal structures have been determined by single-crystal X-ray diffraction. 1 : Monoclinic, a = 16.056(2), b = 22.086(6), c = 22.701(2) Å, β = 90.57(1)° (T = 210 K), space group C2/c, Z = 4. 2 : Monoclinic, a = 14.828(9), b = 20.201(7), c = 15.519(5) Å, β = 124.13(4)° (T = 255 K), space group P21/c, Z = 2. The polyhydrates are structurally related host-guest compounds with three-dimensional host frameworks composed of oligomeric [Si8O20]8? anions and H2O molecules which are linked via hydrogen bonds. The silicate anions possess a cube-shaped double four-ring structure and a characteristic local environment formed by 24 H2O molecules and six cations (TMPA, [C8H20N2]2+, or DDBO, [C8H18N2]2+). The cations themselves reside as guest species in large, irregular, cage-like voids. Studies employing 29Si NMR spectroscopy and the trimethylsilylation method have revealed that the saturated aqueous solutions of 1 and 2 contain high proportions of double four-ring silicate anions. Such anions are also abundant species in the saturated solution of the heteronetwork clathrate [DMPI]6[Si8O18(OH)2] · 48.5 H2O ( 3 ) with 1,1-dimethylpiperidinium (DMPI, [C7H16N]+) guest cations.  相似文献   

2.
On the Compound BaO · Al2O3 · 7 H2O On the basis of investigations using 27Al, 1H NMR, IR and thermoanalytical methods for the compound BaO · Al2O3 · 7 H2O a constitution as Ban[Al2(OH)8]n · 3n H2O with condensed AlO6 groups, sharing edges, is proposed. Relations between the Ba/Al ratio and the constitution of anions of barium aluminate hydrates are discussed.  相似文献   

3.
Hydrothermal reaction of K7H[Nb6O19]·13H2O with Na2SiO3·9H2O (220 °C, 24 h) produces a lacunary siliconiobate [Si4Nb16O56]16?, which was isolated as mixed salt NaK8H6[Na@Si4Nb16O56]·26H2O (1). Changing the silicon source to Ph2Si(OH)2 under the same conditions slightly improves the yield of [Si4Nb16O56]16?, which was isolated as K14H[K@Si4Nb16O56]·26H2O (2). Extending the reaction time leads to rearrangement of [Si4Nb16O56]16? into Keggin-type silicododecaniobate [SiNb12O40]16?, which was isolated and characterized as K8H2(Nb2O2)[SiNb12O40]·20H2O (3). The complexes were characterized by X-ray single crystal analysis, elemental analysis, thermogravimetry, 29Si NMR.  相似文献   

4.
The crystal structures of four substituted‐ammonium dichloride dodecachlorohexasilanes are presented. Each is crystallized with a different cation and one of the structures contains a benzene solvent molecule: bis(tetraethylammonium) dichloride dodecachlorohexasilane, 2C8H20N+·2Cl·Cl12Si6, (I), tetrabutylammonium tributylmethylammonium dichloride dodecachlorohexasilane, C16H36N+·C13H30N+·2Cl·Cl12Si6, (II), bis(tetrabutylammonium) dichloride dodecachlorohexasilane benzene disolvate, 2C16H36N+·2Cl·Cl12Si6·2C6H6, (III), and bis(benzyltriphenylphosphonium) dichloride dodecachlorohexasilane, 2C25H22P+·2Cl·Cl12Si6, (IV). In all four structures, the dodecachlorohexasilane ring is located on a crystallographic centre of inversion. The geometry of the dichloride dodecachlorohexasilanes in the different structures is almost the same, irrespective of the cocrystallized cation and solvent. However, the crystal structure of the parent dodecachlorohexasilane molecule shows that this molecule adopts a chair conformation. In (IV), the P atom and the benzyl group of the cation are disordered over two sites, with a site‐occupation factor of 0.560 (5) for the major‐occupied site.  相似文献   

