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1.
The First Binuclear Oxoferrate(II): ?Cs2K4[O2FeOFeO2]”? For the first time ?Cs2K4[Fe2O5]”? was obtained by annealing intimate mixtures of Cs2O, K2O, and CsFeO2 (molar ratio Cs : K : CsFeO2 1.3 : 2.1 : 1) in a closed Fe-cylinder (74 d; 470°C) in the form of red single crystals. The structure determination (four-circle diffractometer, MoKα , 760 out of 857 Io(h kl); R = 5.8%, Rw = 4.6%) confirms the space group C2/m; a = 707.4, b = 1138.5, c = 699.7 pm, β = 91.76°, Z = 2. Essential part of the structure is the binuclear, planar [O(1)2Fe? O(2)? FeO(1)2]6? group which is for the first time observed with oxoferrates(II). Despite different space groups the crystal structure is related to that of Rb2Na4[Co2O5].  相似文献   

2.
“Fragmentation” and “Aggregation” on Lead Oxides. On the Oligooxoplumbate(IV) K2Li6[Pb2O8] For the first time, the dinuclear Oxoplumbate(IV) K2Li6[Pb2O8] has been prepared as transparent colourless single crystals by heating mixtures of K2PbO3, Li2O, and “PbO2” with K:Li:Pb = 1:3:1 e. g. [Ag-cylinders, sealed under vacuum in Supremax-glass ampoule, 660°C, 120 d]. The structure determination verifies the space group P1 with a = 6.9720(9), b = 5.9252(6), c = 5.9312(7) Å, α = 88.05(1)°, β = 107.94(1)°, γ = 107.30(1)°; dx = 4.95 g · cm?3, dpyk = 4.91 g · cm?3; Z = 1, [2107 symmetry independent hkl, fourcircle-diffractometer Philips PW 1100, ω—2Θ—scan, MoKα, R = 5.07%, Rw = 4.59%, absorption not considered]. The structure is characterized by the group [Pb2O8] — two edge connected (equatorial/apical) trigonal bipyramids — that is observed for the first time. Several ways of synthesis are given. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated.  相似文献   

3.
New Oxides with the “Butterfly-Motive”: Rb6[Fe2O5] and K6[Fe2O5] Rb6[Fe2O5] and K6[Fe2O5] were obtained for the first time by annealing intimate mixtures of “Rb6CdO4” with CdO (molar ratio 1 : 1.1) and KO0.48 with CdO (molar ratio 5.9 : 1) respectively in closed Fe-cylinders. Determination and refinement of the crystalstructure confirms the space group C2/m (four-circle-diffractometer data). Rb6[Fe2O5]: Ag Kα , 720 out of 1220 Io(hkl), R = 9.68%, Rw = 6.09%; a = 718.9pm, b = 1183.1 pm, c = 695.4pm, β = 95.05°, Z = 2; K6[Fe2O5]: MoKα , 1214 Out of 12141o(hkl), R = 3.20070, Rw = 2.48%, a = 691.21 pm, b = 1142.78pm, c = 665.50pm, β = 93.82°, Z = 2. The binuclear unit [O2FeOFeO2]6? already known to be planar with oxoferrates(II) now was observed to be angular here and closely related to Na6[Be2O5].  相似文献   

4.
A New Oxoferrate with “Butterfly-Motiv”: K2Na4[Fe2O5] Dark red-brown single-crystals of K2Na4[Fe2O5] were obtained for the first time by heating “K3Na3CdO4” at 500°C in closed Fe-cylinders. Determination and refinement of the crystal structure confirms the space group P42/mnm (No. 136). Four-circle diffractometer data: MoKα , 373 out of 373 Io(hkl); R = 5.3%; Rw = 4.6%; a = 645.94(5), c = 1 039.2(1) pm. In contrast to the already known oxoferrates(II) with the “Butterfly-Motiv”, Rb6[Fe2O5] and K6[Fe2O5] [1], we now found an isotypic structure for K2Na4[Fe2O5] with the oxocobaltates of Rb2Na4[Co2O5] and K2Na4[Co2O5] [2].  相似文献   

