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1.
Carbonate Isostructural Anions [SnX3]5? in the Compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi The metallic shining compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi were prepared from the melt starting from adequate mixtures of the elements and SnO2. They crystallize in the hexagonal system (space group P63/mmc, No. 194, Z = 2) with the lattice constants mentioned in ?Inhaltsübersicht”?. In the structures of the isotypic compounds tin and the main group(V) elements build up trigonal planar anions [SnX3]5? with X = As, Sb, and Bi isostructural to the carbonate anion, oxygen forms isolated O2? ions. The bond lengths Sn? X are significantly shortened with respect to the sums of Pauling covalent radii. The atoms of the units [SnX3]5? are coordinated by alkali metal cations forming trigonal prisms and the O2? anions occupy octahedral holes. 相似文献
2.
Zintl-Compounds with Gold: M3AuSn4 with M = K, Rb, Cs and M3AuPb4 with M = Rb, Cs Silver coloured, brittle single crystals of the compounds M3AuSn4 with M = K, Rb, Cs and M3AuPb4 with M = Rb, Cs were synthesized by reactions of alkali metal azides (MN3) with gold sponge and tin (lead) powder at T = 923 K. The structures of the isotypic compounds (space group Pmmn, Z = 2) were determined from X-ray single-crystal diffractometry data (see ‘‘Inhaltsübersicht”︁”︁). The Zintl-compounds M3AuE(14)4 with E(14) = Sn, Pb contain [AuE(14)4]-chains with P4-analogous E(14)4-tetrahedra which are connected by μ2-bridging gold atoms. 相似文献
3.
Zintl‐Compounds with Gold and Germanium: M3AuGe4 with M = K, Rb, Cs Black, brittle single crystals of M3AuGe4 with M = K, Rb, Cs were synthesized by reactions of alkali metal azides (MN3) with gold sponge and germanium powder at T = 1120 K. The structures of the compounds (space group Pmmn, Z = 2, K3AuGe4: a = 6.655(1)Å, b = 11.911(2)Å, c = 6.081(1)Å; Rb3AuGe4: a = 6.894(1)Å, b = 12.421(1)Å, c = 6.107(1)Å; Cs3AuGe4: a = 7.179(1)Å, b = 12.993(2)Å, c = 6.112(2)Å) were determined from X‐ray single‐crystal diffractometry data. The semiconducting compounds contain equation/tex2gif-stack-2.gif[AuGe4]‐chains with P4‐analogous Ge4‐tetrahedra which are connected by μ2‐bridging gold atoms in a distorted tetrahedral Ge‐coordination. 相似文献
4.
Ca6GaN5 and Ca6FeN5: Compounds Containing [CO3]2?-isosteric Anions [GaN3]6? and [FeN3]6? The isotypic phases Ca6GaN5 and Ca6FeN5 (hexagonal, P63/mem; a = 627.7(3)/ 623,7(1) pm, c = 1219.8(3)/1233.2(6) pm; Z = 2) are prepared by reaction of Ca/Ga mixtures (molar ratio 6:1) and Fe/Ca3N2/Ca mixtures (molar ratios from 3:1:13 to 5:2:15) with nitrogen at temperatures of 850°C and 950°C to 1100°C, respectively. The structures contain trigonal-planar anions [MN3]6? which are isosteric to carbonate ions (Ga? N: 195,1(28) pm; Fe? N: 177,0(15) pm). The structures are closely related to those compounds of the hydrotalcite group. 相似文献
5.
Synthese und Kristallstruktur von Alkalimetalldiamidodioxosilicaten M2SiO2(NH2)2 mit M ≙ K,Rb und Cs
Synthesis and Crystal Structure of Alkali Metal Diamido Dioxosilicates M2SiO2(NH2)2 with M ? K, Rb and Cs SiO2 – α-quartz – reacts with alkali metal amides MNH2 (M ? K, Rb, and Cs) in molar ratios from 1:2 to 1:10 at 450°C ≤ T ≤ 600°C and P(NH3) = 6 kbar in autoclaves to diamidodioxosilicates M[SiO2(NH2)2]. Crystals of the colourless compounds which hydrolyze rapidly were investigated by x-ray methods. Following data characterize the structure determination on the isotypic compounds: The structures of the diamidodioxosilicates are closely related to the β? K2SO4 type. They contain isolated [SiO2(NH2)2]2? ions. K+ ions and hydrogen bridge bonds N? H…?O (with 2.68 Å ≤ d(N…?O) ≤ 2.78 Å for the K compound) connect the tetrahedral anions. 相似文献
6.
