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1.
Ｔｈｅｔｒｉｍｏｌｙｂｄｅｎｕｍｃｌｕｓｔｅｒｓｗｉｔｈｇｅｎｅｒａｌｆｏｒｍｕｌａ[Ｍｏ3(μ3Ｓ)(μＳ)3(μｄｔｐ)(ｄｔｐ)3Ｌ](ｄｔｐ=(Ｓ2Ｐ(ＯＣ2Ｈ5)2)-,Ｌ=Ｈ2Ｏ,ｐｙ,ＳＣ(ＮＨ2)2ｅｔｃ.)[1](ｒｅｆｅｒｒｅｄｔｏａｓＭ1ｔｙｐｅ[2]),ａｎｄ[Ｍｏ3(μ3Ｓ)(μＳ2)3(ｄｔｐ)3]Ｘ(Ｘ=Ｃｌ,Ｉ)[3](ｒｅｆｅｒｒｅｄｔｏａｓＭ2ｔｙｐｅ),ａｒｅｔｗｏｍａｉｎｔｙｐｅｓｏｆｔｒｉｍｏｌｙｂｄｅｎｕｍｃｌｕｓｔｅｒｓｅｖｅｒｉｎｖｅｓｔｉｇａｔｅｄｂｙｏｕｒｒｅｓｅａｒｃｈｇｒｏｕｐ.Ａｓｗｅｈａｖｅａｌｒｅａｄｙ…  相似文献   

2.
１　ＩＮＴＲＯＤＵＣＴＩＯＮＤｉｍｏｌｙｂｄｅｎｕｍａｌｋｙｎｅｃｏｍｐｌｅｘｅｓ〔Ｍｏ２（μＲ１Ｃ≡ＣＲ２）（ＣＯ）４（η５Ｃ５Ｈ５）２〕ｃａｎｒｅａｃｔｗｉｔｈａｖａｒｉｅｔｙｏｆｒｅａｇｅｎｔｓｓｕｃｈａｓｐｈｏｓｐｈｉｎｅｓ,ｔｈｉｏｌｓ,ｅｌｅｍｅｎｔａｌｓｕｌｆｕｒ,Ｒｕ３（ＣＯ）１２ａｎｄＣｏ２（ＣＯ）８〔１－４〕．Ｉｎｔｈｅｐｒｏｄｕｃｔｓｔｈｅａｌｋｙｎｅｌｉｇａｎｄｉｓｕｓｕａｌｌｙｒｅｔａｉｎｅｄ．Ｓｏｍｅｔｉｍｅｓ,ａｌｋｙｎｅｓｃｉｓｓｉｏｎｏｃｃｕｒｓ．Ｂｅｉｎｇ…  相似文献   

3.
１　ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｏｕｒｅｆｆｏｒｔｓｔｏｄｅｖｅｌｏｐｔｈｅｌｏｗ－ｖａｌｅｎｃｅＭｏ－ＳＲｃｏｍｐｏｕｎｄｓ,ｗｅｈａｖｅｆｏｕｎｄａｎＭｏ（０）－ｃｏｍｐｏｕｎｄ,〔Ｍｏ２（ＳＲ）２（ＣＯ）８〕２－,ｗｈｉｃｈｉｓｏｂｔａｉｎｅｄｆｒｏｍｔｈｅｒｅａｃｔｉｏｎｏｆＭｏ（ＣＯ）６ｗｉｔｈＲＳ－ｉｎｈｉｇｈｙｉｅｌｄ,ｐｏｓｓｅｓｓｅｓａｎｉｎｔｅｒｅｓｔｉｎｇｔｗｏ－ｅｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｐｒｏｐｅｒｔｙ．Ｎｕｍｅｒｏｕｓｋｉｎｄｓｏｆｄｉｎｕｃｌｅａｒｍｏｌｙｂｄｅ…  相似文献   

