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1.
Trigonal Crystallizing Metal(II) Hexacyanoferrates(II) M2II[Fe(CN)6] According to X-ray powder diagrams, Ca2[Fe(CN)6], Cd2[Fe(CN)6], Zn2[Fe(CN)6] · 2 H2O, Pb2[Fe(CN)6] and the firstly described compounds Zn2[Fe(CN)6] · 2 NH3 and Sn2[Fe(CN)6] crystallize trigonal containing one formula unit in the unit cell. Ca2[Fe(CN)6] and Cd2[Fe(CN)6] are belonging to the space group D—P3 1m, the other compounds to D—P3 m1. The latters are described as coordination polymers with a coordination number 4 for Zn and 3 for Sn and Pb, respectively.  相似文献   

2.
Preparation and Properties of Vanadyl(IV) Pentacyanonitrosylferrate(II), VO[Fe(CN)5NO] · 2 H2O The preparation of VO[Fe(CN)5NO] · 2 H2O is described for the first time. Its electronic, infrared, and 57Fe-Mössbauer spectra were recorded and discussed. The thermal degradation was investigated by means of TG and DTA measurements and shows a very complex behaviour. A new preparative method for (VO)2[Fe(CN)6] · 10 H2O is also described and some of its spectroscopic properties were investigated and compared with those of VO[Fe(CN)5NO] · 2 H2O.  相似文献   

3.
Two new hetero-tetranuclear complexes, [Sm2(o-phen)2(DMF)6(H2O)2(µ-CN)4Fe2(CN)8]·;5H2O·;CH3OH (1) and [Sm2(o-phen)2(DMF)6(H2O)2(µ-CN)4Co2(CN)8]·;5H2O (2), have been prepared from reaction of SmCl3·;6H2O, K3[Fe(CN)6]·;3H2O or K3[Co(CN)6], and o-phen in methanol/DMF, and characterized. The structure of 1 consists of a cyano-bridged discrete cyclic tetranuclear complex in which the Sm(III) and Fe(III) centers are linked by four CN groups. Mössbauer spectrum of 57Fe indicates that both Fe(III) atoms in 1 have the same low-spin (S?=?1/2) electronic ground state. From comparison of the magnetic data of 1 and 2, at low temperature for 1 indicates weak ferromagnetic coupling between Sm(III) and Fe(III).  相似文献   

4.
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2] to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2] link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.  相似文献   

5.
The methyl viologen dication, used under the name Paraquat as an agricultural reagent, is a well‐known electron‐acceptor species that can participate in charge‐transfer (CT) interactions. The determination of the crystal structure of this species is important for accessing the CT interaction and CT‐based properties. The title hydrated salt, bis(1,1′‐dimethyl‐4,4′‐bipyridine‐1,1′‐diium) hexacyanidoferrate(II) octahydrate, (C12H14N2)2[Fe(CN)6]·8H2O or (MV)2[Fe(CN)6]·8H2O [MV2+ is the 1,1′‐dimethyl‐4,4′‐bipyridine‐1,1′‐diium (methyl viologen) dication], crystallizes in the space group P 21/c with one MV2+ cation, half of an [Fe(CN)6]4− anion and four water molecules in the asymmetric unit. The FeII atom of the [Fe(CN)6]4− anion lies on an inversion centre and has an octahedral coordination sphere defined by six cyanide ligands. The MV2+ cation is located on a general position and adopts a noncoplanar structure, with a dihedral angle of 40.32 (7)° between the planes of the pyridine rings. In the crystal, layers of electron‐donor [Fe(CN)6]4− anions and layers of electron‐acceptor MV2+ cations are formed and are stacked in an alternating manner parallel to the direction of the −2a + c axis, resulting in an alternate layered structure.  相似文献   

6.
Structurally Chemical Investigation of Monoammin Copper (I) Complexes : [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 The preparation and the properties of [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 are described. I.R. and Raman spectra have been recorded and assigned. According to X-ray powder diagrams, [CuNH3]2[Pt(CN)6] crystallizes in the trigonal space group D–P3 ml, a = 7.771, c = 5.988 Å, Z = 1. According to the spectroscopic and crystallographic data, it is concluded that the CuI ion is coordinated with one NH3 group and with the N atoms of the cyanometallate anions. The coordination number of the Cu+ is 4 in [CuNH3]2[Pt(CN)6] and 3 in [CuNH3]2[Pt(CN)4]. In the Cu3[Co(CN)6] · 2 NH3 complex two Cu atoms have the coordination number 2, the third Cu atom 4.  相似文献   