The new hexathiodiphosphate(IV) hydrates K4[P2S6] · 4 H2O ( 1 ), Rb4[P2S6] · 6 H2O ( 2 ), and Cs4[P2S6] · 6 H2O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na4[P2S6] · 6 H2O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K4[P2S6] · 4 H2O ( 1 ) crystallizes in the monoclinic space group P 21/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb4[P2S6] · 6 H2O ( 2 ) crystallizes in the monoclinic space group P 21/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs4[P2S6] · 6 H2O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P2S6]4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P2S6]4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P2S6]4? group. The thermogravimetric analysis showed that K4[P2S6] · 4 H2O converted to K4[P2S6] as it was heated at 100 °C. 相似文献
7.
New Alkalioxoarsenates (V). On Rb2Li[AsO4] and Cs2Li[AsO4] By heating of well-grounded mixtures of the binary oxides (A2O, Li2O2, and As2O3; A : Li : As = 2 : 1 : 1; Ni-tube, 550°C, 21 d; A = Rb, Cs) colourless single crystals of Rb2Li[AsO4] and Cs2Li[AsO4] were obtained for the first time. These new orthoarsenates(V) crystalize orthorhombic (space group C mc21? C, No. 36) with Z = 4. As expected they are isotypic with the according orthovanadates(V) [2] A2Li[VO4], A = Rb, Cs. The lattice constants of Rb2Li[AsO4]: a = 582.1(4) pm, b = 1171.1(7) pm, c = 792.4(5) pm and Cs2Li[AsO4]: a = 596.4(2) pm, b = 1223.4(2) pm, c = 819.7(3) pm were taken from Guinier-Simon powder data. The structure was determined by four-circle-diffractometer data [Siemens AED II, MoKα , 6290 I0 (hkl), R = 3.5%, Rw = 3.2% to Rb2Li[AsO4]; 3518 I0 (hkl), R = 2.8%, Rw = 2.6% to Cs2Li[AsO4]; 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
8.
Bernhard Neumüller My-Linh Ha-Eierdanz Ulrich Müller Sylvia Magull Gertrud Kruter Kurt Dehnicke 《无机化学与普通化学杂志》1992,609(3):12-18
Syntheses and Crystal Structures of the Polyselenido Complexes (PPh4)6[M(Se4)2]2[WSe4] · DMF with M = Zinc and Mercury The title compounds have been prepared by the reactions of the acetates of zinc and mercury, respectively, with excess (PPh4)2 WSe4 in boiling dimethylformamide, forming black-red single crystals. According to the X-ray structure determinations both compounds crystallize isotypically in the space group 12/a with four formula units per unit cell. (PPh4)6[Zn(Se4)2]2[WSe4] · DMF: a = 2888.1(6), b = 1740.3(2), c = 2893.9(4) pm, β = 90.47(1)°. 3230 observed unique reflections, R = 0.009. (PPh4)6[Hg(Se4)2]2[WSe4] · DMF: a = 2891.8(5), b = 1738.0(4), c = 2920.1(5) pm, β = 90.29(2)°. 2978 observed unique reflections, R = 0.115%. The compounds consist of PPh4+ ions, spirocyclic octaseleno metallates [M(Se4)2]2?, tetrahedral WSe42-ions, and disordered DMF Molecules. 相似文献
9.
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
10.
The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+, and the Adduct CH3CN · SbF5. The Crystal and Molecular Structures of [M(NCCH3)4][SbF6]2 · CH3CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)4][Sb2F11]2, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb2F11]– into [SbF6]– and the molecular adduct CH3CN · SbF5 according to: [M(CO)4][Sb2F11]2 + 7 CH3CN → [M(NCCH3)4][SbF6]2 · CH3CN + 2 CH3CN · SbF5 + 4 CO M = Pd, Pt The monosolvated [M(NCCH3)4][SbF6]2 · CH3CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH3)2][SbF6] and the adduct CH3CN · SbF5 are completely characterized by vibrational spectroscopy. 相似文献
11.
