共查询到20条相似文献,搜索用时 562 毫秒
1.
Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO 4)- and (BO 4)-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[B 2(SO 4) 4] and Co[B 2(SO 4) 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: Ni II is located between the borosulfate layers, while Co II—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
2.
Borosulfates are an ever‐expanding class of compounds and the extent of their properties is still elusive. Herein, the first two copper borosulfates Cu[B 2(SO 4) 4] and Cu[B(SO 4) 2(HSO 4)] are presented, which are structurally related but show different dimensionalities in their substructure: While Cu[B 2(SO 4) 4] reveals an anionic chain, [B(SO 4) 4/2] ?, with both a twisted and a unique chair conformation of the B(SO 4) 2B subunits, Cu[B(SO 4) 2(HSO 4)] reveals isolated [B 2(SO 4) 4(HSO 4) 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 p Ka values of the two conformers of the [B 2(SO 4) 4(HSO 4) 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
3.
Two new borosulfates were obtained either by an open vessel synthesis from sulfuric acid and B(OH) 3, yielding (NH 4) 3[B(SO 4) 3] or from solvothermal synthesis in oleum enriched sulfuric acid and B(OH) 3, yielding Sr[B 2(SO 4) 4]. (NH 4) 3[B(SO 4) 3] crystallizes homeotypic to K 3[B(SO 4) 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(SO 4) 2(SO 4) 2/2] 3–}. Sr[B 2(SO 4) 4] crystallizes as an ordered variant of Pb[B 2(SO 4) 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(SO 4) 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[B 2(SO 4) 4] towards Sr[B 2O(SO 4) 3]. 相似文献
4.
Three compounds ASb 2(SO 4) 2(PO 4) ( A = H 3O +, K, Rb) were obtained from the reactions of Sb 2O 3, A2CO 3 ( A = Li, Rb) or K 2SO 4 and NH 4H 2PO 4 in H 2SO 4 (98 %) at 220–250 °C. Their structures were determined by single‐crystal X‐ray diffraction. All compounds crystallize in the triclinic space group P$\bar{1}$ (no.2) and are isostructural. The crystal structures consist of two‐dimensional 2∞[Sb 2(SO 4) 2(PO 4)] – anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO 4] ψ‐trigonal bipyramids, [SbO 5] ψ octahedra, [SO 4] tetrahedra, and [PO 4] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT‐IR spectroscopy, and Raman spectroscopy. 相似文献
5.
Preparation, Raman Spectra, and Crystal Structures of V 2O 3(SO 4) 2, K[VO(SO 4) 2], and NH 4[VO(SO 4) 2] The oxo-sulfato-vanadates(V) V 2O 3(SO 4) 2, K[VO(SO 4) 2], and NH 4[VO(SO 4) 2] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V 2O 3(SO 4) 2 consists of a threedimensional network of pairs of cornershared VO 6 octahedra with one terminal oxygen atom each, and SO 4 tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH 4[VO(SO 4) 2] and K[VO(SO 4) 2] are isostructural. VO 6 octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO 3 molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO 4) 2] ? K[VO 2(SO 4)] + SO 3 at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V 2O 3(SO 4) 2, monoclinic, space group P2 1/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(R w) = 0.039(0,033); K[VO(SO 4) 2], orthorhombic, space group P2 12 12 1, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(R w) = 0,11(0,10); NH 4[VO(SO 4) 2], orthorhombic, space group P2 12 12 1, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(R w) = 0.088(0.083). 相似文献
6.
Red single crystals of Pt 2(HSO 4) 2(SO 4) 2 were obtained by the reaction of elemental platinum with conc. sulfuric acid at 350 °C in sealed glass ampoules. The crystal structure (monoclinic, P2 1/ c, Z = 2, a = 868.6(2), b = 826.2(1), c = 921.8(2) pm, β=116.32(1)°, R all = 0.0348) shows dumbbell shaped Pt 26+ cations which are coordinated by four SO 42— and two HSO 4— ions. Each of the sulfate ions is attached to another Pt 26+ ion yielding layers according to equation/tex2gif-stack-1.gif[Pt 2(SO 4) 4/2(HSO 4) 2/1]. The layers are connected by hydrogen bonds with the OH group of the hydrogensulfate ion as donor and the non‐bonding oxygen atom of the sulfate ion as acceptor. 相似文献
7.
