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1.
(SO4)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3) were obtained by solvothermal reaction with SO3, and the electronic properties were investigated by means of density functional theory–based calculations. [Au3Cl4][B(S2O7)2] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au2Cl4][B(S2O7)2](SO3) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.  相似文献   

2.
The reaction of oleum (65 % SO3) with the tetrachlorides of silicon, germanium, and titanium, respectively, led to the complex disulfates Sr2[M(S2O7)4] (M=Si, Ge), Ba[M(S2O7)3] (M=Si, Ge, Ti) and Pb[M(S2O7)3] (M=Ge, Ti) if strontium, barium, and lead were used as divalent counter cations. The strontium compounds exhibit the unique tetrakis‐(disulfato)‐metallate anions [M(S2O7)4]4? with the silicon and germanium atoms in octahedral coordination of two chelating and two monodentate disulfate groups. All of the other compounds display tris‐(disulfato)‐metallate anions [M(S2O7)3]2? with three chelating disulfate groups surrounding the M atoms. Thermoanalytical investigations on the germanium compounds Sr2[Ge(S2O7)4] and Ba[Ge(S2O7)3] revealed their decomposition in multi‐step processes leading to a mixture of BSO4 and BGe4O9 (B=Sr, Ba), while the thermal degradation of Pb[Ti(S2O7)3] yields PbTiO3. For selected examples, IR data are additionally presented.  相似文献   

3.
Bis(disulfido)bridged NbIV cluster oxalate complexes [Nb2(S2)2(C2O4)4]4– were prepared by ligand substitution reaction from the aqua ion [Nb2(μ‐S2)2(H2O)8]4+ and isolated as K4[Nb2(S2)2(C2O4)4] · 6 H2O ( 1 ), (NH4)6[Nb2(S2)2(C2O4)4](C2O4) ( 2 ) and Cs4[Nb2(S2)2(C2O4)4] · 4 H2O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.  相似文献   

4.
Borosulfates are an ever‐expanding class of compounds and the extent of their properties is still elusive. Herein, the first two copper borosulfates Cu[B2(SO4)4] and Cu[B(SO4)2(HSO4)] are presented, which are structurally related but show different dimensionalities in their substructure: While Cu[B2(SO4)4] reveals an anionic chain, [B(SO4)4/2]?, with both a twisted and a unique chair conformation of the B(SO4)2B subunits, Cu[B(SO4)2(HSO4)] reveals isolated [B2(SO4)4(HSO4)2]4? anions showing exclusively a twisted conformation. The complex anion can figuratively be obtained as a cut‐out from the anionic chain by protons. Comparative DFT calculations based on magnetochemical measurements complement the experimental studies. Calculation of the pKa values of the two conformers of the [B2(SO4)4(HSO4)2]4? anion revealed them to be more similar to silicic than to sulfuric acid, highlighting the close relationship to silicates.  相似文献   

5.
Two new borosulfates were obtained either by an open vessel synthesis from sulfuric acid and B(OH)3, yielding (NH4)3[B(SO4)3] or from solvothermal synthesis in oleum enriched sulfuric acid and B(OH)3, yielding Sr[B2(SO4)4]. (NH4)3[B(SO4)3] crystallizes homeotypic to K3[B(SO4)3] in space group Ibca (Z = 8, a = 728.58(3) pm, b = 1470.84(7) pm, c = 2270.52(11) pm), comprising open branched vierer single chains {1[B(SO4)2(SO4)2/2]3–}. Sr[B2(SO4)4] crystallizes as an ordered variant of Pb[B2(SO4)4] in space group Pnna (Z = 4, a = 1257.4(4) pm, b = 1242.1(4) pm, c = 731.9(2) pm), consisting of loop branched vierer single chains {1[B(SO4)4/2]2–}. Vibrational spectroscopy confirms both refined structure models. Thermal analysis of the dried powders, showed a decomposition towards the binary and ternary components, whereas a thermal treatment in the presence of the mother liquor promotes a decomposition of Sr[B2(SO4)4] towards Sr[B2O(SO4)3].  相似文献   

6.
The reaction of ZrCl4 with oleum (65 % SO3) in the presence of Ag2SO4 at 250 °C yielded colorless single crystals of Zr(S2O7)2 [orthorhombic, Pccn, Z = 4, a = 709.08(6) pm, b = 1442.2(2) pm, c = 942.23(9) pm, V = 963.5(2) × 106 pm3]. Zr(S2O7)2 shows Zr4+ ions in an eightfold distorted square antiprismatic coordination of oxygen atoms belonging to four chelating disulfate units. Each S2O72– ion is connected to a further Zr4+ ion leading to chains according to 1[Zr(S2O7)4/2]. The same reaction at a temperature of 150 °C resulted in the formation of Ag4[Zr(S2O7)4] [monoclinic, C2/c, Z = 4, a = 1829.35(9) pm, b = 704.37(3) pm, c = 1999.1(1) pm, β = 117.844(2)°, V = 2277.6(2) × 106 pm3]. Ag4[Zr(S2O7)4] exhibits the unprecedented [Zr(S2O7)4]4– anion, in which the central Zr4+ cation is coordinated by four chelating disulfate units. Thus, in Ag4[Zr(S2O7)4] the 1[[Zr(S2O7)4/2] chains observed in Zr(S2O7)2 are formally cut into pieces by the implementation of Ag+ ions.  相似文献   