4.
ＩｎｔｒｏｄｕｃｔｉｏｎＡｓｅａｒｌｙａｓ１８５１,Ｄｅｖｉｌｌｅ［１］ｆｉｒｓｔｉｄｅｎｔｉｆｉｅｄｓｅｖｅｒａｌｄｏｕｂｌｅｃａｒｂｏｎａｔｅｓｏｆｔｈｅｆｏｒｍｕｌＡ２ＣＯ３·ＭＣＯ３·４Ｈ２Ｏ（Ａ＝Ｎａ,ＫａｎｄＭ＝Ｍｇ,Ｎｉ,Ｃｏ）ａｎｄｒｅｐｏｒｔｅｄｔｈｅｐｏｔａｓｓｉｕｍｃｏｍ－ｐｏｕｎｄｓｗｉｔｈａｎｏｒｔｈｏｒｈｏｍｂｉｃｓｙｓｔｅｍ［１］．Ｓｉｎｃｅｅａｃｈｏｆｔｈｅｔｈｒｅｅｃａｒｂｏｎａｔｅｏｘｙｇｅｎｓｉｓａｂｌｅｔｏｐａｒｔｉｃｉｐａｔｅｉｎｃｏｏｒｄｉｎａｔｉｏｎ…  相似文献   

5.
1　ＩＮＴＲＯＤＵＣＴＩＯＮＡｌｔｈｏｕｇｈｔｈｅｂｉｎｕｃｌｅａｒｏｘｏｍｏｌｙｂｄｅｎｕｍ (Ｖ )ｃｏｍｐｏｕｎｄｓｏｆｅｔｈｙｌｅｎｅｄｉ ａｍｉｎｅｔｅｔｒａａｃｅｔａｔｅ (ＥＤＴＡ)ｃｈｅｌａｔｅｌｉｇａｎｄｗｅｒｅｗｉｄｅｌｙｓｔｕｄｉｅｄｄｕｒｉｎｇｌａｔｅｒ 50ｓ[1～ 4],ｔｈｅｆｉｒｓｔｓｕｃｈｃｒｙｓｔａｌｓｔｒｕｃｔｕｒｅｏｆｐｏｔａｓｓｉｕｍｓａｌｔｄｉｄｎｏｔａｐｐｅａｒｕｎｔｉｌ1 967[5 ],ａｎｄａｎ ｏｔｈｅｒｓｔｒｕｃｔｕｒｅｏｆｓｏｄｉｕｍｓａｌｔｗａｓｒｅｐｏｒｔｅｄｉ…  相似文献   

6.
1　ＩＮＴＲＯＤＵＣＴＩＯＮＣｅｒｔａｉｎｃｏｐｐｅｒｃｏｍｐｌｅｘｅｓｈａｖｅｂｅｅｎｓｈｏｗｎｔｏｈａｖｅｕｎｕｓｕａｌｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｓｕｃｈａｓｏｘｙｇｅｎｔｒａｎｓｆｅｒ,ｏｘｉｄａｔｉｖｅａｄｄｉｔｉｏｎａｎｄｈｏｍｏｇｅｎｏｕｓｃａｔａｌｙｔｉｃｈｙｄｒｏｇｅｎａｔｉｏｎ[1].Ｏｘｉｄａｔｉｖｅａｄｄｉｔｉｏｎｒｅａｃｔｉｏｎｓａｒｅｋｅｙｓｔｅｐｓｉｎｔｈｅａｃｔｉｖａｔｉｏｎｏｆσｂｏｎｄｓｉｎａｇｒｅａｔｎｕｍｂｅｒｏｆｃａｔａｌｙｔｉｃｐｒｏｃｅｓｓ.Ｃｏｐ…  相似文献   

7.
１ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｒｅｃｅｎｔｙｅａｒｓ,ａｓｅｒｉｅｓｏｆｌａｎｔｈａｎｉｄｅ ａｌｕｍｉｎｉｕｍｃｏｍｐｌｅｘｅｓｗｈｉｃｈａｒｅａｃｔｉｖｅｆｏｒｐｏｌｙ ｍｅｒｉｚａｔｉｏｎｏｆｏｌｆｉｎｓ〔１〕ｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄ．...  相似文献   