The crystal structure of oxonium neodymium bis(sulfate), (H 3O)Nd(SO 4) 2, shows a two‐dimensional layered framework assembled from SO 4 tetrahedra and NdO 9 tricapped trigonal prisms. One independent sulfate group makes four S—O—Nd linkages, while the other makes five such connections to generate an unprecedented anhydrous anionic [Nd(SO 4) 2] − layer. To achieve charge balance, H 3O + cations are inserted between adjacent layers where they participate in hydrogen‐bonding interactions with the sulfate O atoms of adjacent layers. 相似文献
8.
K 4[BS 4O 15(OH)], Ba[B 2S 3O 13], and Gd 2[B 2S 6O 24] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO 4) 4] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO 4) 4] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B 2S 3O 13] with band‐silicate topology and Gd 2[B 2S 6O 24] with cyclosilicate topology) and the first hydrogen borosulfate K 4[BS 4O 15(OH)]. 相似文献
9.
The preparation and structures of three diborane(4) compounds are described. The compound B 2(3,4‐S 2C 4H 2‐1‐S) 2 [2,2′‐bi(1,3,5,2‐trithiaborapentalene), C 8H 4B 2S 6] is planar and lies at a crystallographic inversion centre. The amine adducts [B 2(C 3S 5) 2(NHMe 2) 2] [2,2′‐bis(dimethylamino)‐2,2′‐bi(1,3,4,6,2‐tetrathiaborapentalene‐5‐thione), C 10H 14B 2N 2S 10] and [B 2(1,2‐S 2C 2H 4) 2(NHMe 2) 2]·0.33CH 2Cl 2 [1,2‐bis(di‐methylamino)‐1,1:2,2‐bis(dimethylenedithioxy)diborane(4) dichloromethane solvate, C 8H 22B 2N 2S 4·0.33CH 2Cl 2] contain dimethylamine ligands bound to each boron in an anti conformation about the B—B bond, with tetrahedral geometry at the B atoms. The crystal structures display a number of S?S interactions, which appear to dictate the packing arrangements. 相似文献
10.
Sr 3(BS 3) 2 and Sr 3(B 3S 6) 2: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr 3(BS 3) 2 and Sr 3(B 3S 6) 2 were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr 3(BS 3) 2 crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr 3(B 3S 6) 2 is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr 3(BS 3) 2 contains isolated [BS 3] 3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr 3(B 3S 6) 2 consists of cyclic [B 3S 6] 3— anions and strontium cations, respectively. 相似文献
11.
A novel organically templated copper pentaborate, [Cu(C 3N 2H 4) 4][Cu(CH 3COO) 2(C 3N 2H 4) 2(H 2O) 2]‐ [B 5O 6(OH) 4] 2, was synthesized by hydrothermal reaction and characterized by elemental analysis, single‐crystal X‐ray diffraction, FT‐IR spectroscopy, Raman spectroscopy and TGA. The crystal structure of this compound consists of two copper‐centered polyhedra and two discrete [B 5O 6(OH) 4] ? pentaborate anions, which are linked together through intensive hydrogen bonding interactions, forming a 3D framework with large channels along c axis. The discrete pentaborate anions form infinite layers by hydrogen bonds. Moreover, the two crystallographically different octahedral coppers are connected by common oxygen atom to form an infinite chain. 相似文献
12.
Antimony pentafluoride is a strong Lewis acid and fluoride-ion acceptor that has not previously demonstrated any discreet fluoride-ion donor properties. The first donor-stabilised [SbF 4] + cations were prepared from the autoionisation of SbF 5 in the presence of bidentate N-donor ligands 2,2’-bipyridine (bipy) and 1,10-phenanthroline (phen) as their [SbF 6] − salts. The [SbF 4(N−N)][Sb 2F 11] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF 5⋅SO 2 to [SbF 4(N−N)][SbF 6] in liquid SO 2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF 4(phen)][SbF 6] ⋅ 3CH 3CN and [SbF 4(phen)][SbF 6] ⋅ 2SO 2 were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron-pair donation from N to Sb stabilizes [SbF 4] + with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand-centred. 相似文献
13.