5.
On the Crystalline Phases of the Systems M O? Al2O3? H2O (MI = K, Na) In the system K2O? Al2O3? H2O the compounds K2O · Al2O3 · 3 H2O, K2O · Al2O3 · 2 H2O and K2O · Al2O3 · 1 H2O exist. The results of 27Al and 1H NMR and IR spectroscopic investigations as well as thermoanalytical measurements confirm the existence of dimeric anions with tetrahedrally coordinated Al for the 3-hydrate. In the case of the two other hydrates higher molecular anions occur, also formed by AlO4 tetrahedra. In the system Na2O? Al2O3? H2O a compound with a composition Na2O · Al2O3 · 2,5 H2O and two alkali oxide rich phases (Na/Al > 3) are observed. In monosodium aluminate hydrate there are highly polymerized anions with tetrahedrally coordinated Al, whereas the alkali oxide rich phases are probably built up by monomeric [Al(OH)6]3? anions.  相似文献   

6.
29Si NMR spectra of polycrystalline Ca6[Si2O7¦(OH)6] and [(CH3)4N] 8Si8O20·69H2O were measured using the cross polarization double-resonance technique. Observed shielding tensors are related to the known Si-O bond systems. The arrangement of the four Si-O bonds in the SiO4 tetrahedra is reflected by the 29Si shielding tensor. The most shielded direction corresponds to the shortest Si-O bond.  相似文献   

7.
Sealing of components for high temperature applications with coefficients of linear thermal expansion (CTE) > 10·10−6 K−1 can be achieved by glasses from which crystalline phases with high CTE are precipitated. Many sealing glasses also contain further components as e.g. aluminium and hence, not only the desired phase is crystallized, but also additional phases. For this purpose, high temperature XRD was performed in order to determine the CTE of BaAl2Si2O8, CaAl2Si2O8, and Ca2Al2SiO7. In the case of BaAl2Si2O8 and Ca2AlSi2O7 the CTEs were 7.8·10−6/K and 7.9·10−6/K, respectively. In the case of CaAl2Si2O8 the CTE is 4.4·10−6/K. Especially the formation of the latter phase should be avoided for a sealing material of high temperature fuel cells. Sintered specimens of the respective compounds were also characterized by dilatometry.  相似文献   

8.
The crystal structures of quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate trihydrate, C9H8N+·C7H5O6S·3H2O, (I), 8‐hydroxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate monohydrate, C9H8NO+·C7H5O6S·H2O, (II), 8‐amino­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate dihydrate, C9H9N2+·C7H5O6S·2H2O, (III), and 2‐carboxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate quinolinium‐2‐carboxylate, C10H8NO2+·C7H5O6S·C10H7NO2, (IV), four proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases, reveal in each the presence of variously hydrogen‐bonded polymers. In only one of these compounds, viz. (II), is the protonated quinolinium group involved in a direct primary N+—H⋯O(sulfonate) hydrogen‐bonding interaction, while in the other hydrates, viz. (I) and (III), the water mol­ecules participate in the primary intermediate interaction. The quinaldic acid (quinoline‐2‐carboxylic acid) adduct, (IV), exhibits cation–cation and anion–adduct hydrogen bonding but no direct formal heteromolecular interaction other than a number of weak cation–anion and cation–adduct π–π stacking associations. In all other compounds, secondary interactions give rise to network polymer structures.  相似文献   

9.
The Crystal Structures of K8Ta6O19 · 16H2O and K7NaTa6O19 · 14H2O By alkaline digestion of Ta2O5 with p.a. KOH transparent single crystals of the composition K8Ta6O19 · 16H2O are formed. When technical grade KOH is used, the same kind of synthesis yields crystals of the composition K7NaTa6O19 · 14H2O. The latter compound has been given the formula K8Ta6O19 · 14H2O until now. In both cases the isopolyoxoanion [Ta6O19]8 consists of six TaO6-octahedra connected by edge sharing. This means that the heavy atom partial structure found by Lindquist et al. is confirmed. Additionally the complete structures including the atomic positions of the oxygen atoms of the polyanions as well as those of the cations and crystal water molecules (without hydrogen positions) are determined.  相似文献   