8.
ＣｏｍｐｏｕｎｄｓｆｏｒｍｅｄｆｒｏｍＣｕ ,ＡｇａｎｄＡｕｗｉｔｈｄｉｔｈｉｏ ｌａｔｅｌｉｇａｎｄｓ ,ｓｕｃｈａｓｔｈｅｄｉａｌｋｙｌｄｉｔｈｉｏｃａｒｂａｍａｔｅ (ＤＴＣ) ,ｍｅｒｃａｐｔｏｔｈｉａｚｏｌｉｎｅ (ＨＭＴ)ａｎｄｄｉａｌｋｙｌｄｉｔｈｉｏｐｈｏｓｐｈａｔｅｓ(ＤＤＰ) ,ｈａｖｅｐｌａｙｅｄａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｔｅｃｈｎｏｌｏｇｙ .1Ｃｕ(Ｉ) Ｓｃｌｕｓｔｅｒｓａｌｓｏｈａｖｅｂｅｅｎｉｍｐｌｉｃａｔｅｄｉｎｂｉｏｌｏｇｙａｓａｎ ｔｉ ｏｘｉｄａｎｔｓ .2Ｔｈｅｃｕｂａｎ…  相似文献   

9.
ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_５）_２Ｙｂ（ＮＣ_４Ｈ_４）（ＯＣ_４Ｈ_８）ＷａｎｇＳｈａｏ－Ｗｕ；ＹｕＹｏｎｇ－Ｆｅｉ；ＨｕＪｉ－ｐｉｎｇ；ＹｅＺｈｏｎｇ－Ｗｅｎ（ＩｎｓｔｉｔｕｔｅｏｆＯｒｇａｎｉｃＣｈ...  相似文献   

10.
刘志宏  高世扬  胡满成  夏树屏 《中国化学》2002,20(12):1519-1522
ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｒｅａｒｅｍａｎｙｋｉｎｄｓｏｆｍａｇｎｅｓｉｕｍｂｏｒａｔｅｓ ,ｂｏｔｈｎａｔｕｒａｌａｎｄｓｙｎｔｈｅｔｉｃ .Ａｂｏｒａｔｅｄｏｕｂｌｅｓａｌｔ (2ＭｇＯ·2Ｂ2 Ｏ3 ·ＭｇＣｌ2 · 14Ｈ2 Ｏ)ｎａｍｅｄｃｈｌｏｒｏｐｉｎｎｏｉｔｅｗａｓｏｂ ｔａｉｎｅｄｆｒｏｍｔｈｅｎａｔｕｒａｌｃｏｎｃｅｎｔｒａｔｅｄｓａｌｔｌａｋｅｂｒｉｎｅ .1Ｉｎｏｒｄｅｒｔｏｆｉｎｄｔｈｅｆｏｒｍｉｎｇｒｅｌａｔｉｏｎｂｅｔｗｅｅｎｔｈｅｄｏｕｂｌｅｓａｌｔａｎｄｍａｇｎｅｓｉｕｍ ｂｏｒａ…  相似文献   

11.
The title compound, tetrakis(tetraethylammonium) cyclo‐tetra‐μ‐oxo‐tetrakis[dioxovanadium(V)] dihydrate, (C8H20N)4[V4O12]·2H2O, was obtained by reacting V2O5 with (C2H5)4NOH. It consists of a discrete centrosymmetric molecular anion, [V4O12]4?, where four tetrahedral VO4 units share two vertices with each other to form a ring. A water mol­ecule is attached on each side of the ring through hydrogen bonds.  相似文献   

