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The ammoniate [K17(Sb8)2(NH2)] · 17.5NH3 was synthesized by reduction of antimony with potassium in liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. [K17(Sb8)2(NH2)] · 17.5NH3 crystallizes in the space group P21/c (No. 14) with a = 12.976(1) Å, b = 24.536(1) Å, c = 22.858(1) Å and β = 99.17(1)°. The ammoniate contains crown‐shaped [Sb8]8? Zintl anions which are analogous to S8 rings. The presence of amide NH2? as an additional anion is deduced from coordination observations and the close similarity of structural features to the structure of KNH2. 相似文献
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The title compound [K([2,2,2]crypt)]12[Sn9]2[Sn9HgSn9] has been obtained by reaction of elemental mercury with the binary phase K4Sn9 in ethylenediamine after addition of [2,2,2]crypt and layering with toluene. The X‐ray single crystal analysis shows that the compound consists of two isolated Sn9 clusters and two Sn9 clusters connected by a mercury atom. 相似文献
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A new phase has been prepared by methanolothermal reaction of Cs2CO3, BiCl3 and Li3AsSe3 at 130 °C for 36 hours. Cs4BiAs3Se7 ( I ) reveals the first Bi‐selenoarsenate polyanionic chain [Bi(As2Se4)(AsSe3)]4–, consisting of Bi3+ ions in a distorted octahedral environment of [AsSe3]3– and trans‐[As2Se4]4– units. The latter anion consists of a central “As24+” dumb‐bell whereby two Se atoms are attached to each of the As atoms. Structural Data: Space Group P21/n, a = 13.404(4) Å, b = 23.745(8) Å, c = 13.880(4) Å, β = 99.324(6)°, Z = 8. 相似文献
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The compound [Rb(18‐crown‐6)]2Rb2[Sn9](en)1.5 ( 1 ) was synthesized from an alloy of formal composition K2Rb2Sn9 by dissolving in ethylenediamine (en) followed by the addition of 18‐crown‐6 and toluene. 1 crystallizes in the monoclinic space group P21/n with a = 10.557(2), b = 25.837(5), c = 20.855(4)Å, β = 102.39°, and Z = 4. The structure consists of [Sn9]4— cluster anions, which are connected via Rb atoms to infinite [Rb4Sn9] layers. The layers of binary composition are separated by the crown ether molecules. The crown ether molecules are bound by one side via the Rb atoms to the [Sn9]4— anions. The other side, which is turned away from the Rb atoms, shows only weak van der Waals interactions to the crown ether molecules of the next layer. Comparison with other compounds of similar composition shows, that the variation of the alkali metals and the complexing organic molecules leads to the low dimensional arrangement of the clusters. 相似文献
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Bi37InBr48: a Polar Subhalide with Bi95+ Polycations, Complex Bromobismuthate(III) Anions [Bi3Br13]4— and [Bi7Br30]9—, and Pentabromoindate(III) Anions [InBr5]2— Black crystals of Bi37InBr48 were synthesized from bismuth, indium and BiBr3 by cooling stoichiometric melts from 570 K to 470 K. X‐ray diffraction on powders and single‐crystals revealed that the compound crystallizes with space group P 63 (a = 2262.6(4); c = 1305.6(2) pm). The Bi95+ polycations in the polar crystal structure have the shape of heavily distorted tri‐capped trigonal prisms with approximate Cs symmetry. The high complexity of the structure results from three coexisting types of anionic groups: Three edge‐sharing [BiBr6] octahedra constitute the trigonal bromobismuthate(III) anion [Bi3Br13]4—. Four [BiBr6] and three [BiBr5] polyhedra share common vertices to form the [Bi7Br30]9— hemi‐sphere, in which the trigonal bipyramid of the pentabromoindat(III) ion [InBr5]2— is embedded. 相似文献
