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1.
Inhaltsübersicht. Einkristalle von NaInBr4 und NaInI4 erhält man aus Gemengen der binären Komponenten durch langsames Abkühlen der Schmelze. NaInBr4 gehört zum NaAlCl4-Typ: Orthorhombisch, P212121, Z = 4; a = 1108,1(1); b = 1050,7(1); c = 676,1(1) pm. NaInI4 ist isotyp mit LiAlCl4: Monoklin, P21/c, Z = 4; a = 852,1(2); b = 766,1(2); c = 1558,3(3) pm; β = 92,65(2)°. In beiden Strukturen treten annähernd tetraedrische Baugruppen [InX4] (X = Br, I) auf. Die Koordinationszahl von Na+ ist C.N. = 6 (NaInI4; leicht verzerrt oktaedrisch) bzw. C.N. = 6+1+1 (NaInBr4; verzerrtes, doppelt bekapptes Prisma). Synthesis and Crystal Structures of NaInBr4 and NaInI4 Single crystals of NaInBr4 and NaInI4 are obtained from mixtures of the binary components by slow cooling of the melts. NaInBr4 belongs to the NaAlCl4 type of structure: Ortho-rhombic, P212121, Z = 4, a = 1108.1(1), b = 1050.7(1), c = 676.1(1) pm. NaInI4 is isotypic with LiAlCl4: Monoclmic, P21/c, Z = 4, a = 852.1(2), b = 766.1(2), c = 1558.3(3) pm, β = 92.65(2)°. Almost tetrahedral polyhedra [InX4] (X = Br, I) are characteristic for both structures. The coordination number of Na+ is C.N. = 6 (NaInI4; slightly distorted octahedron) and C.N. = 6+1+1 (NaInBr4; distorted bicapped trigonal prism), respectively.  相似文献   

2.
The Crystal Structures of the Vanadium Weberites Na2MIIVIIIF7 (MII ? Mn, Ni, Cu) and of NaVF4 At single crystals of the vanadium(III) compounds NaVF4 (a = 790.1, b = 531.7, c = 754.0 pm, β = 101.7°; P21/c, Z = 4), Na2NiVF7 (a = 726.0, b = 1031.9, c = 744.6 pm; Imma, Z = 4) and Na2CuVF7 (a = 717.6, b = 1043.5, c = 754.6 pm; Pmnb, Z = 4) X-ray structure determinations were performed, at Na2MnVF7 (a = 746.7, c = 1821.6 pm; P3221, Z = 6) a new refinement. NaVF4 crystallizes in the layer structure type of NaNbO2F2. The fluorides Na2MIIVF7 represent new orthorhombic (MII ? Ni; Cu) resp. trigonal (MII ? Mn) weberites. The average distances within the [VF6] octahedra of the four compounds are in good agreement with each other and with data of related fluorides (V? F: 193.3 pm). The differences between mean bond lengths of terminal and bridging F ligands are 5% in NaVF4, but less than 1% in the weberites. Details and data for comparison are discussed.  相似文献   

3.
Alkaline Metal Oxoantimonates: Synthesis, Crystal Structures, and Vibrational Spectroscopy of ASbO2 (A = K, Rb), A4Sb2O5 (A = K, Rb, Cs), and Cs3SbO4 The compounds ASbO2 (A = K/Rb; monoclinic, C2/c, a = 785.4(3)/799.6(1) pm, b = 822.1(4)/886.32(7) pm, c = 558.7(3)/559.32(5) pm, β = 124.9(1)/123.37(6)°, Z = 4) are isotypic with CsSbO2 and the corresponding bismutates. The structures of the antimonates A4Sb2O5 (A = K/Rb: orthorhombic, Cmcm, a = 394.9(1)/407.34(7) pm, b = 1807.4(1)/1893.5(1) pm, c = 636.34(9)/655.60(8) pm, Z = 2) and Cs4Sb2O5 (monoclinic, Cm, a = 1059.81(7) pm, b = 692.68(8) pm, c = 811.5(1) pm, β = 98.7(1)°, Z = 2) both contain the anion [O2SbOSbO2]4–. Cs3SbO4 (orthorhombic, Pnma, a = 1296.1(1) pm, b = 919.24(8) pm, c = 679.95(6) pm, Z = 4) crystallizes with the K3NO4 structure type.  相似文献   