The solid-state structures of two non-metal pentaborates [Me 3NCH 2CH 2OH][B 5O 6(OH) 4] ( 1) and [4-MepyH, 4-Mepy][B 5O 6(OH) 4] ( 2) have been determined by single-crystal X-ray diffraction methods. Structures 1 and 2 both contain supramolecular pentaborate frameworks held together by extensive H-bond interactions. The framework of 1 exists essentially as planes of pentaborate anions linked via three pairwise ‘planar’ β → α interactions, with a fourth β → β interaction crosslinking the planes. The framework of 2 is very similar except that one of the three pairwise linkages within the plane is replaced by pairwise ‘step-like’ bifurcated H-bonds to both α sites of a neighboring anion. The cations in 1 and the cations and neutral 4-Mepy ligands in 2 are present in the framework cavities and channels, with additional H-bond interactions existing between cations and anions. 相似文献
14.
New radical cation salts (TMTSF) 2[3,3′-Co(1,2-C 2B 9H 11) 2] ( 1), (TTF)[3,3′-Co(1,2-C 2B 9H 11) 2] ( 2) and (ET)[3,3′-Co(1,2-C 2B 9H 11) 2] ( 3) were synthesized and their crystal structures and electrical conductivities were determined. Compound 1 has layered structure with conducting stacks of the TMTSF cations, whereas compounds 2 and 3 contain separated pairs of fulvalenium cations. Conductivity of crystals 1 at room temperature was found to be 15 Ohm −1 cm −1, that is the maximum value found for fulvalenium metallacarborane salts. 相似文献
15.
The reaction of MCl 4(thf) 2 (M = Zr, Hf) with 1,4-dilitiobutane in diethyl ether at –25 °C or at 0 °C with a molar ratio of 1 : 3 yields the homoleptic “ate” complexes [(thf) 4Li] [{(thf)Li}M(C 4H 8) 3] 1 - Zr (M = Zr) and 1 - Hf (M = Hf). The crystalline compounds form ion lattices with solvent-separated [(thf) 4Li] + cations and [{(thf)Li}M(C 4H 8) 3] – anions. The NMR spectra at –20 °C show magnetic equivalence of the M–CH 2 and of the β-CH 2 groups of the butane-1,4-diide ligands on the NMR time scale. Analogous reactions of MCl 4(thf) 2 with 1,4-dilithiobutane with a molar ratio of 1 : 2 proceed unclear. However, single crystals of [Li(thf) 4] [HfCl 5(thf)] ( 2 ) can be isolated with the hafnium atom in a distorted octahedral coordination sphere of five chloro and one thf ligand. NMR spectra allow to elucidate the time-dependent degradation of 1-Hf and 1-Zr in THF and toluene at 25 °C via THF cleavage. Addition of tmeda to a solution of 1-Zr allows the isolation of intermediately formed [{(tmeda)Li} 2Zr( nBu) 2(C 4H 8) 2] ( 3 ). 相似文献
16.
The interaction of ethylenediamine with iodic acid by the slow evaporation method at room temperature gives rise to the crystals of α-C2H10N2(IO3)2 and β-C2H10N2(IO3)2 denoted as α-EBI and β-EBI, respectively. The acentric crystal structures of both polymorphs that consist of [C2H10N2]2+ cations and [IO3]? anions connected together by N–H…O hydrogen bonds are discussed and compared. The optical properties of both polymorphs were determined using UV-vis diffuse reflectance spectroscopy (DRS) showing a wide transparency windows. The DFT calculations using the mixed B3PW91/[6–31?+?(d, p), LanL2Dz] basis set of optimized geometries, dipole moment (μ), polarizability (α), first static hyperpolarizability (β), and population analysis were also reported. The experimental and theoretical IR and Raman spectra were compared, and the careful and complete assignment of the vibrational motions of both compounds was undertaken with the aid of potential energy distribution (PED) analysis. DSC and AC conductivity analysis revealed that α-C2H10N2(IO3)2 and β-C2H10N2(IO3)2 undergo a first-order phase transition around 360 K. The electrical σtot (ω, T) conductivity obeyed to Jonscher’s power law and the temperature dependence of the S(T) parameter showed that the electrical conductivity of both polymorph phases might be treated using the correlated barrier hopping (CBH) model. 相似文献
17.