7.
Sm4S3[Si2O7] and NaSm9S2[SiO4]6: Two Sulfide Silicates with Trivalent Samarium The sulfide silicates Sm4S3[Si2O7] and NaSm9S2[SiO4]6 are obtained as light yellow transparent crystals by the reaction of Sm, Sm2O3, S, and SiO2 with fluxing SmCl3 or NaCl, respectively, in suitable molar ratios in fused evacuated silica tubes (850 °C, 7 d). Tetragonal crystals of Sm4S3[Si2O7] (I41/amd; Z = 8; a = 1186.4(1); c = 1387.0(2) pm) with ecliptically conformed [Si2O7]6–‐groups of corner sharing [SiO4]‐tetrahedra are formed. These double tetrahedra as well the sulfide anions (S2–) coordinate two crystallographically independent metal cations. They provide coordination numbers of 8 + 1 (5 S2– and 3 + 1 O2–) for Sm1 and 9 (3 S2– and 6 O2–) for Sm2. NaSm9S2[SiO4]6 crystallizes hexagonally (P63/m; Z = 1; a = 975.32(9); c = 676.46(7) pm) in a modified bromapatite‐type structure. The coordination spheres about the two crystallographically different Sm3+ cations are built up by oxygen atoms of the orthosilicate units ([SiO4]4–) and sulfide anions (S2–). As a result, Sm1 and Sm2 have coordination numbers of 9 and 8, respectively. Na+ and (Sm1)3+ occupy the position 4 f in a molar ratio of 1 : 3 whereas the lower coordinated (Sm2)3+ occupies the 6 h position.  相似文献   

8.
Red single crystals of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2 (triclinic, , Z = 1, a = 844.02(9), b = 908.50(9), c = 939.49(8) pm, α = 107.73(1)°, β = 112.10(1)°, γ = 103.53(1)°) were obtained by the reaction of [Gd(NO3)(H2O)7][PtCl6]·4H2O with sulfuric acid at 320 °C in a sealed glass ampoule. In the crystal structure, Pt2 dumbbells are coordinated by four chelating sulfate groups and two monodentate hydrogensulfate ions. Two further HSO4? ions are not bonded to the Pt2 dumbbell. The Gd3+ ions are eightfold coordinated by oxygen atoms. The IR data of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2 are typical for these type of compounds. The thermal decomposition of the compound leads to elemental platinum and Gd2O3.  相似文献   

9.
Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO4)- and (BO4)-tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present Ni[B2(SO4)4] and Co[B2(SO4)4], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: NiII is located between the borosulfate layers, while CoII—in contrast—is embedded within the layer. Detailed analysis of these two structures based on single-crystal X-ray diffraction, magnetochemical investigations, X-ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species.  相似文献   

10.
Zusammenfassung Die Kristallstruktur des Kaliumtetragermanats, K2[Ge4O9], wurde mit Hilfe dreidimensionaler Röntgendaten bestimmt. K2[Ge4O9] kristallisiert trigonal mit der Raumgruppe P033034c1 (Nr. 165) und den Gitterparametern:a=11.84 undc=9.80 Å. Die vorgeschlagene strukturchemische Beziehung zum Wadeit, K2Zr[Si3O9], wird durch die Existenz tetraedrischer [Ge3O9]-Ringe, die über [GeO6]-Oktaeder zu einem dreidimensionalen Gerüst verknüpft sind, bestätigt. Es wurden folgende mittlere Ge–O-Abstände gefunden: 1.762 (Tetraeder) und 1.886 Å (Oktaeder).
The crystal structure of potassium tetragermanate K2[Ge4O9]
The crystal structure of potassium tetragermanate K2[Ge4O9] has been determined by means of three-dimensional x-ray data. K2[Ge4O9] crystallizes trigonal with space group P033034c1 (No. 165) and lattice parametersa=11.84 andc=9.80 Å. The proposed structural relationship to wadeite K2Zr[Si3O9] is confirmed by the existence of [Ge3O9] rings built by tetrahedra, which are linked by [GeO6] octahedra forming a three-dimensional network. The mean Ge–O distances are found to be: 1.762 (tetrahedra) and 1.886 Å (octahedra).


