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1.
The synthesis and crystal structure of a novel molybdenum-copper cluster compound with [(μs-S)Cus] core is reported. It was prepared from Cu2Br2 upon reaction with molybdenum sulfur compound [CH3CH2)4N]2[Mo2O2S2-(S2)(S4)]. The title compound crystallizes in the monoclinic system space group Cc with cell dimensions: a=21.320(5), b=21.869(3), c=13.029(5)A,β=118.28(1)°,Z=4, V=5349A3 and Dc=2.48 g.m-3. The structure has been determined by Patterson and Fourier methods and then refined by the least squares method to a final R of 0.053. There are some distortions from octahedron in configuration of the [(μs-S)Cu6]6 core with three weak Cu-Cu bonds.  相似文献   

2.
The crystal structure of two isomorphic cluster compounds with formula (C_5H_7S_2)-[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (X=Cl for compound (Ⅰ) and compound (Ⅱ)) has been investigated by X-ray diffraction method. The parameters of two crystals are: a=10.423(1),b=17.095(4), c=14.062(7), β=97.54(4)(°); Dc=2.20gcm~(-3), D_o=2.17g cm~(-3) for compound (Ⅰ). and a=10.511(3), b=11.213(2), c=14.053(3), β=96.12(2)(°); D_c=2.52g cm~(-3), D_o=2.53gcm~(-3) for compound (Ⅱ). The space groups are P2_1/C. Z=4. The 2621 and 2548 independent reflections with I>3σ(I) were collected on a CAD-4 four-circle diffractometer by means of MoKα radiation. The crystal structures were solved by heavy atom method and refined by full-matrix least-squares technique to a final discrepancy factors of R=0.061 and 0.051 respectively. The results of investigation show that the molecule consists of the cation (C_5H_7S_2)+ and the trinuclear Mo cluster anion, the configuration of which is similar to that of (Et_4N)_2[Mo_3(μ_3-O)(μ  相似文献   

3.
The oxidation-reduction reaction of the molybdenum cluster compound Mo_3(μ_3-S)(μ-S)_2-[μ-SOP(OEt)_2] [S_2P(OEt)_2]_3(O)_2 with CuCl_2·2H_2O has been investigated and the chemical components of its product, Cu_8Cl_2[S_2P(OEt)_2]_6, were confirmed. The crystal belongs to the triclinic system and the space group is P with the following unit cell parameters: a=11.578 (5), b=12.663 (3), c=14.317 (4); α=55.54 (2)°, β=57.35 (3)°, γ=72.23 (3)°; Z=1; D_(calc)=1.926 g·cm~(-3). Final discrepancy factor of R is 0.075 for 3573 unique reflections with I≥3σ(I). The results of investigation show that the crystal structure consists of molecular chains with Cu_8Cl_2[S_2P(OEt)_2]_6 as structural unit, in which eight Cu atoms form a cube-shaped cage. The coordination sphere of each Cu atom is a tetrahedron configuration. The distances between Cu atoms are 3.018-3.437, which indicates that there are no metal-metal bonds between Cu atoms. It is worthwhile to study further the phenomenon how Cu(+2) captures the  相似文献   

4.
When trinuclear molybdenum cluster compound with "loose coordination site", Mo_3(μ_3-S)(μ-S)_3(μ-dtp)(dtp)_3·H_2O(A) (dtp=diethyldithiophos-phinato anion), is reacted with an excess of imidazole, the H_2O ligand and the bidentate bridging ligand μ-dtp are found to be simultaneously substituted by the imidazole to form the title compound. The title crystal belongs to the space group P(?), Z =2, with the following unit cell parameters: a=14.465(2), b=14.653(4), c=14.886(6), α=99.36(3),β=93.11(2),γ=114.29(2),V=2812(3). The crystalline compound consists of an ordered array of the cluster cation and dtp anion with acetone as packed molecule. The cation possesses a symmetry of C_3. Three Mo atoms form basically an equilateral triangle with three Mo—Mo bond lengths of 2.763 (1), 2.762(1), 2.756(1) respectively.  相似文献   