5.
On Tantalates and Niobates ‘rich in Cations’. On Na5TaO5 and Na5NbO5 Colourless, transparent single crystals of Na5TaO5 [annealed mixtures of Na2O, Li2O, and Ta2O5, Na : Li : Ta = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] as well as Na5NbO5 [annealed mixtures of Na2O, Li2O, and Nb2O5, Na : Li : Nb = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] have been prepared. Single crystal data show that both isotypic oxides represent a deformed variant of the NaCl-type of structure [Na5TaO5: 1154 from 1250 I0 (hkl), four-cycle diffractometer Philips PW 1100, ω2-θ scan, Ag? Kα , R = 4.88%, space group c2/c with a = 629.3(1) pm, b = 1025.4(2) pm, c = 1004.6(2) pm, b? 106.80(2)°, z = 4 and Na5NbO5: 998 from 1247 I0(hkl), four-cycle diffractometer Philips PW 1100, ω-2θ scan, Ag? Kα , R = 8.58% and Rw = 7.67%, space group C2/2 with a = 629.1(1) pm, b = 1024.4(2) pm, c = 1004.2(2) pm, b? = 106.80(2)°, Z = 4]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Fictive Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.  相似文献   

6.
Employing a “one‐pot” synthesis strategy, the reaction of Na2WO4·2H2O, Na2HAsO4·7H2O, FeCl3·6H2O, various Ln3+ ions, and hexamethylenetetramine (HMTA) in aqueous solutions with pH values ranging from 5.5 to 6.5 results in the isolation of polytungstoarsenate‐based iron aggregates, ‐K8Na14[HMTA]4[(FeIII3FeII0.25(OH)3)(AsO4)(AsW9O34)]4·24H2O ( 1 ) (HMTA = hexamethylenetetraamine). The polyoxoanion of 1 contains a mixed‐valent {FeIII12FeII3‐OH)124‐AsO4)4} cluster surrounded by four [B‐α‐AsW9O34]9? units. It is the first polytungstatoarsenate‐based mixed‐valent {FeIII12FeII} aggregate and the largest iron cluster based on [AsW9O34]9? ligands. The compound was characterized by elemental analyses, IR, UV/Vis absorption, and diffuse‐reflectance UV/Vis spectroscopy, TG analyses, XRPD, XPS and gel‐filtration chromatography. The electrochemical and electrocatalytical properties were also investigated. Crystal data for 1 , orthorhombic, Fddd, a = 28.156(6) Å, b = 36.003(7) Å, c = 42.126(8) Å, α = 90°, β = 90°, γ = 90°, Z = 8.  相似文献   

7.
The First Mixed-valent Oxoplumbate with Isolated Anions. On KNa7[PbIVO4][PbIIO3] For the first time KNa7Pb2O7 has been prepared by reaction of K and Na Oxides with ?PbO2”? rsp. PbOred [e. g.: KO0.48:NaO0.36:?PbO2”? = 1:7:2 (Ag-cylinders, reduced Ar-pressure, sealed in supremax-glas ampoules, 600°C, 14 d): redorange single crystals of plated shape]. The structure determination [3269 Io(hkl), four-circle diffractometer PW 1100 (Fa. Philips), ω-scan, MoKα, R = 9.52%, Rw = 7.67%, absorption not considered] proves the space group P21/c with a = 1758.48(10), b = 596.76(3), c = 1066.46(8) pm, β = 90.682(8)°, Z = 4, dx = 4.311, dpyk = 4.28 g/cm3. The structure is characterized by isolated [PbIVO4] (symmetry nearly Td) and [PbIIO3] groups (symmetry nearly C3v), the latter connected by cations to double-layers. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.  相似文献   

8.
The Mixed‐Valent Oxoferrate(II,III) K3[Fe2O4] – A Stuffed Variant of the K2[Fe2O4] Type of Structure K3[Fe2O4] has been obtained by tempering “Cs3K3CdO4” in sealed Fe containers (36 d at 450–480 °C) as dark red transparent single crystals of rectangular shape. The structure determination (IPDS diffractometer data, MoKα, 1891 collected reflections, 234 symmetry independent, R1 = 0.033, wR2 = 0.088) confirms the space group Fddd; a = 596.11(9), b = 1140.3(1), c = 1717.9(3) pm; Z = 8. K3[Fe2O4] exhibits a structure with [FeO4] tetrahedra connected via corners leading to a three‐dimensional network closely related to the KFeO2 type of structure. From the oxidation at 520 °C of iron metal with KO2 in the presence of Na2O black single crystal of K2[Fe2O4] have been obtained. K2[Fe2O4] crystallizes in the space group Pbca with Z = 8 and a = 559.18(7), b = 1122.1(1), c = 1592.8(2) pm (IPDS diffractometer data, MoKα, collected refelctions: 9543, 1213 symmetry independent, R1 = 0.043, wR2 = 0.102).  相似文献   