7.
Binary complex salts, [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH3, hydrocarbons, and ethylenediamine.  相似文献   

8.
Kinetic features of the reactions of K4[Fe(CN)6] with radicals initiated by water-soluble azo-initiator 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) at 37 °C were studied using the potentiometric method. Potassium ferrocyanide was shown to be a radical acceptor, whereas K3[Fe(CN)6] formed by the oxidation with the radicals in combination with K4[Fe(CN)6] is an electrochemical system, the study of which makes it possible to determine kinetic characteristics of radical reactions. The rate constants for the reactions of peroxide radicals RO2 · with K4[Fe(CN)6] were calculated.  相似文献   

9.
《Journal of Coordination Chemistry》2012,65(17-18):1603-1609
Reaction of K3[Fe(CN)6], NiCl2 and diethylenetriamine (dien) resulted in the formation of a cyanide-containing heterometallic compound [Ni(dien)2]2[Fe(CN)6]·4H2O 1. The structure consists of two octahedral [Ni(dien)2]2+ cations, one octahedral [Fe(CN)6]4? anion and four crystallization water molecules, which are held together by hydrogen-bonding interactions. Its TG curve exhibits two stages of mass loss. Compound 1 in DMF solutions has a very strong third-order non-linear optical (NLO) behavior with an absorption coefficient and refractive index α2?=?1.10?×?10?11?m?w?1, n 2?=??3.05?×?10?19?m2?w?1, respectively, and third-order NLO susceptibility χ(3) 4.34?×?10?13?esu.  相似文献   

10.
The complexes [Ni(Pn)2]2[Fe(CN)6] · 3H2O (I), [Ni3(Pn)5][Fe(CN)6]2 · 9H2O (II), [Ni5(Pn)9][Fe(CN)6]3 · 9H2O (III), and [Ni(Pn)2]3[Fe(CN)6]2 · 6H2O (IV) (Pn = 1,3-diaminopropane) were obtained. Their thermolysis was studied in oxidative (air), reductive (hydrogen), and inert atmospheres (argon) in a temperature range from 20 to 1000°C. Solid and gaseous products of the thermolysis were identified. In air thermolysis, the carbon of the ligands is eliminated as CO and CO2; the solid residues consist of nickel oxide, iron oxides, and the intermetallide Ni3Fe. In hydrogen thermolysis, the ligands are eliminated partially unchanged and partially hydrogenated to ammonia and hydrocarbons. The solid residue at >550°C consists of bimetallic phases with a small carbon impurity. In argon thermolysis, the ligands are eliminated partially unchanged or as fragments of the Pn molecule. The solid residues produced by calcination contain a mixture of metal and oxide phases and 10 to 20% of the initial carbon content.  相似文献   

11.
The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ2N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2O, was crystallized from an aqueous reaction mixture initially containing CuSO4, K3[Fe(CN)6] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)2(H2O)2]2+ and [Cu(en)2(H2O)1.87]2+, there being a deficiency of aqua ligands in the latter, [Fe(CN)6]4− anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)6]4− anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).  相似文献   

12.
[Ni(dien)2]3[W4S4(CN)12]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O were obtained by evaporating water-ammonia solutions containing K6[W4S4(CN)12]·2H2O·2CH3OH, diethylene triamine, and NiCl2·6H2O or CuCl2·6H2O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)2]3[W4S4(CN)12]·20H2O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) Å3, Z = 2; for the complex [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) Å3, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.  相似文献   

13.
Self-assembly of the precursor [Cu(L)]2+ (L = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) with hexacyanometalate [Fe(CN)6]3− produces a 3-D cyano-bridged Cu(II)–Fe(III) bimetallic assembly, [CuL]2[Fe(CN)6]ClO4 · H2O (1), characterized by single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that each hexacyanoferromate(III) ion connects four copper(II) ions using four co-planar CN groups which axially coordinate to the copper ion in a trans fashion forming trans-CuL(N≡C)2 moieties in (1). Magnetic studies reveal that (1) displays a ferromagnetic interaction between Cu(II) and Fe(III) through the CN linkage.  相似文献   

