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1.
On K2Na4[O2BeOBeO2] For the first time colourless single crystals of K2Na4[Be2O5] which are isotypic with K2Na4[Co2O5] [2] and Rb2Na4[Co2O5] have been prepared by heating e.g. a well ground mixture of K2O, Na2O and BeO (K:Na:Be = 2.2:4.4:2; 750°C; 21 d; Ni-tube). The crystal structure was solved by four-circle diffractometer data [Siemens AED 2; 389 Io(hkl); space group P42/mnm; Z = 2; a = 595.17(4) pm, c = 1 002.66(9) pm; R = 4.1%; Rw = 2.3%]. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, the Madelung Part of Lattice Energy, MAPLE, and the charge distribution are calculated.  相似文献   

2.
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   

3.
K10[Co4O9], a New Oligooxocobaltate(II) For the first time dark-red single crystals of K10[Co4O9] were obtained by heating mixtures of KO0.48 and CdO (molar ratio 2.7:1) in closed Co-cylinders at 450°C during 73 d. Structure solution and refinement (four-circle diffractometer data, Mo Kα , 2 996 out of 2 996 Io(hkl), R = 5.20%, Rw = 3.03%) confirm the space-group P1 and show structural relationship with Na10[Co4O9] [2]. The lattice constants are a = 667.84(5) pm, b = 917.91(9) pm, c = 908.49(7) pm, α = 119.400(7)°, β = 90.851(7)°, γ = 110.260(6)°, Z = 1 . (powder data (Guinier-Simon), standard deviations in parentheses) MAPLE calculations are made and a comparative survey of MAPLE values of oxocobaltates(II) is given.  相似文献   

4.
Preparation of Crystal Structure of K6[Al2O6] and Rb6[Al2O6] Colourless single crystals of K6[Al2O6] have been prepared from intimate mixtures of KAlO2 and K2O (550°C, 90 d). The structure determination from four-circle diffractometer data (MoKα , 742 Io(hkl), R = 2.2%, Rw = 2.1%) confirms the space group C2/m with Z = 2; a = 698.25 pm, b = 1 103.54 pm, c = 646.49 pm, β = 102.49°. Colourless single crystals of hitherto unknown Rb6[Al2O6] have been prepared from intimate mixtures of RbAlO2 and Rb2O (520°C, 120 d). The structure determination from four-circle diffractometer data (MoKα , 1 240 Io(hkl)) results in the residual values R = 7.2%, Rw = 4.9%; space group C2/m; a = 725.92 pm, b = 1 143.33 pm, c = 678.06 pm, β = 104.05°; Z = 2. K6[Al2O6] and Rb6[Al2O6] are isostructural with K6[Fe2O6]. A characteristic structure unit is the anion [Al2O6]6? consisting of two edge-sharing [AlO4] tetrahedra. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.  相似文献   

5.
The First Oligooxoindate(III): K14[In4O13] For the first time K14[In4O13] was obtained by heating intimate mixtures of K2O, CdO and elementar In (molar ratio 3.1:1.0:1.0) in closed Ag-cylinders (30 days, 450°C) in form of yellow-brown single crystals. The structure determination by four circle diffractometer data MoKα, 3 689 out of 3 689 Io(hkl), R = 4.22, Rw = 2.45) confirms the space group P21/c with lattice constants a = 687.7 pm; b = 3 118.5 pm; c = 686.4 pm; β = 119.3°; Z = 2. The characteristic feature of the structure is [In4O13]14? groups, oligomers consisting of four corner-sharing InO4 tetrahedra. These groups are connected by crystallographically distinct potassium atoms. The structure is isotypic with Na14[Al4O13] [2] and K14[Fe3O13] [3]. ECoN and MAPLE calculationes are discussed.  相似文献   