4.
Isothiocyanate Complexes of Copper(II) with Square-Planar and Tetragonal-Pyramidal Coordination: Structure, Phase Transitions, and Redox-Properties In dependence on the kind and size of the counter-cations Cu2+-ions form isothiocyanate complexes with different coordination number and geometry. The structures of compounds with square-planar coordination [(NEt4)2[Cu(NCS)4] · CHCl3 (brown): Space group 14/mmm, Z = 2; a = 1204.3(2) pm, c = 1154.2(3) pm] and with tetragonal-pyramidal polyhedra [(NEt4)3[Cu(NCS)5] · SM (green, SM: unidentified solvent molecule): Space group P21/c, Z = 4; a = 1154.2(6) pm, b = 2291.6(10) pm, c = 1739.9(9) pm, ß = 95.98(5)°] are reported. The green complex transforms into a brown compound at room-temperature; the transformation is (partly) reversibly. Solutions of NCS-anions and Cu2+ are redox unstable. The structure of a resulting product: (PPh4)2[Cu2(NCS)2] [Space group C2/c, Z = 4; a = 1235.4(1) pm, b = 1347.1(2) pm, c = 2953.4(11) pm, ß = 99.36(2)°] with Cu(I) dimers and two bridging NCS- ligands is also reported.  相似文献   

5.
Preparation and Crystal Structure of SnTl4Se3 with a Note on TlSe We describe the preparation and crystal structure of SnTl4Se3. It crystallizes as a low symmetric distorted derivative with the In5Bi3 type of structure, which itself should be considered as a subfamily of the Cr5B3 type of structure: a = 852.2(2) pm, c = 1 272.2(6) pm, c/a = 1.49, Z = 4. Short Sn? Se distances of 311 pm, and 326 pm, respectively, are obtained in [SnSe2/2] chains running along [001]. Furthermore, short Tl? Se distances are found in quasimolecular bent moieties Tl2Se: 300 pm, 313 pm, and 347 pm, respectively. SnTl4Se3 is a semiconductor. The conductivity of some closely related phases are also reported. Finally, the structure of the well known compound TlSe has been refined for the first time, in order to get some more information about Tl1+? Se distances for square-antiprismatic coordinated Tl1+ ions.  相似文献   

6.
New Fluorozirconates and ‐hafnates with V2+ and Ti2+ During investigations of the systems MF2/KF/MF4 e. g. MF2/NaF/MF4 (M2+ = Ti2+, V2+, M4+ = Zr4+, Hf4+) we obtained blue crystals of VZrF6, VHfF6, KVZrF7, blue‐green crystals of NaVHf2F11, yellow crystals of TiHfF6 and NaTiHf2F11, and yellow to rubyred crystals of TiZrF6, respectively. According to single crystal data, VZrF6 VHfF6 and TiZrF6 crystalizes in the ordered ReO3‐type (cubic, Fm3m, a = 812,1(5), 804,2(8), and 821,0(2) pm, Z = 4). TiHfF6 crystalizes in a high‐temperature‐modification (cubic, ReO3‐type, Pm3m, a = 392,3(2) pm, Z = 2). KVZrF7 is isotyic to KPdZrF7 (orthorhombic, Pnna, a = 1109,8(6), b = 788,0(7), c = 648,0(15) pm, Z = 4). NaTiHf2F11 and NaVHf2F11 crystalizes monoclinic (C2/m, a = 910,5(7), b = 675,9(7), c = 773,6(5) pm, β = 116,10(6)° and a = 917,7(5), b = 685,7(5), c = 752,4 pm, β = 118,28(1)°, Z = 2, respectively) and are also isotypic to already known AgPdZr2F11.  相似文献   