10.
The synthesis and crystal structures of a series of six crystalline potassium salts of hypodiphosphoric acid, H4P2O6, are reported, namely potassium hydrogen phosphonophosphonate, K+·H3P2O6, (I), dipotassium dihydrogen hypodiphosphate monohydrate, 2K+·H2P2O62−·H2O, (II), dipotassium dihydrogen hypodiphosphate dihydrate, 2K+·H2P2O62−·2H2O, (III), pentapotassium hydrogen hypodiphosphate dihydrogen hypodiphosphate dihydrate, 5K+·HP2O63−·H2P2O62−·2H2O, (IV), tripotassium hydrogen hypodiphosphate tetrahydrate, 3K+·HP2O63−·4H2O, (V), and tetrapotassium hypodiphosphate tetrahydrate, 4K+·P2O64−·4H2O, (VI). All the hypodiphosphate anions, viz. H3P2O6, H2P2O62−, HP2O63− and P2O64−, adopt a staggered conformation. The P—P bond lengths [2.1722 (7)–2.1892 (10) Å] do not depend on the basicity of the anion. The compounds are organized into different types of one‐, two‐ or three‐dimensional polymeric hydrogen‐bonded networks, or simply exist in the form of isolated or dimeric units. The coordination numbers of the K+ cations range from 6 to 9, and the cationic sublattices are polymeric one‐, two‐ or three‐dimensional networks, or isolated [KO6] or dimeric [K2O12] polyhedra.  相似文献   

11.
The1H NMR spectra of the hydrated monocationic forms of clinoptilolite M6[Al6Si30O72]·nH2O (M=Li, Na, K, Cs, NH4; n=12–22) and M 3 [Al6Si30O72]·nH2O (M′=Mg, Ca, Sr, Ba; n=20–24) and heulandite M8[Al8Si28O72]·21H2O (M=Na, K) are divided into three types differing in the symmetry of tensors of magnetic dipole-dipole interactions of protons in zeolite water molecules. On the basis of model calculations it is shown that water molecules in the Cs, K, and Ba forms of clinoptilolite and the K form of heulandite are ordered in structural positions. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Zeorex Ltd., Sofia. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 5, pp. 891–900, September–October, 1996. Translated by L. Smolina  相似文献   

12.
The structure of zeolite water in single crystals of natural zeolites represented by clinoptilolite Na2K2Ca[Al6Si30O72]·22H2O and heulandite Ca3Mg[Al8Si28O72]·24H2O is studied with 1H NMR. Below 170 K the distribution of H2O over the structural positions is shown to be fixed but different for the two minerals. Above 290 K translational and orientational diffusion of zeolite water molecules is observed and the structure of water is almost identical in both heulandite and clinoptilolite. Diffusion mechanism may be associated with the interaction between librational modes of H2O and high-frequency oscillations of aluminosilicate framework. The microwave absorption is shown to be caused in certain conditions by this type of interaction.  相似文献   

13.
The system hexafluorosilicic acid-water was studied by low-temperature difference thermal analysis and X-ray powder diffraction in the water-rich range of 80--100 mol% H2O. A quasi-binary behavior was found and the melting diagram constructed. It shows the existence and stability ranges of three crystalline hydrates H2SiF6 · nH2O with n = 4, 6, and 9.5. They melt congruently at 20 and ?12°C, and incongruently at ?54°C, respectively. The hydrates were further characterized by determination of their structures from single-crystal MoKα diffractometer data. They were found to be oxonium salts. The ionic formulae, in the order of increasing water content, are (H5O2)2SiF6, (H5O2)2SiF6 · 2 H2O, and (H5O2)(H7O3)SiF6 · 4.5 H2O. The structures are governed by extensive O? H ?O and O? H ?F hydrogen bonding. The water structure of the 9.5-hydrate, with the cationic and neutral species taken together, is an unusual three-dimensional network which hydrogen-bonds the anions in channels.  相似文献   