Green single crystals of trans‐tetraamminedibromidochromium(III) trans‐diamminetetrabromidochromate(III), [CrBr 2(NH 3) 4][CrBr 4(NH 3) 2], are found to contain two symmetry‐independent sixfold coordinated Cr III cations on centres of inversion. The structure is composed of octahedral trans‐[CrBr 2(NH 3) 4] + cations and octahedral trans‐[CrBr 4(NH 3) 2] − anions, and adopts a distorted CsCl‐type lattice. The cations and anions are linked by N—H...Br interactions. This is the first example in which both ions are mixed ammine–bromide Cr III complexes. 相似文献
18.
Reactions of [B 12H 12–n(OH) n] 2–, n = 1, 2 with Acid Dichlorides and Crystal Structure of Cs 2[1,2-B 12H 10(ox)] · CH 3OH By treatment of [B 12H 11(OH)] 2– with organic and inorganic acid dichlorides in acetonitrile the bridged dicluster compounds [B 12H 11(ox)B 12H 11)] 4– ( 1 ), [B 12H 11( p-OOCC 6H 4COO)B 12H 11] 4– ( 2 ), [B 12H 11( m-OOCC 6H 4COO)B 12H 11] 4– ( 3 ), [B 12H 11(SO 3)B 12H 11] 4– ( 4 ), [B 12H 11(SO 4)B 12H 11] 4– ( 5 ) are obtained in good yields. The dihydroxododecaborates [1,2-B 12H 10(OH) 2] 2– and [1,7-B 12H 10(OH) 2] 2– afford clusters with an anellated ring: [1,2-B 12H 10(ox)] 2– ( 6 ), [1,2-B 12H 10(SO 4)] 2– ( 7 ) and [1,7-B 12H 10(OOC(CH 2) 8COO)] 2– ( 8 ). Isomerically pure [1,7-B 12H 10(OH) 2] 2– ( 9 ) is formed by reaction of (H 3O) 2[B 12H 12] with ethylene glycol. All new compounds are characterized by vibrational, 11B, 13C and 1H NMR spectra. The crystal structure of Cs 2[1,2-B 12H 10(ox)] · CH 3OH (monoclinic, space group P 2 1/c, a = 9.616(2), b = 10.817(1), c = 15.875(6) Å, β = 95.84(8)°, Z = 4) reveals a distortion of the B 12 icosahedron caused by the anellated six-membered heteroring. 相似文献
19.
New selenidoantimonats [Ni(dien) 2] 2Sb 2Se 6 ( 1 ), [Mn(dien) 2] 2(SbSe 4)(Cl) ( 2 ), [Co(dien) 2] 2(SbSe 4)(Br) ( 3 ), and [Co(dien) 2] 3(SbSe 4) 2 ( 4 ) (dien = diethylenetriamine) were solvothermally synthesized in dien solvent at 180 °C. The crystal structure of 1 consists of two octahedral [Ni(dien) 2] 2+ cations and a mixed‐valent [Sb 2Se 6] 4? anion. The isolated [Sb 2Se 6] 4? anion is formed by a Sb IIISe 3 trigonal pyramid and a Sb VSe 4 tetrahedron sharing a common corner. 2 and 3 are composed of octahedral [M(dien) 2] 2+ cations, tetrahedral [SbSe 4] 3? anions and halide ions forming an extended network through hydrogen‐bonding interactions. In 4 the [Co(1)(dien) 2] 2+, [Co(2)(dien) 2] 2+ and [SbSe 4] 3? ions form layered structures via N–H···Se hydrogen bonds. The [Co(3)(dien) 2] 2+ ion is located between the layers, and interacts with the layers by N–H···Se bonds. The synthesis and solid state structural studies on the title compounds show that the higher reaction temperature is helpful for the formation of selenidoantimonate(V) compounds in the synthesis of selenidoantimonate from the M 2+/Sb/Se/dien system. 1 – 4 start to decompose at temperature about 210 °C in N 2 atmosphere. They lose dien ligands at a wide temperature range of 210–450 °C with multisteps for 1 – 3 and a single step for 4 . 相似文献
20.
Two new crystalline zirconium phospho-sulfates, α- and β-Zr 2(PO 4) 2(SO 4) were prepared by the gel method followed by drying and calcining at controlled temperatures. Their X-ray patterns were indexed and their infrared spectra interpreted. They belong to the NaZr 2P 3O 12 or [NZP] structural family, and constitute the first example with S 6+ in the tetrahedral site. 相似文献
|