12.
Polyoxometallates are capable of including transition metals in their crystal structures as either discrete cations or heteroatoms. The title compound crystallizes with triclinic symmetry and consists of a centrosymmetric [V10O28]6? anion, a trimeric {[Na(H2O)3][Ni(H2O)6][Na(H2O)3]}4+ cation, an [Ni(H2O)6]2+ cation and four water molecules of crystallization. The compound possesses two Ni atoms (each on independent inversion centres), one as a discrete cation and one in a disodium–nickel trimeric cation involved in the one‐dimensional polycation–polyanion hybrid polymer. The polymers are bound together via hydrogen bonds to the water mol­ecules and the nickel(II) hexahydrate cation. Several structures of decavanadate compounds having transition metal atoms, monovalent cations and [V10O28]6? anions in the ratio 2:2:1 have been reported previously. However, the present compound differs from these in its arrangement of monovalent cations and transition metal atoms.  相似文献   

13.
A polymeric VIV‐Cd compound, {(NH4)2[(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]·H2O}n (H3nta = nitrilotriacetic acid), has been prepared and characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group C2/c with a = 17.3760(2) Å, b = 8.0488(1) Å, c = 17.3380(2) Å, β = 107.9690(10)°, V = 2306.55(5) Å3, Z = 4, and R1 = 0.0303 for 1958 observed reflections. The structure exhibits a heterometallic three‐dimensional network formed by polymeric [(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]2? anions.  相似文献   

14.
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   

15.
The title compound, tri­ammonium cis‐di­aqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing VIV to VV in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO2(SO4)2(OH2)2]3? anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.  相似文献   

16.
[Mn(H2O)2]4[HNC5H4(COO)]2[C6H2(COO)4]2·4H2O — A Three‐dimensional Coordination Polymer with Guest Water Molecules in Channel‐like Voids Single crystals of [Mn(H2O)2]4[HNC5H4(COO)]2[C6H2(COO)4]2·4H2O have been prepared in aqueous solution at 55 °C. Space group P1¯ (no. 2), a = 999.7(2), b = 1314.4(2), c = 1645.8(2) pm, α = 101.096(8)°, β = 92.796(14)°, γ = 96.03(2)°, V = 2.1053(5) nm3, Z = 2. There are four unique Mn2+ which are coordinated in a distorted, octahedral manner by two water molecules, three oxygen atoms of the pyromellitate anions and one oxygen atom of isonicotinic acid (Mn—O 208.6(2) — 227.3(3) pm). The connection of Mn2+ and [C6H2(COO)4]4— yields a three‐dimensional coordination polymer with two different, channel‐like voids extending parallel to [110]. The first channel accomodates water molecules, the second channel is filled by isonicotinic acid molecules. Thermogravimetric analysis in air revealed that the loss of water of crystallisation occurs in two steps between 97 and 200 °C. The dehydrated sample was stable between 200 and 340 °C. Further decomposition yielded Mn3O4.  相似文献   

17.
The new polyoxovanadate (POV) compound {[Cu(H2O)(C5H14N2)2]2[V16O38(Cl)]} · 4(C5H16N2) was synthesized under solvothermal conditions and crystallizes in the tetragonal space group I41/amd with a = 13.8679(6), c = 45.558(2) Å, V = 8761.7(7) Å3. The central structural motif is a {V16O38(Cl)} cluster constructed by condensation of 16 square‐pyramidal VO5 polyhedra. The cluster hosts a central Cl– anion. According to valence bond sum calculations, chemical analysis and magnetic properties the cluster anion may be formulated as [V15IVVVO38(Cl)]12–, i.e., only one vanadium atom is not reduced. To the best of our knowledge this is the first reported {V16O38(X)} cluster in this VIV:VV ratio. The presence of the two different vanadium oxidation states is clearly seen in the IR spectrum. An unusual and hitherto never observed structural feature is the binding mode between the [Cu(H2O)(C5H14N2)2]2+ complexes and the [V15IVVVO38(Cl)]12– anion. The Cu2+ ion binds to a μ2‐O atom of the cluster anion whereas in all other transition metal complex‐augmented POVs bonding between the transition metal cation and the anion occurs through terminal oxygen atoms of the POV. The magnetic properties are dominated by strong antiferromagnetic exchange interactions between the V4+ d1 centers, whereas the Cu2+ d9 cations are magnetically decoupled from the cluster anion. Upon heating, the title compound decomposes in a complex fashion.  相似文献   