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Selenium Polycations Stabilized by Polymeric Chlorobismuthate Anions: Syntheses and Crystal Structures of Se4[Bi4Cl14] and Se10[Bi5Cl17] Reactions of selenium with selenium(IV) chloride and bismuth(III) chloride in sealed evacuated glass ampoules at temperatures between 110 and 155 °C yield a series of compounds which are composed of discrete selenium polycations and polymeric chlorobismutate anions. Besides the already known Se8[Bi4Cl14] two new compounds have been identified by crystal structure analyses as Se4[Bi4Cl14] (tetragonal, P4/n, a = 1089.1(2) pm, c = 993.7(2) pm, Z = 2) and Se10[Bi5Cl17] (monoclinic, P21/c, a = 1079.24(8) pm, b = 2062.9(2) pm, c = 1676.1(2) pm, β = 90.87(1)°, Z = 4). Se4[Bi4Cl14] was obtained as red transparent platelike crystals and is the first example of a compound with (chalcogen4)2+ ions of exact square‐planar symmetry and molecular point group D4h in the solid state. The cations are surrounded by layers of two‐dimensional polymeric anions [Bi4Cl14]2–. Se10[Bi5Cl17] forms dark grey crystals with a reddish luster. The structure contains the known bicyclic polycation Se102+ which is disordered over two positions and the first three‐dimensional polymeric chlorobismutate anion [Bi5Cl17]2–. The different BiClx polyhedra are linked by sharing common vertices, edges, and faces. 相似文献
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The Novel cis‐[Bi3I12]3?‐Anion in Tri(n‐butyl)methylammoniumdodecaiodo‐tribismutate By reaction of equivalent amounts of BiI3, KI and I2 in [N(CH3) (n‐C4H9)3][N(SO2CF3)2] as Ionic Liquid, transparent reddish crystals with the composition [N(CH3)(n‐C4H9)3]3[Bi3I12] are formed. Concerning to X‐ray diffraction investigations based on single crystals as well as powders, [N(CH3)(n‐C4H9)3]3[Bi3I12] crystallizes monoclinic (P21/c; a = 2383.0(5); b = 1241.0(3); c = 2493.0(5) pm; β = 97.50(3)°; Z = 4). The anion consists of distorted (BiI6)‐octahedra, which are face‐shared via cis‐oriented octahedral faces. With the cis‐[Bi3I12]3?‐anion such a connectivity is firstly described. 相似文献
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The reactions of the Zintl phase K2Cs2Sn9 with elemental tellurium and selenium in ethylenediamine have been investigated. From the reaction of K2Cs2Sn9 with elemental tellurium [K‐(2,2,2‐crypt)]4Te6Te4 ( 2 ) and [K‐(2,2,2‐crypt)]2Sn2Te3 ( 3 ) were obtained, whereas the reaction of K2Cs2Sn9 with elemental selenium led to the formation of [K‐(2,2,2‐crypt)]2Sn(Se4)3 ( 4 ) and [K‐(2,2,2‐crypt)]2Cs2Sn2Se6·2en ( 5 )1). Compounds 2 , 4 , 5 have been characterized by single crystal X‐ray structure determination. 相似文献
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The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO3) : terpy.; [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy) · (η2‐NO3)2] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N0 = 2319. 相似文献
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Mehmet Somer Wilder Carrillo‐Cabrera Karl Peters Hans Georg von Schnering 《无机化学与普通化学杂志》2000,626(4):897-904
Synthesis, Crystal Structure, and Vibrational Spectra of Compounds with the Linear Dipnictidoborate (3–) Anions [P–B–P]3–, [As–B–As]3–, and [P–B–As]3– The alkali metal boron compounds M3[BX2] with X = P, As are synthesized from the alkali metals M and the binary components MX or M4X6 and BX in sealed steel ampoules (phosphides) or niobium ampoules (arsenides) at 1000 K. The compounds are obtained as bright yellow prisms (M3[BP2]) or plates (K2Na[BP2]) and yellow‐red prismatic crystals (M3[BAs2], Cs3[BPAs]) which are very sensitive against oxidation and hydrolysis. Three different structure types are formed, namely K2Na[BP2] (C2/m (No. 12); Z = 4; a new mC24 structure type); Na3[BP2] (P21/c (No. 14); Z = 4, β‐Li3[BN2] type), M3[BX2] with M = K, Rb, Cs and X = P, As and Cs3[P–B–As] (C2/c, (No. 15); Z = 4, K3[BP2] type). The bond lengths of the linear [BX2]3– anions are hardly changed and correspond to a Pauling bond order PBO = 1.9 (d(B–P) = 176.7–177.1 pm; d(B–As) = 186.5–188.0 pm). The vibrational spectra confirm the existence of unmixed and mixed units [P–B–P]3–, [As–B–As]3– and [P–B–As]3– with D∞h and C∞v symmetry, respectively. The valence force constants f(B–X) and the corresponding Siebert bond orders, calculated from the frequencies, are discussed and compared with those of the isoelectronic anions and molecules. 相似文献