9.
The First Diniobate with ‘Isolated’ Anions: KLi4[NbO5]=K2Li8[Nb2O10] [1] . By heating of well ground mixtures of the binary oxides [K2O, Li2O, Nb2O5, K:Li:Nb=1.1:4.4:1, Pt-tube, 1100°C, 3d] colourless, triclinic single crystals of KLi4NbO5 have been prepared for the first time: space group P1 (Nr. 2) with a=816.9(2) pm, b=592.2(2) pm, c=589.7(2) pm, α=121.00(2)º, β=91.78(2)°, γ=99.23(2)°, Z=2. The crystal structure was solved by four-cycle diffractometer data [Mo-Kα , 1386 from 1386 Io(hkl), R=3.4%, Rw=2.6%], parameters see text. Characteristic for this structure are “isolated” groups of [Nb2O10] and the tetrahedral coordination of Li(1), Li(2), and Li(3). Li(4) has a tetragonal-pyramidal coordination. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution have been calculated and discussed.  相似文献   

10.
The oxoplatinates Na2PtO2, Na2PtO3, ?K2PtO3”? and ?Rb2PtO3”?. Hitherto unknown Na2PtO2 (greyish black) was prepared. Na2PtO2 (orthorhombic, D—Immm; a = 4.585, b = 3.119, c = 9.588 Å) is isotypic with Li2CuO2. α-Na2PtO3 (darkyellow; red as single-crystals) is monoclinic, C—C2/c (a = 5.419, b = 9.385, c = 10.752 Å, β = 99.67°), Li2SnO3-type. According to 3-dimensional single crystal data hitherto unknown β-Na2PtO3 (red crystals) is an orthorhombic variant of the Li2SnO3-type (a = 18.838, b = 6.282, c = 9.062 Å, Z = 16, D—Fddd; parameters see text); R = 0.0809, R' = 0.0948 [256 reflexes (hk0—hk6)]. The Madelung part of the lattice energy (MAPLE) is calculated and discussed for α-, β-Na2PtO3, α- and β-PtO2. For the first time we got K2PtO3 and Rb2PtO3.  相似文献   

11.
The First ?Lithovanadate”?: K2{LiVO4} By heating of well ground mixtures of the binary oxides [K2O, Li2O, V2O5, K:Li: V = 2.2:1.1:1.0; Ni-tube, 900°C, 46 d] colourless monoclinic single crystals of K2[LiVO4] have been prepared for the first time: space group C2/m; a = 835.7(1) pm, b = 774.5(1) pm, c = 753,3(1) pm, β = 90.23(1)°. The structure was determined by four-circle diffractometer data [MoKα, 1018 form 1262 I0 (hkl), R = 8.65%, Rw = 5.67%], parameters see text. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, have been calculated.  相似文献   

12.
New Oxoferrates(III). On the Knowledge of Na14[Fe6O16] Na14Fe6O16 crystallizes triclinic (P1 ) with a = 11.427, b = 8,271, c = 5.953 Å, α = 109.3, β = 87.7, γ = 111.4°, Z = 1, 2166 independent reflexions, R = 0.051. FeO4 tetrahedra are connected by common cornes forming ?Zweier-Doppel-Ketten”? Effektive Coordination Numbers, ECoN, and the Madelung Part of Lattive Energy, MAPLE, are calculated and discussed.  相似文献   