5.
IR and NMR spectra of novel bionics insecticide—C_5NS_4O_6H_(12)Na·H_2O have been studied. The molecular and crystal structures of the compound also have been determined. The compound crystallizes in the monoclinic space group C_(2h)~5, - P2_1/n with α= 8.0972. (9) , b =16.262(4), c = 10.370(3), β= 94.26(2)° and z = 4.The result shows that N atom in this compound captures a proton to form HN~ group, Na~ is in statistical disorder. Therefore, the structural formula of tho compound is (CH_3)_2HN~ —CH(CH_2S_2O_3~-)_2·1/2 (Na~ )_2·H_2O.  相似文献   

6.
The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)wasobtained by the ligand substitution reaction of tetranuclear molybdenum cluster[Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in thepresence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c,Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4;Dc=1.78g/cm~3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]clustercore and t-(dtp)~(-1)ligands are retained and only μ-bridged(dtp)~(-1)ligands aresubstituted by(C_6H_5CO_2)~(-1)in the substitution reaction,thus producing the newtitle cluster compound,the structure of which contains two species of bidentateligand.  相似文献   

7.
All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori  相似文献   

8.
A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) , β = 97.531(4)o, V = 4161.0(15) A3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N+C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O–H···N and O–H···O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N+C5H5)3] ions are bound by electrostatic force to form an ionic compound.  相似文献   

9.
The reaction of Fe_2(μ_3-Te)_2(CO)_9 with Mo_2(CO)_6(η~5-C_5H_5) affords the title compound. Its X-ray analysis shows a butterfly structure for the Mo_2Fe_2 core; the two molybdenum atoms occupy the hinge with a Mo—Mo bond distance of 2.819 and the two iron atoms are on the tops of the wings with an average Mo—Fe bond distance of 2.932(2). Each molybdenum is bonded to a Cp ring, and three CO ligands are terminally bonded to each iron atom. One tellurium atom quadruply bridges Mo_Fe_2 with Mo—Te(μ_4)=2.625(2). and Fe—Te(μ_4)=2.713(2). Two tellurium atoms triply bridge the two triangular Mo_2Fe faces with Mo—Te(μ_3)=2.678(1) and Fe—Te(μ_3)=2.513(3). The molecule has C_(2v) symmetry and a bicapped triangle bipyramidal skeleton. Crystallographic parameters are as follows: space groupImm2(orthorhombic), a=14.562(3), b=10.391(1), c=7.139(4), V=1080.2(i)~3, Z=2, ρ(cald)=1.819g·cm~(-3). The final R factor was 2.2% for 620 independent reflections(I>2σ(I)).  相似文献   

10.
The title compound, [Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2 (Hdbm = dibenzoylmethane), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1, with a = 10.729(3), b = 12.269(3), c = 13.085(4) , α = 106.367(3), β = 107.643(2), γ = 94.771(2)o, V = 1547.9(7) 3, Z = 1, C50H64Cl4Mn4O24, Mr = 1410.57, Dc = 1.513 g/cm3, F(000) = 724, Rint = 0.0147, T = 293(2) K and μ = 1.046 mm–1. The final R = 0.0359 and wR = 0.0938 for 5791 observed reflections with I > 2σ(I). The structure of the complex consists of one [Mn4(μ3-O)2]8+ core with four coplanar Mn atoms disposed in an extended “butterfly-like” arrangement and two O atoms triply bridging each “wing”, and the peripheral ligation is provided by six μ2-MeCO2– , two terminal μ2-dbm– groups at the two ends of the molecule, and two MeOH molecules on the central Mn atoms. Intermolecular O…H–O hydrogen bonding interactions are found within the structure of the compound.  相似文献   