Angela Mller 《无机化学与普通化学杂志》1997,623(11):1685-1692
Synthesis, Crystal Structures, and Absorption Spectra of the New “Cupriosilicates”: K6[CuSi2O8] and Rb4[CuSi2O7] K6[CuSi2O8] and Rb4[CuSi2O7] were obtained by annealing intimate mixtures of K2O and Rb2O, respectively, CuO and SiO2 in sealed Ag cylinders at 500°C as transparent greenish-blue single crystals. The structure solution (IPDS-data Mo Kα; K6[CuSi2O8]: 1292 F2(hkl), R1 = 0.059; wR2 = 0.103 and Rb4[CuSi2O7]: 763 F2(hkl), R1 = 0.049; wR2 = 0.114) confirms the space group P1 for both compounds. K6[CuSi2O8]: a = 619.4(2); b = 665.5(2); c = 753.0(2) pm; α = 83.66(3); β = 87.71(3); γ = 70.19(3)°; Z = 1. Rb4[CuSi2O7]: a = 631.9(9); b = 707.5(10); c = 715.2(6) pm; α = 114.2(1); β = 100.7(1); γ = 107.9(1)°; Z = 1. The Madelung Part of the Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these calculated via Mean Effective Ionic Radii, MEFIR, are given. The absorption spectra of K6[CuSi2O8] and Rb4[CuSi2O7] are discussed in terms of the Angular Overlap Model, AOM. 相似文献
12.
13.
Dynamical Behaviour of Linear Molecular Anions in the Hydrogensulfides of Sodium, Potassium and Rubidium: Differential Scanning Calorimetry, X-ray and Neutron Diffraction Hydrogensulfides of the alkali metals M ? Na, K, Rb were prepared in autoclaves by the reaction of the corresponding metals with H2S and D2S, respectively, in the temperature range from 50°C to 150°C. Differential scanning calorimetry, X-ray and neutron diffraction methods reveal that both, the HS?-and DS?-compounds occur in three crystalline modifications with HT ? high-, MT ? medium- and LT ? low-temperature form: The temperatures and enthalpies for the changes of modifications of the H- and D-compounds are given and the atomic arrangements revealed mainly by neutron diffraction data are discussed, in relation to, for example, size of cations. 相似文献
14.
A. Müller E. Krickemeyer F. El-Katri D. Rehder A. Stammler H. Bgge F. Hellweg 《无机化学与普通化学杂志》1995,621(7):1160-1170
Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS3)2]2? (E = Sn, Zn, Cd), [E(CS3)3]3? (E = As, Sb, Bi, Co), {Cu(CS3)?}∞ and [Zn(CS4)2]2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh4)2[Zn(CS3)2] ( 2 ), (PPh4)2[Cd(CS3)2] ( 3 ), (PPh4)2[Sn(CS3)2] ( 4 ), (PPh4)3[As(CS3)3] ( 5 ), (PPh4)3[Sb(CS3)3] ( 6 ), (PPh4)3[Bi(CS3)3] ( 7 ), (PPh4)3[Co(CS3)3] ( 8 ) and (PPh4)Cu(CS3) ( 9 ) have been isolated. (PPh4)2[Zn(CS4)2] · CH3NO2 ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh4)2[C2S6] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, 113Cd/59Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht. 相似文献
15.
Thiosilicates of the Rare‐Earth Elements: III. KLa[SiS4] and RbLa[SiS4] – A Structural Comparison Pale yellow, platelet shaped, air‐ and water resistant single crystals of KLa[SiS4] derived from the reaction of lanthanum (La) and sulfur (S) with silicon disulfide (SiS2) in a molar ratio of 2 : 3 : 1 with an excess of potassium chloride (KCl) as flux and source of potassium ions in evacuated silica ampoules at 850 °C within seven days. The analogous reaction utilizing a melt of rubidium chloride (RbCl) instead also leads to yellow comparable single crystals of RbLa[SiS4]. The potassium lanthanum thiosilicate crystallizes monoclinically with the space group P21/m (a = 653.34(6), b = 657.23(6), c = 867.02(8) pm, β = 107.496(9)°) and two formula units per unit cell, while the rubidium lanthanum thiosilicate has to be assigned orthorhombically with the space group Pnma (a = 1728.4(2), b = 667.23(6), c = 652.89(6) pm) and four formula units in its unit cell. In both compounds the La3+ cations are surrounded by 8+1 sulfide anions in the shape of tricapped trigonal prisms. The Rb+ cations in RbLa[SiS4] show a coordination number of 9+2 relative to the S2? anions, which form pentacapped trigonal prisms about Rb+. This coordination number, however, is apparently too high for the K+ cations in KLa[SiS4], so that they only exhibit a bicapped trigonal prismatic environment built up by eight S2? anions. The isolated thiosilicate tetrahedra [SiS4]4? of the rubidium compound are surrounded by La3+ both edge‐ and face‐capping, but terminal as well as edge‐ and face‐spanning by Rb+. In the potassium compound there is no change for the La3+ environment about the [SiS4]4? tetrahedra, but the K+ cations are only able to attach terminal and via edges. The whole structure is built up by anionic equation/tex2gif-stack-1.gif{La[SiS4]}? layers that are separated by the alkali metal cations. In direct comparison the two thiosilicate structures can be regarded as stacking variants. 相似文献
16.
Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc2?]? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((nBu4N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc2?]?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (nBu4N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of b(PNP)[Mg(Cl)Pc2?] · CH3COCH3 reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (Niso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? Niso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (b(PNP)+: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed. 相似文献
17.
Compounds in the Systems Potassium(Rubidium)/Gold/Antimony: K3Au3Sb2, Rb3Au3Sb2, and K1,74Rb0,26RbAu3Sb2 Brittle, silver coloured single crystals of K3Au3Sb2, Rb3Au3Sb2 and K1,74Rb0,26RbAu3Sb2 were obtainded by reaction of the alkali metal azides (KN3, RbN3) with gold and antimon powder at 550°C. The structures of the isotypic compounds (R3 m, Z = 3) were determined by X-ray single-crystal diffractometer data: K3Au3Sb2, a = 6,198(2) Å, c = 21,520(5) Å, R/Rw (w = 1) = 0,046/0,058, Z(F) ? 3σ(F) = 175, Z(Var.) = 14; Rb3Au3Sb2, a = 6,443(3), c = 21,69(2), R/Rw (w = 1) = 0,059/0,082, Z(F) ? 3σ(F02) = 258, Z(Var.) = 14; K1,74Rb0,26RbAu3Sb2, a = 6,288(2) Å, c = 21,617(5) Å, R/Rw (w = 1) = 0,049/0,069, Z(F) ? 3σ(F) = 390, Z(Var) = 14. The compounds crystallize with the K3Cu3P2-structure type. The Au? Sb partial structures consist of [AuSb2/3] layers with linear Sb? Au? Sb dumb-bells and SbAu3 pyramids. The layers are separated by two crystallographically independent alkali metal atoms along [001]. 相似文献
18.
Synthesis and Crystal Structure of Rb8[P4N6(NH)4](NH2)2 with the Adamantane-like Anion [P4N6(NH)4]6? RbNH2 reacts with P3N5 (molar ratio 6:1) at 400°C within 5 d to colourless Rb8[P4N6(NH)4](NH2)2. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P4N6(NH)4]6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly. 相似文献
19.
20.
Synthesis and Spectroscopical Properties of Di(phthalocyaninato(1?))lanthanidepolybromide; Crystal Structure of α-Di(phthalocyaninato)samariumpolybromide, α-[Sm(Pc)2]Br1.45 and α-Di(phthalocyaninato)samariumperchlorate, α-[Sm(Pc)2](ClO4)0.63 Bronze-coloured di(phthalocyaninato)lanthanidepolybromide, [Ln(Pc?)2]Bry (Ln = La…(? Ce, Pm)…Lu; y > 1.5) is prepared by oxidation of (nBu4N)[Ln(Pc2?)2] with bromine in excess. The UV-VIS-NIR spectra show the typical B and Q1 bands of the Pc? ligand at ~ 14 kK and ~ 20 kK. For the [Ln(Pc?)2]+ cation a NIR(D) band between 9,14 kK (La) and 11,50 kK (Lu) is characteristic for dimeric cofacial Pc? radicals. Within the row La…Lu, there is a linear relationship of the hypsochromic shift of the strong bands and the LnIII radius. In the case of La? Nd the D band shifts successively with longer time of bromination to ~ 3 kK as a result of increasing electron delocalisation. Characteristic vibrational bands are at ~ 1350/1450 cm?1 (IR) and ~ 560/1120/1170/1600 cm?1 (RR). In the FT-Raman spectra the totally symmetric Ln? N stretching vibration between 141 cm?1 (La) and 172 cm?1 (Lu) is selectively enhanced. As shown by α-[Sm(Pc)2]Br1,45 and α-[Sm(Pc)2](ClO4)0,63 only partially ringoxidized complexes are obtained by the anodic oxidation. Both crystallize in the tetragonal space group P4/nnc. The [Sm(Pc)2] molecular building block contains two nearly planar staggered (~41°) Pc rings packed in columns parallel along [001] leading to the quasi-one-dimensional structure. There is a statistical disorder of the SmIII and the ClO4? resp. Br?/Br3? ions over two incompletely filled crystallographic positions for the cation resp. anion. This results in a partial oxidation of the Pc ligand, which in the picture of localized valence states for α-[Sm(Pc)2](ClO4)0,63 corresponds to [SmPc?Pc2?] · 2[Sm(Pc?)2](ClO4). Accepting the same valence state for [Sm(Pc)2]Br1,45 five positive charges are compensated by two Br? and three Br3?. The spectroscopic differences of the partially and fully oxidized complexes are discussed. 相似文献