13.
About Perrhenates. 3 On the Structure of the Mesoperrhenate Na3[ReO5] By tempering powder samples (prepared from mixtures of binary oxides: Na2O2/ReO2 and Na2O/ReO3 respectively, Na : Re = 3 : 1, Ar and O2 atmosphere respectively, 400–450°C, corundum boat) in a closed Ag cylinder (500–550°C, 10 d) yellow single crystals of Na3ReO5, sensitive to moisture, were grown. The compound crystallizes trigonal, space group P31, P32 respectively, with a = 5.544(1), c = 13.580(7) Å, Z = 3, drö. = 4.62 g/cm3. The crystal structure [4-circle diffractometer data, 1091 I0(hkl), AgKα, R = 6.14, Rw = 6.08%] is characterized by “isolated” bipyramids ReO5. Na+ ions are occupying all the tetrahedral (Na2, Na3) and octahedral (Na1) holes of the pseudocubic face centred (c/a = 2.441) Re part of the lattice; resulting in a Na3Re kation framework corresponding to the Li3Bi type of structure. Effective Coordination Numbers (ECoN), the Madelung Part of Lattice energy (MAPLE) and the charge distribution (CHARDI) are computed and discussed.  相似文献   

14.
On Oxotitanates of the Alkaline Metals: On Na4Ti5O12 Colourless single crystals of the new titanate Na4Ti5O12 (starting from mixtures Na2O/TiO2, 1000°C, 6 d, Au-crucible, open system) crystallize in the monoclinic system, space group C2/m, a = 26.544(9), b = 2.952(1), c = 6.322(3) Å, β = 95.79(3)°, Z = 2, d = 3.45 and dpyk = 3.38 g · cm?3 (four-cycle-diffractometer data, PW 1100, 2?-scan, MoKα). R = 5.09% and Rw = 4.87% for 1178 independent I0(hkl) with 3° ≤ 2? ≤ 34°. Corrugated layers of Ti5O12, held together by Na+, are stacked along [001]. Details about partially occupied positions of Na+, Effective Coordination Numbers (ECoN), the Madelung part of lattice energy (MAPLE), and the structural differences to Na2Ti3O7 are discussed.  相似文献   

15.
On Oxostannates(II). V. Na4[SnO3] – The First Oxostannate (II) with Island Structure The new oxid Na4SnO3 (yellow, transparant single crystals) has been prepared by heating of mixtures of: 1. NaO0.45 and SnO (Na:Sn2+ = 4.1:1; Ag-cylinders; 600–730°C, 7–66 d); 2. NaO0.45′ SnO2 and Sn±0 (Na:Sn4+:Sn±0 = 8.2:1:1; Ag-cylinders; 650–680°C, 2–66 d); 3. NaO0.45′ Na2SnO3 and Sn±0 (Na:Na2SnO3:Sn±0 = 6.1:1:1; Ag-cylinders; 650–670°C, 5 d). Na4SnO3:804 I0(hkl); four circle diffractometer PW 1100; ω-scan; MoKα; R = 5.14%; Rw = 4.64%; monoclin, Cc? C; a = 582.77(11), b = 1667.44(24), c = 589.42(10) pm, β = 110.187(13)°; dx = 3.20 g/cm3; dpyk = 3.19 g/cm3; Z = 4; parameter look for text. It is a NaCl-variant with systemathical blanks of the anion part and “isolated” groups of [SnO3]. \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm N}\mathop {\rm a}\limits^{\rm 1} $\end{document} has the uncommon coordination number 2. The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated. The structure is described using ?Erweiterte Schlegeldiagramme”?.  相似文献   

16.
Chains consisting of Rings: K5{Li[Ge2O7]} — the First ‘Litho-Digermanate’ By heating of a well-ground mixture of the binary oxides KO0.55, Li2O and GeO2 (K: Li: Ge = 6.1 : 2.2 : 2; Ni-tube; 600°C; 49 d) we obtained for the first time single crystals of K5{Li[Ge2O7]}. This ‘lithodigermanate’ represents a completely new type of structure: monoclinic, space group P21/c, a = 624.9(2) pm, b = 1586.6(8) pm; c = 1058.3(6) pm and β = 109.38(4)°; Guinier-Simon data, Z = 4. The structure was solved by four-circle diffractometer data [Siemens AED II, Mo? Kα ; 2872 Io(hkl); R = 4.5%, Rw = 3.3%], parameters see text. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, as well as charge distribution CHARDI, are calculated and discussed.  相似文献   

17.
New obtained is K2Cd2O3 (brownish red), which – according to single crystal work [487 h 01–h 41, Mo? Kα, R = 9.73%, R′ = 10.76%] – crystallises monoclinic with a = 6.417, b = 6.723, c = 6.586 Å, β = 116.0° in P21/c–C [K+, Cd2+ and O(1)2? in 4(e), O(2)2? in 2(a)] and is isotypic with Na2Zn2O3. [Parameters see text]. The Madelung Part of Lattice Energy is calculated and discussed.  相似文献   