11.
The title compound forms black crystals shaped like pseudo-octahedrons, which belong to the orthorhombic system The space group is Pna 2_1 with unit cell parametrs of a=17.815(1), b=16.629(2), c=12.003(1), and with Z=4, D_(obs)=1.80g·cm~(-3), and D_(calc)=1.804g·cm~(-3). The crystal structure was solved by the heavy atom method and refiened by fullmatrix least-squares to a final conventional R factor of 0.048 for 2584 unique reflections with I≥σ(Ⅰ). The investigation confirms that the crystal structure consists of tetraethylammonium cations and trinuclear Mo cluster anions. The anion is a μ_3-O monocapped trinuclear cluster with an average Mo-Mo bond length of 2.60 (2). On the side of the Mo_3 triangular plane opposite to the μ_3-O atom, each two Mo atoms are bridged by a Cl atom with the result that these seven atoms (3 Me, 1 O and 3 Cl atoms)form an apex-deficient quasicubane configuration. In addition, each Mo atom is coordinated to three additional atoms resulting in a pseudo-octahedral geome  相似文献   

12.
Under anaerobic and water-free condition and pure dinitrogen atmosphere, the title com-pound has been synthesized from FeCl_2, (NH_4)_2WS_4, NaS_2CN(C_2H_5)_2 and (C_2H_5)_4NBr. Thecompound crystallizes in the monoclinic space group Cc with cell constants a = 22. 125(6)A,b = 11.313(3) A, c = 25.053(8) A, β= 118.05(2)°, V = 5534.2A~3, Z = 4. It contains cubane-like Fe_4S_4 core. Each Fe atom in the compound is coordinated by a disulfide-chelate ligand.The determination results of the Mossbauer spectrum arid XPS, and quantum-chemical cal-culation all show that the compound contains two kinds of Fe in different valence states butin an equal amount. The scheme of the formation reaction for the compound is given. Thespectra of IR and UV-vis, and redox properties for the compound are reported.  相似文献   

13.
<正>A sandwich-type tungstophosphate, (1,3-H_2dap)_8H_4[Co_4(H_2O)_2(α-B- PW_9O_(34))_2]_2·5H_2O (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and UV spectroscopy. The title compound crystallizes in triclinic, space group P1 with a = 13.691(3), b = 17.744(4), c = 20.620(5), α =113.466(5), β = 91.184(5), γ = 104.223(5)°, V = 4414.3(17)~3, C_(24)H_(96)Co_8N_(16)O_(145)P_4W_(36), M_r = 10143.09, D_c = 3.816 g/cm~3, μ(MoKα) = 24.210 mm~(-1), F(000) = 4452, Z = 1, the final R = 0.0694 and wR = 0.1519 for 9910 observed reflections (I > 2σ(I)). The compound consists of two sets of tetra-transition metal-substituted sandwich frameworks, [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) having an inversion centre. Two lacunary α-B-[PW_9O_(34)]~(9-) Keggin units are linked by a rhomb-like Co_4O_(14)(H_2O)_2 cluster, in which the Co~(2+) ions are coordinated by one water molecule. Isolatedly protonated 1,3-H2dap~(2+) units act as counter-ions to interact with the [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) heteropolyanions via hydrogen bonds, resulting in a three-dimensional framework.  相似文献   

14.
[Me4N]10[Fe4(OH)4(PW10O37)2] · 15H2O was synthesized by the reaction of FeCl3 ·6H2O, with △-Na8HPW9O34 and Me4NBr. Crystal data: M = 6225.75, space group P21/c with the monoclinic parameters: a = 1.3228(5), b = 3.5634(3), c = 1.5226(2) nm, β = 94.20(2)°, V = 7.1576nm3, 7 = 2,DC = 2.888 g/cm3, Mo Kαradiation (λ = 0.071069 nm), μ= 168.534 cm-1, F(000)=5576, final R = 0.0428 and Rw = 0.1204 for 7086 observed reflections with I > 2σ( I) . The structure of the title compound is the first structurally characterized heteropolymetalate with hydroxo-bridging metal aggregation Fe4OH4 encapsulated in the dimer of Keggin polyoxoanion.  相似文献   