6.
The First Oxide with the Formula Type K5[MO4]: K5[TlO4] Light yellow powder and pale yellow transparent single crystals of K5[TlO4] were newly prepared from mixtures of binary oxides (K2O/Tl2O3) preheated and levigated several times [closed Ag-cylinder, 580°C, 24 h and 600°C, 20 d]. Space group Pbca with a = 1170.4(3), b = 686.1(1), c = 2079.2(5) pm, Z = 8 [four-circle-diffraktometer data, 997 I0(hkl), R = 7.87%, Rw = 5.63%, MoKα] (parameter s. text). The crystal structure belongs to the Na5[GaO4] type. Structural aspects, ECoN and MAPLE are discussed.  相似文献   

7.
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   

8.
New Metal Oxides with Doubles of Tetrahedra as Building Units: Rb6[Tl2O6] and Cs6[In2O6] We prepared the hitherto unknown Rb6[Tl2O6] and Cs6[In2O6] by heating mixtures of Tl2O3 and RbO0.60 (Rb:Tl = 3.5:1) as well as In2O3 and CsO0.53 (Cs:In = 3.5:1) as single crystals [closed Ag-cylinder, 650°C, 14 d]. The single crystals of Rb6[Tl2O6] are yellow, those of Cs6[In2O6] pale yellow, all transparent and rude. The new type of structure was elucidated by 4-circle-diffractometer (PW 1100) data. Rb6[Tl2O6]: P21/a; a = 1145,7(3), b = 713,3(1), c = 783,9(2) pm, β = 93,73° (2), Z = 2; Ag–Kα, 2100 out of 2531 I0(hkl), R = 9,6% and Rw = 8,9%. Cs6[In2O6]: P21/a; a = 1178,5(4), b = 730,7(2), c = 816,3(2) pm, β = 95,38° (3), Z = 2; Mo–Kα, 1584 out of 2032 I0(hkl), R = 9,25%, and Rw = 8,44%. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.  相似文献   

9.
The First Oxocobaltate(II) with Dinuclear Anion: Rb2Na4[Co2O5] and K2Na4[Co2O5] By heating of well ground mixtures of the binary oxides [A2O, Na2O, ?CoO”?, A:Na:Co = 1.00:2.00:1, (A = K, Rb); Ag-tube, 600°C, 14 d] we obtained Rb2Na4[Co2O5] and K2Na4[Co2O5] rough, transparent, red single crystals. We find a new type of structure with the anion [O2CoOCoO2]6?. Space group P42/mnm; a = 634.4 pm, c = 1030.3 pm, Z = 2 (A = K) a = 647.6 pm, c = 1021.1 pm, Z = 2 (A = Rb); four-circle diffractometer data; MoKα -radiation; 360 from 364 I0(hkl), R = 4.34%, Rw = 3.54% (A = K); 361 from 366 I0(hkl), R = 6.54%, Rw = 2.70% (A = Rb). The anion is planar, the CN of Co is 3. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.  相似文献   

10.
A New Oxoindate K2Na3[InO4] We prepared the hitherto unknown K2Na3[InO4] on two different ways as single crystals
  • a) by heating mixtures of In2O3, NaO0.48 and KO0.60 (In:Na:K = 1:3.3:2.2) [Ag-cylinder, 580°C, 42 d].
  • b) by the oxidation of NaIn with Na2O2 and KO0.87 (In:Na:K = 1:2:6) [Ag-cylinder, 480°C, 8 d].
The single crystals of K2Na3[InO4] are colourless, all transparent and rough. The type of structure was elucidated by 4-circle diffractometer (Siemens AED 2) data: Pnnm; a = 955.5(4), b = 927.6(4), c = 753.4(2) pm; Z = 4; MoKα; 909 of 1031 I0(hkl); R = 9.7%, Rw = 3.9%. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.  相似文献   