14.
On the Crystal Structures of the Cyano Complexes [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O, and [Cu(en)2][Ni(CN)4] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH3)6][Fe(CN)6] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH3)6][Co(CN)6] type structure. [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H2O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)2][Ni(CN)4] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.  相似文献   

15.
The reaction of lucigenin (Lc) with potassium hexacyanoferrate is accompanied by the appearance of charge-transfer bands in the visible spectral region and yields Lc{H}2[Fe(CN)6] · 4H2O in an acidic medium and Lc4[Fe(CN)6](NO3)5 · 18H2O in a neutral medium in air.  相似文献   

16.
A new hydroxo-cyanide of quadrivalent molybdenum K4[Mo(CN)2(OH)6] · 4 H2O has been isolated in pure state as yellowish green crystalline solid and has been characterised by analytical and physicochemical investigations. The new anion [Mo(CN)2(OH)6]4? has been established also by isolating two salts Cu2[Mo(CN)2(OH)6] · H2O und Ag4[Mo(CN)2(OH)6] · H2O as violet and brown solid respectively in pure state.  相似文献   

17.
Mössbauer- and IR Spectra from the Addition Compounds of K4[Fe(CN)6] with Antimony Trihalides By the reaction of K4[Fe(CN)6] with SbX3 in the melt (X = Cl, Br) or in SO2 solution (X = F) the addition compounds K4[Fe(CNSbX3)6] (X = F, Cl) and K4[Fe(CNSbX3)4(CN)2] (X = Cl, Br) are formed. The IR spectra of these compounds have been interpreted. The MÖSSBAUER spectra are single lines which exhibit a slight broadening compared with K4[Fe(CN)6] · 3 H2O. The values of the isomer shifts following the order of the LEWIS acid strengths of the SbX3 molecules correspond to a small but significant increase of the s-electron density, which is explained by the increasing influence of the π-acceptor function of the ligands.  相似文献   

18.
In the title compound, [RuII(C10H8N2)3]2[FeIII(CN)6]Cl·8H2O, the [Ru(bpy)3]2+ (bpy is 2,2′‐bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)6]3− anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen‐bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)6]3− lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N⋯O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in‐plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N⋯O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.  相似文献   

19.
Reactions of [Mn(H2dapsc)Cl2] ⋅ H2O (dapsc=2,6- diacetylpyridine bis(semicarbazone)) with K3[Fe(CN)6] and (PPh4)3[Fe(CN)6] lead to the formation of the chain polymeric complex {[Mn(H2dapsc)][Fe(CN)6][K(H2O)3.5]}n ⋅ 1.5n H2O ( 1 ) and the discrete pentanuclear complex {[Mn(H2dapsc)]3[Fe(CN)6]2(H2O)2} ⋅ 4 CH3OH ⋅ 3.4 H2O ( 2 ), respectively. In the crystal structure of 1 the high-spin [MnII(H2dapsc)]2+ cations and low-spin hexacyanoferrate(III) anions are assembled into alternating heterometallic cyano-bridged chains. The K+ ions are located between the chains and are coordinated by oxygen atoms of the H2dapsc ligand and water molecules. The magnetic structure of 1 is built from ferrimagnetic chains, which are antiferromagnetically coupled. The complex exhibits metamagnetism and frequency-dependent ac magnetic susceptibility, indicating single-chain magnetic behavior with a Mydosh-parameter φ=0.12 and an effective energy barrier (Ueff/kB) of 36.0 K with τ0=2.34×10−11 s for the spin relaxation. Detailed theoretical analysis showed highly anisotropic intra-chain spin coupling between [FeIII(CN)6]3− and [MnII(H2dapsc)]2+ units resulting from orbital degeneracy and unquenched orbital momentum of [FeIII(CN)6]3− complexes. The origin of the metamagnetic transition is discussed in terms of strong magnetic anisotropy and weak AF interchain spin coupling.  相似文献   

20.
The structure of the [Au(Dien)Cl]2[Re4Te4(CN)12]·5H2O compound prepared in an aqueous medium by the reaction of a gold(III) complex [Au(Dien)Cl]Cl2 with a tetranuclear tetrahedral tellurocyanide cluster complex of rhenium K4[Re4Te4(CN)12]·5H2O is determined by single crystal X-ray diffraction.  相似文献   

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