18.
Reactions of 1,10‐phenanthroline monohydrate, Na2C4H4O4 · 6 H2O and MnSO4 · H2O in CH3OH/H2O yielded a mixture of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O ( 1 ) and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) Å3, Z = 1) consists of the dinuclear [Mn2(H2O)4(phen)2(C4H4O4)2] molecules and hydrogen bonded H2O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H2O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) Å3, Z = 2) is composed of the [Mn(phen)2(H2O)2]2+ cations, [Mn(phen)2(C4H4O4)] complex molecules, (C4H4O4)2– anions, and H2O molecules. The (C4H4O4)2– anions and H2O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.  相似文献   

19.
The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H2O)9]2[B12H12]3·15 H2O and its Oxonium‐Chloride Derivative [La(H2O)9](H3O)Cl2[B12H12]·H2O By neutralization of an aqueous solution of the free acid (H3O)2[B12H12] with basic La2O3 and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H2O)9]2[B12H12]3·15 H2O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H2O)9]2[B12H12]3·15 H2O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B12H12]2− anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La3+ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B12H12]2− anions on La3+ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–Oδ–···+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H3O)2[B12H12] with lanthanum trichloride an anion‐mixed salt with the composition [La(H2O)9](H3O)Cl2[B12H12]·H2O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B12H12]2− anions and H3O+ cations alternate with layers of [La(H2O)9]3+ cations (d(La–O) = 252–260 pm) and Cl− anions along [001]. The [B12H12]2− (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl− anions exhibit no coordinative influence on La3+. Hydrogen bonds are formed between the H3O+ cations and [B12H12]2− anions, also between the water molecules of [La(H2O)9]3+ and Cl− anions, which contribute to the stabilization of the crystal structure.  相似文献   

20.
Rare‐Earth‐Metal Coordination Polymers: Syntheses and Crystal Structures of Three New Glutarates, [Pr2(Glu)3(H2O)4] · 10.5H2O, [Pr(Glu)(H2O)2]Cl, and [Er(Glu)(GluH)(H2O)2] The new rare‐earth dicarboxylates [Pr2(Glu)3(H2O)4] · 10.5H2O ( 1 ), [Pr(Glu)(H2O)2]Cl ( 2 ) and [Er(Glu)(GluH)(H2O)2] ( 3 ) were obtained from the reactions of glutaric acid with PrCl3·6H2O and Er(OH)3, respectively. The crystal structures were determined by single‐crystal X‐ray diffraction. [Pr2(Glu)3(H2O)4] · 10,5H2O crystallizes in the orthorhombic space group Pnma (no. 62) with a = 871.7(4), b = 3105.0(9), c = 1308.3(9) pm and Z = 4. The crystals of [Pr(Glu)(H2O)2]Cl are monoclinic (I2/a; no. 15) with a = 786.2(1), b = 1527.6(2) c = 801.2(1) pm, β = 99.78(1)° and Z = 4. [Er(Glu)(GluH)(H2O)2] crystallizes in the monoclinic space group P21/a (no. 14) with lattice parameters of a = 882.4(1), b = 1375.3(2), c = 1267.4(2) pm, β = 107.13(1)° and Z = 4. The rare‐earth cations have the coordination numbers 10 ( 1 ), 8 + 1 ( 2 ) and 9 ( 3 ). The individual polyhedra are connected to chains and further to sheets in 1 and 2 and to double chains in 3 . Only in the water‐rich compound 1 there are channels that contain crystal water molecules. It, therefore, has a considerably lower density than 2 and 3 .  相似文献   

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