7.
Hydrogenselenates of Rare Earth Elements: Syntheses and Crystal Structures of La(HSeO4)3 and Gd(HSeO4)(SeO4) Colorless transparent single crystals of La(HSeO4)3 (hexagonal, P63/m, Z = 2, a = 971.7(1), c = 616.98(8) pm, Rall = 0.0440) were obtained from the reaction of La2O3 and conc. selenic acid. La(HSeO4)3 is isotypic with the corresponding hydrogensulfate. Its structure can be seen as a variant of the UCl3 type structure with complex anions and contains the La3+ ions in ninefold coordination of oxygen atoms. Single crystals of Gd(HSeO4)(SeO4) crystallize from a solution of Gd2O3 in selenic acid (70% H2SeO4). In the orthorhombic crystal structure (Pbca, Z = 8, a = 920.4(1), b = 1351.6(2), c = 1004.0(1) pm, Rall = 0.0276) the Gd3+ ions are coordinated by eight oxygen atoms belonging to four SeO42– and four HSeO4 ions. These are surrounded by four Gd3+ ions.  相似文献   

8.
Halide Sulfates of Gadolinium: Synthesis and Crystal Structure of GdClSO4 and GdFSO4 Single crystals of GdClSO4 are obtained from the reaction of Gd2(SO4)3 and GdCl3 in silica ampoules. In the monoclinic compound (P21/c, Z = 4, a = 943.7(1), 657.59(8), 680.05(9) pm, β = 104.87(2)?, Rall = 0.0352) Gd3+ is surrounded by five sulfate groups and three chloride ligands. One of the sulfate groups acts as a bidentate ligand so that the coordination number of Gd3+ is nine. The reaction of Gd2(SO4)3 with LiF in sealed gold ampoules yields colorless transparent single crystals of GdFSO4. The compound crystallizes orthorhombic (Pnma, Z = 4, a = 843.6(1), b = 701.76(8), c = 643.38(7) pm, Rall = 0.0207) and contains eight‐coordinate Gd3+ ions. The ligands are six oxygen atoms of five sulfate groups and two fluoride ions.  相似文献   

9.
Single Crystals of La[AsO4] with Monazite‐ and Sm[AsO4] with Xenotime‐Type Structure Brick‐shaped, transparent single crystals of colourless monazite‐type La[AsO4] (monoclinic, P21/n, a = 676.15(4), b = 721.03(4), c = 700.56(4) pm, β =104.507(4)°, Z = 4) and pale yellow xenotime‐type Sm[AsO4] (tetragonal, I41/amd, a = 718.57(4), c = 639.06(4) pm, Z = 4) emerge as by‐products from alkali and rare‐earth metal chloride fluxes whenever the synthesis of lanthanide(III) oxoarsenate(III) derivatives from admixtures of the corresponding sesquioxides in sealed, evacuated silica ampoules is accompanied by air intrusion and subsequent oxidation. Nine oxygen atoms from seven discrete [AsO4]3? tetrahedra recruit the rather irregular coordination sphere of La3+ (d(La3+?O2?) = 248 – 266 pm plus 291 pm) and even a tenth ligand could be considered at a distance of 332 pm. The trigonal dodecahedral figure of coordination consisting of eight oxygen atoms at distances of 236 and 248 pm (4× each) about Sm3+ is provided by only six isolated tetrahedral [AsO4]3? units. Alternating trans‐edge condensation of the latter with the [LaO9+1] polyhedra of monazite‐type La[AsO4] and the [SmO8] polyhedra of xenotime‐type Sm[AsO4] constitutes the main structural chain features along [100] or [001], respectively. The bond distances and angles of the complex [AsO4]3? anions range within common intervals (d(As5+?O2?) = 167 – 169 pm, ?(O–As–O) = 100 – 116°) for both lanthanide(III) oxoarsenates(V) presented here.  相似文献   