11.
Inhaltsübersicht. Erstmals wurden klar durchscheinende, orange-farbene Einkristalle von Cs2Li14[Tb3O14] aus Cs2TbO3 und Li2O (Tb: Li = 1:5) dargestellt [550°C, 21 d, verschlossenes AuRohr]. Es liegt der K2Li14[Pb3O14]-Typ vor [Vierkreisdiffraktometerdaten, PW 1100, MoKä-Strahlung, 660 Io(hkl), R = 4,8%, Rw = 3,4%, Immm, a = 1293,5(8), b = 792,6(3), c = 740,4(3) pm, Z = 2, d = 4,65]. Ebenfalls neu wurde K2Li14[Zr3O14] in Form farbloser Einkristalle durch Tempern inniger Gemenge von K2O, Li2O und ZrO2 (K: Li: Zr = 1:4:1,5) dargestellt [900°C, 14 d, geschlossene Ni-Bombe] und röntgenographisch untersucht. Die Strukturverfeinerung [612 Io(hkl), Vierkreisdiffraktometerdaten, PW 1100, MoKα-Strahlung, R = 5,9%, Rw = 5,3%, Immm, a = 1244,6, b = 776,4, c = 724,3 pm, Z = 2] bestätigt die Isotypie mit K2Li14[Pb3O14]. Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECoN, diese über Mittlere Effektive Ionenradien, MEFIR, wurden berechnet. Für die nun bekannten Vertreter dieses Typs wurde ein Isotypievergleich vorgenommen. New Compounds of the K2Li14[Pb3O14] Type: Cs2Li14[Tb8O14] and K2Li14[Zr3O14] For the first time Cs2Li14[Tb3O14] has been prepared as orange single crystals from Cs2TbO3 and Li2O (Tb: Li = 1:5) [550°C, 21 d, sealed Au-Tube]. Structure Refinement [four-circle diffractometer data, PW 1100, MoKα radiation, 660 Io(hkl), R = 4.8%, Rw = 3.4%, Immm, a = 1293.5(8), b = 792.6(3), c = 740.4(3) pm, Z = 2, d = 4.65] confirms isotypy with K2Li14[Pb3O14]. K2Li14[Zr3O14] has also been prepared as colorless single crystals from K2O, Li2O, and ZrO2 (K: Li: Zr = 1:4:1.5), [900°C, 14 d, closed Ni-cylinder] and investigated by x-ray [612 Io(hkl), four-circle diffractometer data, PW 1100, MoKα radiation, R = 5.9%, Rw = 5.3%, Immm, a = 1244.6, b = 776.4, c = 724.3 pm, Z = 2]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Fictive Ionic Radii, MEFIR, are calculated. A detailed comparison of the structures is carried out.  相似文献   

12.
Na2[Pr4O2]Cl9 and K2[Pr4O2]Cl9, the First Reduced Quaternary Praseodymium Chlorides with Anti-SiS2 Analogous [Pr4/2O] Chains The compounds A2[Pr4O2]Cl9 (A = Na, K) are the first reduced quaternary praseodymium chlorides with anti-SiS2 analogous [Pr4/2O] chains. Synthesis took place in the temperature range from 900 to 600°C in silica-jacketed niobium containers from Pr metal, PrCl3, PrOCl and NaCl (KCl) as starting materials. The X-ray structure analysis of a single crystal of Na2[Pr4O2]Cl9 (monoclinic, P21/m (No. 11), Z = 2, a = 812.2(2) pm, b = 1 134.1(2) pm, c = 937.6(2) pm, β = 106.51(2)°, R = 0.048, Rw = 0.037) exhibits trans-edge connected chains of [Pr4/2O] tetrahedra running along [001] which are connected by surrounding common chloride ions forming layers parallel to (001). These layers are connected by further chloride ions to a three-dimensional network. The sodium ions surrounded by a heavily distorted octahedron of chloride ions are placed between the layers. The X-ray structure analysis of a single crystal of the otherwise isotypic K2[Pr4O2]Cl9 (monoclinic, P21/m (No. 11), Z = 2, a = 820.6(2) pm, b = 1 133.2(4) pm, c = 949.2(3) pm, β = 103.94(2)°, R = 0.073, Rw = 0.054) shows that potassium is coordinated by nine chloride ions.  相似文献   