15.
The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.  相似文献   

16.
The compound (C_5H_7S_2)_3[Mo_3 (μ_3--S)_2 (μ_2--Cl)_3 Cl_6] forms dark black octahedralcrystals with the following crystallographic parameters: a=22.885(10)A, c=25.407(7)A. Thespace group is I4_1/α, Z=16, ρ_(obs.)=2.073g/cm~3, ρ_(calc.)=2.126g/cm~3. The 1621 independentreflections with I≥3σ were collected on a CAD-4 four-circle diffractometer by means of MoK_αradiation. The structure was solved by three-dimensional Patterson synthesis and refined byleast squares technique to a final discrepancy factor of R=0.056. The results of our investiga-tion reveal that the molecule consists of a trinuclear Mo cluster anion and three planar mono-cations.surrounding the cluster anion. As the core of the anion the triad of Mo atoms, possessing anequilateral triangular configuration, is linked by two μ3--S bridging atoms and three μ2--Clatoms. Besides, two terminal Cl atoms are attached to each Mo atom to form an octahedralconfiguration. The diamagnetism and the short Mo-Mo distances (2.556 A, 2.641 A, 2.653 A)clearly indicate the existence of Mo-Mo bonds. The anion as a whole has an idealized D_(3h) localsymmetry.  相似文献   

17.
The synthesis and the structural characterization of the title compound H_2Na_3[W_3O(CCH_3)-(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5 H_2O are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of Na_2WO_4·2H_2O in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS and ~1H NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV)and W(VI)respectively.The crystal is rhombohedral with the space group R32,a=17.058(3),c=49.665(9),γ=120°,V=12516(9)~3,Z=6,final R=0.037 for 2071 reflections with I≥3σ(I).Boththe cluster cation and anion have a C_3 symmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730(2);W—μ_3-O,2.00;W—O(carboxyl),2.12;W—O_t,2.18(2).  相似文献   

18.
The crystal structure of Di-nitratobis(ethylcaprolactam)uranyl(Ⅱ) UO_2[CH_2(CH_2)_4CONC_2H_5]_2(NO_3)_2 was established by a single-crystal X-ray diffraction study.It is triclinie, space group P1, with a=7.171(2), b=8.655(3), c=10.182(5)A, α=78.27(3), β=70.63(3), γ=81.76(3)°, V=581.7(4)A~3, Z=l, Dc=1.94 g.cm~(-3).Final R value is 0.0218.The result reveals that uranyl ion is coordinated to six oxygen atoms, two of them are from two carbonyl groups of ethylcaprolactam and the other four are from two nitrate groups.  相似文献   

19.
<正> Trigallium tris(orthophosphate) hydrate-2-ethanolamine was synthesized from the ethanolamine(EAN)-Ga2O3-P2O5-H2O system. The compound crystallizes in monoclinic system, space group P21/n, with a = 8.669(2), b = 17.932(4), c = 9.097(2) A,β= 108.32(1)°,V=1342.4 A3, Z = 4. The structure was solved by direct methods and refined to final R of 0.048. For the three gallium atoms in an asymmetric unit, the coordination tetrahedron of Ga(3) is nearly regular, while Ga(l) and Ga(2) are each coordinated by five oxygen atoms and their coordination polyhedra show some distortion from a trigonal bipyramid. The three-dimensional net in the crystal lattice is built of two-dimensional nets which are composed of irregular triangles, quadrilaterals, pentagons and octagons formed by Ga and P atoms. Moreover, the corrugated 2D nets running along [101] are linked together by two double-crank-shaft chains of GaPO4, one of which runs along [101] while the other along [101]. The ethanolamine molecule, so called the template,  相似文献   

20.
Employing 4,4-trimethylenedipyridine as a template,a new two-dimensional zinc phosphite (4,4-(C5H4N)2(CH2)3)· [Zn3(HPO3)4 ] has been prepared at room temperature and characterized by single-crystal X-ray diffraction,FTIR,elemental analysis,powder X-ray diffraction,and thermogravimetric analysis.The compound crystallizes in the monoclinic space group P2 1 /c,with cell parameters,a=9.3309(19),b=14.798(3),c=33.637(7),β=91.11(3),V=4643.8(16) nm 3 and Z=4.The connectivity of the ZnO4 tetrahedra and HPO 3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn O P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction.The diprotonated 4,4-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.  相似文献   

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