10.
Cs5Sb8 and β‐CsSb: Two New Binary Zintl Phases The anion in the crystal structure of the new Zintl phase Cs5Sb8 synthesized from the elements (monoclinic, space group P21/c, a = 724.4(2) pm, b = 1135.2(3) pm, c = 2750.9(8) pm, β = 96.663(5)°, Z = 4) consists of two and three bonded Sb atoms, which are connected to form puckered nets with 5 and 28 membered rings. β‐CsSb (monoclinic, space group P21/c, a = 1519.4(3) pm, b = 734.0(2) pm, c = 1432.2(2) pm, β = 113.661(3)°, Z = 4) crystallizes with a superstructure of the LiAs structure type. As in the α phase (NaP type), twobonded Sb atoms form neary ideal 41 screx chains. In contrast to the α phase the helices have opposite chirality.  相似文献   

11.
Structure and Properties of TlZnPO4 and TlZnAsO4 TlZnPO4 and TlZnAsO4 have polymorphic behavior with two phase transitions (TlZnPO4: 263°C, 450°C; TlZnAsO4: 562°C, 752°C) between room temperature and the congruent melting point at 1 090°C for TlZnPO4 and 930°C for TlZnAsO4. X-ray diffraction powder patterns have shown, that the compounds are isotypic and crystallize in the monoclinic system with the lattice constants a = 882.8(2), b = 546.2(1), c = 872.9(1) pm, β = 90.61(2)° for TlZnPO4, a = 895.4(1), b = 562.3(1), c = 892.8(1) pm, β = 91.08(2)° for TlZnAsO4, Z = 4, space group P21. TlZnPO4 and TlZnAsO4 belong to the „stuffed derivatives”︁ of the Icmm structure type with a [ZnXO4] network of corner linked alternating ZnO4 and XO4 tetrahedra (X = P, As) with channels of six-membered rings in the direction of the c axis. These cavities contain the Tl cations. The results of 31P MAS-NMR measurement of TlZnPO4 may be correlated with its structure. The Tl+ ionic conductivity at 300°C reaches only values of 4.4 × 10−8 Ω−1 cm−1 for TlZnPO4 and 4.5 × 10−8 Ω−1 cm−1 for TlZnAsO4.  相似文献   

12.
BaClSCN and Na4Mg(SCN)6: Two New Thiocyanates of the Alkaline Earth Metals The reaction of BaCl2 and NaSCN yielded single crystals of BaClSCN (P 21/m, Z = 2, a = 588.6(1) pm, b = 465.8(1) pm, c = 864.4(2) pm, β = 100.20(3)°, Rall = 0.0214). According to X‐ray single crystal investigations, the structure consists of anionic SCN and Cl layers, respectively, alternating in [001] direction. The SCN‐ions are connected via the N and the S atoms to the cations. Na4Mg(SCN)6 (P 3 1c, Z = 2, a = 863.8(1) pm, c = 1399.3(2) pm, Rall = 0.0870), which was obtained from a melt of NaSCN and MgCl2, consists of anionic layers with the cations between the sheets. The holes are filled altenatingly by Na+ or Na+ and Mg2+. Regarding only the C‐atoms of the SCN group, the structure can be described as a hexagonal closest packing whith the cations occupying 5/6 of the octahedral voids.  相似文献   