Mit 2 Abbildungen

Herrn Prof. Dr.H. Nowotny in Verehrung gewidmet.  相似文献   

11.
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   

12.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN.  相似文献   

13.
The crystal structure of the compound K2Ba[Ge4O9]2 has been determined by means of three-dimensional X-ray data resulting a finalR-value of 0.034. The lattice constants of the trigonal unit cell ( ) are:a=11.729 (I) andc=19.278 (3) Å. There is a close structural relationship to the tetragermanates K2Ge4O9 and BaGe4O9. The new compound also consists of three-membered rings built up by [GeO4] tetrahedra, which are linked by [GeO6] octahedra forming a three-dimensional network.According to their powder diagrams the following compounds are isostructural to K2Ba[Ge4O9]2: Na2Ba[Ge4O9]2, Rb2Ba[Ge4O9]2, Na2Sr[Ge4O9]2 and K2Sr[Ge4O9]2.  相似文献   

14.
利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。  相似文献   

15.
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   

16.
Iron nitrosyl complexes with general formula [Q4N]2[Fe2(S2O3)2(NO)4] (Q = Me, Et, n-Pr, n-Bu) were synthesized by the exchange reaction of K2[Fe2(S2O3)2(NO)4] with tetraalkylammonium bromides. The molecular and crystal structure of [(CH3)4N]2[Fe2(S2O3)2(NO)4] were studied by X-ray diffraction analysis. The iron atom in the four-membered cycle of the [2Fe–2S] anion is bound to another Fe atom and to two sulfur atoms and is coordinated by two nonequivalent NO groups, each bridging sulfur atom being bound to the SO3group. The structurally equivalent iron atoms are in the state Fe1–(S= 1/2). The Mössbauer spectroscopy method shows that the complexes are diamagnetic due to the strong Fe–Fe bond. It is found that the SO3group provides higher stability of the thiosulfate anion than the anion in Roussin's red salt [Fe2S2(NO)4]2–.  相似文献   

17.
Pr4S3[Si2O7] and Pr3Cl3[Si2O7]: Derivatives of Praseodymium Disilicate Modified by Soft Foreign Anions For synthesizing both the disilicate derivatives Pr4S3[Si2O7] and Pr3Cl3[Si2O7], Pr, Pr6O11 and SiO2 are brought to reaction with S and PrCl3, respectively, in suitable molar ratios (850 °C, 7 d) in evacuated silica tubes. By using NaCl as a flux, Pr4S3[Si2O7] crystallizes as pale green, transparent single crystals (tetragonal, I41/amd, a = 1201.6(1), c = 1412.0(2) pm, Z = 8) with the appearance of slightly compressed octahedra. On the other hand, Pr3Cl3[Si2O7] emerges as pale green, transparent platelets and crystallizes monoclinically (space group: P21, a = 530.96(6), b = 1200.2(1), c = 783.11(8) pm, β = 109.07(1)°, Z = 2). In both crystal structures ecliptically conformed [Si2O7]6– units of two corner‐linked [SiO4] tetrahedra with Si–O–Si bridging angles of 131° in the sulfide and 148° in the chloride disilicate are present. In Pr4S3[Si2O7] both crystallographically independent Pr3+ cations show coordination numbers of 8 + 1 (5 S2– and 3 + 1 O2–) and 9 (3 S2– and 6 O2–). For Pr1, Pr2 and Pr3 in Pr3Cl3[Si2O7] coordination numbers of 10 (5 Cl and 5 O2–) and 9 (2 ×; 4 Cl and 5 O2– or 3 Cl and 6 O2–, respectively) occur.  相似文献   

18.
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   

19.
K4[Ag404] Structure Type M4[Ag4O4] (M ? Li? Cs) and M4[Cu4O4] (M ? Li? Rb) have been prepared anew; as an example the crystal structure of K4[Ag4O4] has been revised. Contrary to our first report [2, 3] it crystallizes in the space-group I4 m2 with the “ring” [Ag4O4]4? which is not plane, however. Each two O2? (trans-arrangement) are rather (0.02 Å) above and below the plane of the “ring”, respectively. The new parameters are given in the text. The distances, for example d(Ag+·O2?) = 2.058 Å and the Madelung Part of Lattice Energy, MAPLE, are both in a very good agreement with the measurements and calculations, respectively, which have been done on other ternary oxides with silver.  相似文献   

20.
A new magnesium borate Mg2[B2O4(OH)2]·H2O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg2[B2O4(OH)2]·H2O in 0.9764 mol L–1 HCl was determined. With the incorporation of the enthalpies of solution of H3BO3 in HCl (aq), of MgO in (HCl+H3BO3) (aq), and the standard molar enthalpies of formation of MgO(s), H3BO3(s), and H2O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol–1 of Mg2[B2O4(OH)2]·H2O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

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