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Ibrahim Abdelhalim Ahmed Roger Blachnik Guido Kastner Wolfgang Brockner 《无机化学与普通化学杂志》2001,627(9):2261-2268
The phase diagram of the system [Ph4P]Br/BiBr3 was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr3 and [Ph4P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph4P]3[Bi2Br9] · CH3COCH3, which crystallises with monoclinic symmetry in the S. G. P21/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) Å3, Z = 4 and the crystal structures of two modifications of the compound [Ph4P]4[Bi6Br22]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) Å3, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) Å3, Z = 2. Lattice parameters of [Ph4P]4[Bi8Br28] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 are presented and discussed. 相似文献
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Polymeric, Band Shaped Tellurium Cations in the Structures of the Chloroberyllate Te7[Be2Cl6] and the Chlorobismutate (Te4)(Te10)[Bi4Cl16] Te7[Be2Cl6] is obtained at 250 °C in an eutectic Na2[BeCl4] / BeCl2 melt from Te, TeCl4 und BeCl2 in form of black crystals, which are sensitive towards hydrolysis in moist air. (Te4) (Te10)[Bi4Cl16] is prepared from Te, TeCl4 und BiCl3 by chemical vapour transport in sealed evacuated glass ampoules in a temperature gradient 150 ° → 90 °Cin form of needle shaped crystals with a silver lustre. The structures of both compounds were determined based on single crystal X‐ray diffraction data (Te7[Be2Cl6]: orthorhombic, Pnnm, Z = 2, a = 541.60(3), b = 974.79(6), c = 1664.4(1) pm; (Te4)(Te10)[Bi4Cl16]: triclinic, P1¯, Z = 2, a = 547.2(3), b = 1321.1(7), c = 1490(1) pm, α = 102.09(5)°, β = 95.05(5)°, γ = 96.69(4)°). The structure of Te7[Be2Cl6] consists of one‐dimensional polymeric cations (Te72+)n which form folded bands and of discrete [Be2Cl6]2— anions which form double tetrahedraconnected by a common edge. By a different way of folding compared with the cations present in the structures of Te7[MOX4]X (M = Nb, W; X = Cl, Br) the (Te72+)n cation in Te7[Be2Cl6]represents a new, isomeric form. The structure of (Te4)(Te10)[Bi4Cl16] contains two different polymeric cations. (Te102+)n consists of planar Te10 groups in the form of three corner‐sharing Te4 rings connected to folded bands. (Te42+)n forms in contrast to the so far notoriously observed discrete, square‐planar E42+ ions a chain of rectangular planar Te4 rings (Te—Te 274 and 281 pm) connected by Te‐Te bonds of 297 pm. [Bi4Cl16]4— has a complex one‐dimensional structure of edge‐ and corner‐sharing BiCl7 units. 相似文献
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Ibrahim Abdel Ahmed Roger Blachnik Hans Reuter Henning Eickmeier Dietrich Schultze Wolfgang Brockner 《无机化学与普通化学杂志》2001,627(6):1365-1370
[Ph4P]2[Bi2Br8(CH3COCH3)2] ( 1 ) was obtained by the reaction of [Ph4P]Br and BiBr3 in acetone. Single crystals were grown by allowing a layer of n‐hexane to diffuse into the acetonic solution of 1 . The crystal structure was determined by means of X‐ray diffraction. 1 crystallises with monoclinic symmetry in the space group P21/n, No. 14 with the lattice parameters: a = 13.358(2), b = 12.637(2), c = 18.565(3) Å, β = 102.62(1)°, V = 3058.1(8) Å3 and Z = 4. The structure is characterised by the anion [Bi2Br8(CH3COCH3)2]2– which is embedded in a matrix of [Ph4P]+ cations. The anion can be described as two edge‐sharing square pyramids with the apical bromide ions in anti‐position. Acetone co‐ordinates the bismuth atoms via oxygen atoms and increases the co‐ordination number of central bismuth atoms to six which results in the formation of a distorted bi‐octahedron. The distortion is due to the difference in terminal and bridging Bi–Br bond lengths. FT‐IR and Raman spectroscopic data are presented. In addition, the thermal behaviour of the compound was studied with the aid of TG/DSC coupled with MS revealing that acetone leaves the crystal in two steps. The compound melts at 203 °C and transforms into a glass on cooling. 相似文献