13.
Synthesis and Crystal Structures of the Ternary Rare Earth Chlorides NaMCl4 (M = Eu—Yb, Y) Single crystals of NaErCl4 were obtained from the melt of NaCl and ErCl3 (1:1 molar ratio) by slow cooling. It crystallizes in the monoclinic crystal system (space group P2/c) with the structure of α-NiWO4 with a = 632.24(9) pm, b = 759.78(9) pm, c = 674.2(1) pm, b? = 92.310(3)°, Z = 2. Two preparative routes to pure powder samples of the chlorides NaMCl4 are described. At room temperature, these are found to be isotypic with NaErCl4 (M = Tm—Yb; II) while the triclinic structure of NaGdCl4 is adopted with M = Gd—Ho, Y (I). Phase transitions from one structure to the other are observed for all compounds. The transition temperatures decrease with decreasing size of the ion M3+.  相似文献   

14.
Quaternary Chlorides of Divalent Europium and Trivalent Transition Metal Ions: Synthesis and Crystal Structure of Na6Eu3M4Cl24 (M = Ti, V, Cr) The reaction of EuCl2, NaCl and MCl3 (M = Ti, V, Cr) yields the chlorides Na6Eu3M4Cl24. According to X‐ray single crystal investigations, their crystal structure is a variant of the monoclinic cryolite‐type structure. One crystallographic site is occupied by Na1 and Eu simultaneously. For charge compensation the Na2 site is not fully occupied. In Na6Eu3Ti4Cl24 (P21/n, Z = 1/2, a = 663.8(1) pm, b = 718.3(1) pm, c = 953.3(2) pm, β = 91.55(2)°, Rall = 0.0314), Na6Eu3V4Cl24 (P21/n, Z = 1/2, a = 660.4(1) pm, b = 715.8(1) pm, c = 946.5(2) pm, β = 91.41(2)°, Rall = 0.0313) and Na6Eu3Cr4Cl24 (P21/n, Z = 1/2, a = 654.8(1) pm, b = 706.5(1) pm, c = 945.4(2) pm, β = 91.07(2)°, Rall = 0.0368) the ratio of Na1 : Eu amounts to 5 : 3. The colours of the compounds, orange yellow for M = Ti, orange red for M = V and dark red for M = Cr, indicate electronic interactions between Eu2+ and M3+.  相似文献   

15.
Crystal Structures of MgCrO4-type Li2VCl4 and Spinel-type Li2MgCl4 and Li2CdCl4 The crystal structures of the ternary lithium chlorides Li2MCl4 (M = Mg, V, Cd) have been determined firstly by X-ray single-crystal experiments. Li2MgCl4 and Li2CdCl4 crystallize in an inverse spinel structure (space group Fd3 m, Z = 8, a = 1 040.1(2) and 1 062.06(9) pm, structural parameters u = 0.25699(2) and 0.2550(1), R = 1.7 and 3.7% for 218 and 211 unique reflections). The Li? Cl distances of the tetrahedrally coordinated Li+ ions are significantly greater than calculated with Shannon's crystal radii ( > 238 ± 1 instead of 233 pm). Contrary to the results of X-ray powder data reported in the literature, Li2VCl4 crystallizes in the distorted spinel structure of MgCr2O4 type (space group F4 3m, Z = 8, a = 1 037.49(2) pm, R = 5.9% for 217 unique reflections). The decrease of the site symmetry of the octahedrally coordinated ions (V2+, Li+) from 3 m to 3m resulting in contracted and widened tetrahedral M4 entities of the spinel structure is obviously caused by V? V metal—metal bonds (shortest V? V distance 366.2(7) pm).  相似文献   

16.
KEu2Cl6 and K1.6Eu1.4Cl5: Two New Mixed‐Valent Europium Chlorides The reaction of the binary chlorides EuCl3, EuCl2 and KCl yields the mixed‐valent compounds KEu2Cl6 and K1.6Eu1.4Cl5. KEu2Cl6 (hexagonal, P63/m, Z = 1, a = 788.87(13), c = 411.41(6) pm, R1 = 5.40 %) crystallizes with an addition‐variant of the UCl3‐type of structure with tricapped trigonal prismatic coordination for the europium cations. The K+ ions reside in channels along [001] and exhibit extremely large displacement parameters U33. The crystal structure of K1.6Eu1.4Cl5 (orthorhombic, Pnma, Z = 4, a = 1260.49(12), b = 871.05(9), c = 787.18(10) pm, R1 = 4.77 %) is closely related to that one of K2EuCl5 if the K+ and the Eu3+ ions are partly substituted for Eu2+. Absorption spectra show transitions, which can be assigned to Eu2+ and Eu3+ ions, and additional transitions due to interaction of both cations occupying common positions.  相似文献   