18.
A New ?Orthoindate”? of an Alkali Metal: K5[InO4] Hitherto unknown K5[InO4] was prepared by heating intimate mixtures of K2O, In2O3 and elementar In (molar ratio 10.0 : 1.0 : 4.0) in closed Ni-cylinders (30 days, 500°C) in form of pale red, nearly colourless, transparent, single crystals. Same crystals were obtained by heating mixtures of K2O, CdO and elementar In (molar ratio 3.1 : 1.0 : 1.0) in closed Ag-cylinders (30 days, 450°C), too. In this case we also found yellow-brown crystals of K14[In4O13] [1]. Structure determination by four circle diffractometer data (MoKα, 15279 out 17454 Io(hkl), R = 5.60%, Rw = 5.25%). Space group P1 with a = 1827.9 pm; b = 1694.4 pm; c = 1329.4 pm; α = 113.3°; β = 111.4°; γ = 105.2°; Z = 16. Characteristic feature of the structure are isolated [InO4]5?-tetraeder. The Madelung Part of Lattice Energy, MAPLE, the Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and Charge Distribution, VADI, are calculated.  相似文献   

19.
The First Tetraferrate(III): K14[Fe4O13] For the first time K14[Fe4O13] was obtained by annealing intimate mixtures of K2O and LiFeO2 (molar ratio 2.2:1) in closed Ni-cylinders (6 months, 610°C) in the form of yellow-brown single crystals. The structure determination (four circle diffractometer, MoKα, 3377 of 3377 Io(hkl); R = 4,52%, Rw = 2,53%) confirms the space group P21/c; a = 677.9, b = 2956.2, c = 672,1 pm, β = 120.31°, Z = 2. Essential part of the structure are tetranuclear [Fe4O13]14?-groups, oligomers consisting of four corner-sharing FeO4-tetrahedra. Within the structure these groups are connected by two crystallographically distinct K-particles thus forming bands which are arranged according to a ?closest packing of bands”? interconnected by the rest of the K-particles. The structure is described via Schlegel-diagrams. It is isotypic with Na14[Al4O13].  相似文献   

20.
What is “Molybdic Acid” or “Polymolybdic Acid”? According to a comparative study of the literature, supplemented by well-aimed experimental investigations and equilibrium calculations, the terms “molybdic acid” or “polymolybdic acid”, used for many substances, species, or solutions in the literature, are applicable to a species, a solution, and two solids:
  • a) The monomeric molybdic acid, most probably having the formula MoO2(OH)2(H2O)2(? H2MoO4, aq), exists in (aqueous) solution only and never exceeds a concentration of ≈ 10?3 M since at higher concentrations it reacts with other monomemeric molybdenum (VI) species to give anionic or cationic polymers.
  • b) A concentrated (>0.1 M MoVI) aqueous molybdate solution of degree of acidification P = 2 (realized, e. g., by a solution of one of the MoVI oxides; by any molybdate solutions whose cations have been exchanged by H3O+ on a cation exchanger; by suitable acidification of a molybdate solution) contains 8 H3O+ and the well-known polyanion Mo36O112(H2O)168? exactly in the stoichiometric proportions.
  • c) A glassy substance, obtained from an alkali metal salt-free solution prepared according to (b), refers to the compound (H3O)8[Mo36O112(H2O)16]·xH2O, x = 25—29.
  • d) A solid having the ideal composition [(H3O)Mo5O15(OH)H2O·H2O]∞ consists of a polymolybdate skeleton (the well-known ?decamolybdate”? structure), in the tunnels of which H3O+ and H2O are intercalate. The structure is very unstable if only H3O+ cations are present, but it is enormously stabilized by a partial exchange of H3O+ by certain alkali or alkaline earth metal cations.
For the compounds MoO3, MoO3·H2O, and MoO3·2H2O the term ?molybdic acid”? is unjustified. The commercial product ?molybdic acid, ≈85% MoO3”? is the well-known polymolybdate (NH4)2O·4 MoO3 with a layer structure of the polyanion.  相似文献   

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