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The reaction of Rb2S3, Ta and S in a 1.3 : 1 : 5.6 molar ratio at 400 °C yields red‐orange crystals of the new ternary compound Rb6Ta4S22 being the first tantalum polysulfide containing the dimeric complex anion [Ta4S22]6–. The polysulfide anions are composed of two Ta2S11 subunits which are linked to Ta4S22 units via terminal sulfur ligands. The Ta5+ centers are coordinated by S22– and S2– ligands according to [(Ta2(μ2‐η2,η1‐S2)3(η2‐S2)(S)2)2(μ2‐η1,η1‐S2)]6–. Every Ta5+ ion is surrounded by seven sulfur ions forming a strongly distorted pentagonal bipyramid. In the crystal structure the discrete [Ta4S22]6– anions are stacked parallel to the crystallographic b‐axis. The Rb+ cations are located between these stacks. Rb6Ta4S22 crystallizes in the monoclinic space group P21/c (No. 14) with a = 11.8253(9) Å, b = 7.9665(4) Å, c = 19.174(2) Å, β = 104.215(9)°, V = 1751.0(2) Å3, Z = 2. 相似文献
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Pnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)4(E2)2[Sn(E15)4] (with E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) of the Na6[ZnO4] Type and the Superstructure Variant of K4Sr2[SnAs4] The silvery to dark metallic lustrous compounds (E1)4(E2)2[Sn(E15)4] (E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na6[ZnO4]‐type structure (hexagonal, space group: P63mc, Z = 2; Na4Ca2[SnP4]: a = 938.94(7), c = 710.09(8) pm; K4Sr2[SnAs4]: a = 1045.0(2), c = 767.0(1) pm; K4Ba2[SnP4]: a = 1029.1(6), c = 780.2(4) pm; K4Ba2[SnAs4]: a = 1051.3(1), c = 795.79(7) pm; K4Ba2[SnSb4]: a = 1116.9(2), c = 829.2(1) pm; K4Ba2[SnBi4]: a = 1139.5(2), c = 832.0(2) pm). The anionic partial structure consists of tetrahedra [Sn(E15)4]8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K4Sr2[SnAs4] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P63cm, Z = 6; a = 1801.3(2), c = 767.00(9) pm) and an ordered cationic partial structure. 相似文献
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Six polynuclear chlorobismuthates are formed in the reaction between BiCl3 and Ph4PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph4P]3[Bi2Cl9] · 2 CH2Cl2, [Ph4P]3[Bi2Cl9] · CH3COCH3, [Ph4P]2[Bi2Cl8] · 2 CH3COCH3, [Ph4P]4[Bi4Cl16] · 3 CH3CN, [Ph4P]4[Bi6Cl22], and [Ph4P]4[Bi8Cl28]. We report the crystal structure of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) Å3, Z = 2. The anion is formed from two face‐sharing BiCl6‐octahedra. [Ph4P]2[Bi2Cl8] · 2 CH3COCH3 crystallises with monoclinic symmetry in the S. G. P21/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) Å3, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph4P]4[Bi4Cl16] · 3 CH3CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) Å3, Z = 2. Two Bi2Cl8 dimers in syn‐position form the cubic anion. Lattice parameters of [Ph4P]3[Bi2Cl9] · CH3COCH3 are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]3[Bi2Cl9] · CH3COCH3 show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state. 相似文献
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Michael Ruck 《无机化学与普通化学杂志》1998,624(3):521-528
Bi34Ir3Br37: A Pseudo-Symmetric Subbromide with Bi5+ and Bi62+ Polycations, and [IrBi6Br12]– and [IrBi6Br13]2– Cluster Anions The melting reaction of Ir with Bi and BiBr3 yields black, lustrous, air insensitive crystals of the subbromide Bi34Ir3Br37. The triclinic crystal structure (space group P 1, a = b = 1303.4(2) pm, c = 1647.4(4) pm, α = β 90°, γ = 120°, V = 2423.7 × 106 pm3) deceives pseudo symmetry with respect to the rhombohedral space group R 3, which results in multiply twinned crystals. The structure can formally be subdivided in four new types of ionic groups: (a) cuboctahedral [IrBi6Br12]– clusters, (b) [IrBi6Br13]2– clusters with an additional Br atom, (c) Bi5+ square pyramids, and (d) distorted Bi62+ octahedra. The compound shows a range of homogeneity due to variable contributions of the different clusters. 相似文献