17.
Synthesis and Crystal Structure of the known Zintl Phases Cs3Sb7 and Cs4Sb2 Cs3Sb7 and Cs4Sb2 were synthesized from the elements and their crystal structures were determined on the basis of single crystal x‐ray data. Cs3Sb7 crystallizes in the monoclinic system with space group P21/c (a = 1605.7(1) pm, b = 1571.1(1) pm, c = 2793.9(2) pm, β = 96.300(2)°, Z = 16) and contains anions Sb73–. In the structure of Cs4Sb2 (orthorhombic, space group Pnma, a = 1598.5(3) pm, b = 631.9(2) pm, c = 1099.5(2) pm, Z = 4) dumbbells Sb24– are present.  相似文献   

18.
On K4PbO4 and Rb4PbO4 For the first time single crystals of K4[PbO4] have been prepared by heating K4PbO3 in O2. The structure has been refined [K4[PbO4]: 3029 I0(hkl), four circle diffractometer PW 1100, ω-scan, MoKα, R = 6.73%, Rw = 6.64%, P1 ; a = 658.62(15), b = 658.41(12), c = 986.64(21) pm, α = 79.74(2)°, β = 108.45(2)°, γ = 112.49(2)°, dx = 3.79 g · cm?3, dpyk = 3.78 g · cm?3, Z = 2; Rb4[PbO4]: a = 686.94(18), b = 684.43(18), c = 1020.73(21) pm, α = 79.28(2)°, β = 108.40(2)°, γ = 113.02(2)°, dx = 4.87 g · cm?3, dpyk = 4.85 g · cm?3, Z = 2, (from Rb2PbO3 and Rb2O)]. Both compounds are isotypic with K4SnO4. The Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.  相似文献   

19.
Sr5[NbN4]N (transparent, red single crystals) was synthesized by reaction of Sr2N with Nb under nitrogen at ambient pressure and 1223 K. The crystal structure was solved and refined in the space group Pbcm (no. 57), Z = 4, with lattice constants a = 646.6(3) pm, b = 1792.5(9) pm, c = 729.8(4) pm, and R = 0.019, wR2 = 0.034. The crystal structure contains both isolated tetrahedra [NbN4]7‐ as well as chains of corner sharing octahedra 1(Sr4Sr2/2N7+). Strontium is irregularly coordinated by nitrogen (CN = 4 ‐ 6, Sr‐N: 252.3(4) ‐ 340.8(3) pm); nitrogen is located in a distorted octahedral environment by strontium and niobium (Nb‐N: 194.5(4) ‐ 199.2(2) pm). By formal reduction of the structural building units to their centers a close structural relationship to both the NiAs and the CaSi type structure is evident.  相似文献   

20.
On Fluorides of Univalent and Divalent Mercury For the first time Rb2HgF4 and Cs2HgF4, both colourless, have been obtained. From single crystal investigations they crystallize tetragonal in the K2NiF4-type of structure, space group I4/mrnm-D4h17 (No. 139) with a = 455.6 pm, c = 1375.7 pm, Z = 2 for Rb2HgF4 and a = 462.5 pm, c = 1451.8 pm, Z = 2 for Cs2HgF4. The determination of the crystal structure of Hg2F2 confirmed the unit cell [1] with a = 367.00(4) pm, c = 1090.1(2) pm, Z = 2 space group I4/mrnm-D4h17 (No. 139).  相似文献   

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