14.
A novel borophosphate‐hydrate, (Ni3–xMgx)[B3P3O12(OH)6] · 6 H2O (x ≈ 1.5), has been prepared by hydrothermal synthesis (T = 170 °C) from a mixture of NiCl2 · 6 H2O, Mg(OH)2, B2O3 and H3PO4. The crystal structure was determined at 293 K from single‐crystal X‐ray diffraction data (trigonal, R3c (no. 167), a = 14.957(10) Å, c = 13.812(6) Å, V = 2676(2) Å3, Z = 6, R1 = 0.0276, wR2 = 0.0714 for 779 observed reflections with I > 2σ(I)). The crystal structure contains unbranched six‐membered rings [B3P3O12(OH)6]6– of alternating corner linked borate and phosphate tetrahedra, which are stacked along [001] and connected via MIIO2(OH)2(H2O)2 coordination polyhedra. Hydrogen bonding between the tetrahedral six‐membered rings and MIIO2(OH)2(H2O)2 octahedra leads to a further cross‐linking. With respect to the arrangement of isolated six‐membered tetrahedral rings the crystal structure of this borophosphate‐hydrate is closely related to the cyclo‐hexasilicate dioptase, Cu6[Si6O18] · 6 H2O.  相似文献   

15.
Single-crystalline materials of Li[H2N3C3O3] · 1.75 H2O and Mg[H2N3C3O3]2 · 8 H2O were obtained by dissolving stoichiometric amounts of the respective carbonates with cyanuric acid in boiling water followed by gentle evaporation of excess water after cooling to room temperature. Even though both of these compounds crystallize in the triclinic space group P1 according to X-ray structure analyses of their colorless and transparent single crystals, they adopt two new different structure types. Li[H2N3C3O3] · 1.75 H2O exhibits the unit-cell parameters a = 884.71(6) pm, b = 905.12(7) pm, c = 964.38(7) pm, α = 67.847(2)°, β = 62.904(2)° and γ = 68.565(2)° (Z = 4), whereas the lattice parameters for Mg[H2N3C3O3]2 · 8 H2O are a = 691.95(5) pm, b = 1055.06(8) pm, c = 1183.87(9) pm, α = 85.652(2)°, β = 83.439(2)° and γ = 79.814(2)° (Z = 2). In both cases, the singly deprotonated isocyanuric acid forms monovalent anions consisting of cyclic [H2N3C3O3] units, which are arranged in ribbons typical for most hitherto known monobasic isocyanurate hydrates. The structures are governed by the oxophilic strength of the respective cation which means that they fulfil their oxophilic coordination requirements either solely with water molecules ([Mg(OH2)6]2+ for Mg2+) or with crystal water and one or two direct coordinative contacts to carbonyl oxygen atoms (O(cy)) of [H2N3C3O3] anions ([(Li(OH2)2–3(O(cy)1–2]+ for Li+). In both structures occur dominant hydrogen bonds N–H ··· O within the anionic [H2N3C3O3] ribbons as well as hydrogen bonds O–H ··· O between these ribbons and the hydrated Li+ and Mg2+ cations.  相似文献   

16.
The arsenomolybdates [H2As2Mo6O26(H2O)] · (H2biyb)2 · 2H2O ( 1 ) and [H3As2Mo6O26] · (H3pt)2 ( 2 ) [biyb = 1,4‐bis(imidazol‐1‐ylmethyl)benzene, pt = 4′‐(3′′‐pyridyl)‐2,3′:6′3′′‐terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [HxAs2Mo6O26](6–x)–. The structure of 1 is constructed from the B‐type [H2As2Mo6O26(H2O)]4– polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3 · 4 · 53 · 6}{3 · 43 · 52}{3 · 5 · 6}2{3 · 52}2 topology structure. In compound 2 , the A‐type [H3As2Mo6O26]3– clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {43 · 63}2{46 · 66 · 83} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected.  相似文献   