13.
Oxidation of Intermetallic Phases: Na3[AuO2] from NaAu and Na2O2 The hitherto unknown Na3[AuO2] was prepared in transparent, colourless single crystals from NaAu and Na2O2[1:1; sealed Ag-cylinder, 430°C, 6 d]. The crystal structure (P42/mnm); a = 970.5(1), c = 457.8(1) pm; Z = 4; four-circle diffractometer PW 1100, 333 out of 380 I0(hkl), R = 7.0% and [Rw = 6.5%] was solved. Like KAgO-Type there are planar rings [Na2Au2O4]4?. Na(1) has the uncommon coordinations number 2 . The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated.  相似文献   

14.
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   

15.
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   

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.
On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7], and Tl2[Mo4O4Cl14] and the Structure of Tl2[MoCl6] Black crystals of Tl2[MoCl6] are formed in the reaction of TlCl with MoOCl3 in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl2[MoCl6] (cubic, Fm m, a = 986.35(7) pm) adopts the K2[PtCl6] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl4(NCCH3)] was obtained by the reaction of TlCl with MoOCl3 in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl+ cations and octahedral [MoOCl4(NCCH3)] anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl3 in dichloromethane yields Tl[Mo2O2Cl7] and Tl2[Mo4O4Cl14] as green moisture sensitive crystals. The structure of Tl[Mo2O2Cl7] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl+ cations and dinuclear [Mo2O2Cl7] anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl2[Mo4O4Cl14] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl+ cations and [Mo4O4Cl14]2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl5) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.  相似文献   

18.
On the Constitution of Peroxotantalates(V) with Alkali Metals: On the Structure of K3[Ta(O2)4] [1] By solving of recently precipitated Ta2O5 · aq in a 1.5-molar solution of KOH in 3% H2O2 and subsequently cooling at 0°C we obtained colourless single-crystals of K3[Ta(O2)4]. The compound crystallizes tetragonal (spacegroup 142m) with a = 679.5(1) pm, c = 791.2(1) pm, Z = 2 (Guinier-de-Wolff powder data). The determinated crystal structure (four-circle diffractometer, 444 out of 444 I0(hkl); R = 1.51%, Rw = 1.48%, parameters see text) proves that K3[Ta(O2)4] is isotypic with K3[Cr(O2)4] [2]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, as well as charge distribution (CHARDI) are calculated and discussed.  相似文献   

19.
K6[Mn2O6] and K6[Fe2O6] - a Comparison K6[Mn2O6] has been prepared (dark-red single crystals). The structure (a = 8.886, b = 6.760, c = 11.394 Å, γ = 132.1°, space group P21, Z = 2, 1151 symmetry independent reflections hk0–hk9, R = 0.051) shows Al2Cl6-like anions [Mn2O6]6?. By unit-cell transformation to the monoclinic setting P21/a (a = 6.760, b = 11.394, c = 6.638 Å, β = 96,9°) the structural similarity to K6[Fe2O6] becomes evident. The Madelung Part of Lattice Energy, MAPLE, is calculated.  相似文献   

20.
A New Nesoindate: KNa9In2O8 = KNa9[InO4]2 We prepared hitherto unknown KNa9[InO4]2 (colourless, transparent single crystals) from NaIn, Na2O2, and ?K2O2”? (molar ratio NaIn:Na2O2:?K2O2”? = 2:3.5:0.6, Ag-cylinder, 460°C, 6d). A new type of structure is found. The single crystal data are: Pnma, a = 1802.4(3), b = 729.5(2), c = 907.9(3) pm; Z = 4 [four-circle diffractometer PW 1100, MoKα; 1856 out of 1870 I0(hkl); R = 3.7% and Rw = 3.4%]. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.  相似文献   

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