17.
Crystals of hypoxanthinium (6‐oxo‐1H,7H‐purin‐9‐ium) nitrate hydrates were investigated by means of X‐ray diffraction at different temperatures. The data for hypoxanthinium nitrate monohydrate (C5H5N4O+·NO3?·H2O, Hx1 ) were collected at 20, 105 and 285 K. The room‐temperature phase was reported previously [Schmalle et al. (1990). Acta Cryst. C 46 , 340–342] and the low‐temperature phase has not been investigated yet. The structure underwent a phase transition, which resulted in a change of space group from Pmnb to P21/n at lower temperature and subsequently in nonmerohedral twinning. The structure of hypoxanthinium dinitrate trihydrate (H3O+·C5H5N4O+·2NO3?·2H2O, Hx2 ) was determined at 20 and 100 K, and also has not been reported previously. The Hx2 structure consists of two types of layers: the `hypoxanthinium nitrate monohydrate' layers (HX) observed in Hx1 and layers of Zundel complex H3O+·H2O interacting with nitrate anions (OX). The crystal can be considered as a solid solution of two salts, i.e. hypoxanthinium nitrate monohydrate, C5H5N4O+·NO3?·H2O, and oxonium nitrate monohydrate, H3O+(H2O)·NO3?.  相似文献   

18.
Thermal decomposition of iron(II) and cobalt(II) hexaborates has been investigated. The methods applied to investigate the process were differential thermal analysis, derivatography, crystallooptics and x-ray study. The following iron(II) hexaborate hydrates, FeO · 3B2O3 · 7.5H2O, FeO · 3B2O3 · 5H2O, FeO · 3B2O3 · 0.5H2O; iron(III) borates, Fe2O3 · 6B2O3 and 2Fe2O3 · B2O3; cobalt(II)hexaborate hydrates CoO · 3B2O3 · 7.5H2O, CoO · 3B2O3 · 5H2O, CoO · 3B2O3 · 0.5H2O, CoO · 3B2O3 and the decomposition product 2CoO · 3B2O3 have been isolated. Hepta- and semihydrates of cobalt(II) and iron(II) hexaborates have been proved to be isomorphous. It has been established that in the case of cobalt and iron hexaborates the exothermic maximum refers to a decomposition reaction and to the formation of a borate containing a smaller proportion of boron and boric anhydride.  相似文献   

19.
Condensed Phosphates of Melamine The title compounds with the formulae (C3H6N6)n · Hn+2PnO3n+1 (linear phosphates, n = 2; 3) and (C3H6N6 · HOP3)m (cyclic phosphates, m = 3; 4; 6; 8 and high polymeric phosphate) are obtained as crystalline hydrates by interaction of the corresponding sodium phosphates with stoichiometric amounts of melamine hydrochloride and hydrochloric acid or melamine hydrochloride in aqueous solution. With the exception of (C3H6N6 · HPO3)4 · 6H2O ( I ) these hydrates decompose at ~100°C forming a mixture of mono and diphosphate which transforms at ~200°C into pure melamine diphosphate and at ~250°C into melamine polyphosphate. In contrast to this I froms at ~100°C the anhydrous melamine tetrametaphosphate which converts at ~150°C into melamine polyphosphate. Melamine diphosphate and polyphosphate are also formed on heating melamine monophosphate C3H6N6 · H3PO4.  相似文献   

20.
Thermal Dehydration of Lithium Dihydrogenphosphate, -Hydrogen-diphosphate, and -Cyclophosphate Hydrates On heating lithium dihydrogenphosphate, LiH2PO4, is converted to lithium polyphosphate, (LiPO3)n · H2O [2–5]. Seeding LiH2PO4 with lithium cyclohexaphosphate, Li6P6O18, the thermal dehydration proceeds structurally controlled to pure Li6P6O18. On heating lithium hydrogen-diphosphate, Li3HP2O7, reacts to Li4P2O7 form III and lithium cyclotetraphosphate, Li4P4O12 form II , which ist converted to Li6P6O18 at higher temperatures. The thermal dehydration of Li2H2P2O7 and of the cyclophosphate hydrates Li3P3O9 · 3 H2O, Li4P4O12 · (8 and 6) H2O, Li6P6O18 · (6 and 4) H2O and Li8P8O24 · (10 and 6) H2O are described.  相似文献   

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