Synthesis and structure of an open-type trinuclear molybdenum cluster compound[Mo_3(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2]·0.5CH_2Cl_2·2H_2O

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)}.     

STRUCTURE OF (C_5H_7S_2) [Mo_3(μ_3-0) (μ-X)_3(μ-OAc)_3C1_3] (X=Cl,Br)

<正> Introduction. In order to synthesize trinuclear Mo cluster compounds with three bridge-linked acetoxyle groups, we changed the reaction condition described in reference(1) thus obtaining two new cluster compounds with the formula(C_5H_7S_2)[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (referred to beIow as compound (Ⅰ) when X=C1 and compound (Ⅱ) when X=Br). The diffraction work shows that the crystals of these two compounds are isomorphic.     

SUBSTITUTION REACTION OF LIGANDS IN TRINUCLEAR Mo CLUSTERS WITH "LOOSE COORDINATION SITE" AS WELL AS SYN-THESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-S) (μ-S)_3(dtp)_3(C_3H_4N_2)_3 (dtp)·(CH_3)_2CO

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.     

A bi-butterfly W-Cu-S cluster compound:Synthesis and crystal structure of(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]

The compound(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]was obtained by the reaction of Bu_4NBr,(NH_4)_2WS_4,NaS_2NCC_4H_8 and CuCl in CH_3CN and CH_3OH.It crystallizes in the monoclinicspace group P2_1/c with unit cell parameters:a=21.875(5),b=16.843(4),c=17.745(5),β=101.69(6)°,V=6402(6)~3,Z=4,D_o=1.718 g·cm~(-3).The final R and R_w values converged to 0.055and 0.060 respectively.The structure consists of two‘butterfly’units[WS_4Cu_2]linked togetherby two weak Cu—S bonds and two bridging S_2CNC_4H_8 ligands.Infrared spectra gave charac-teristic absorptions at 495 cm~(-1) for W=S and 450,435,412 cm~(-1) for W—μ-S.     

SYNTHESIS,STRUCTURE,PROPERTIES AND QUANTUM-CHEMICAL STUDIES OF CUBANE-LIKE CLUSTER COMPOUND WITH ALL-CHELATING LIGANDS [(C_2H_5)_4N]_2{Fe_4S_4[S_2CN(C_2H_5)_2]_4}

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.     

STUDY ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF THE TWO TRINUCLEAR MOLYBDENUM CLUSTERS(C_5H_7S_2)[Mo_3(μ_3-O )(μ-X)_3(μ-OAc)_3Cl_3](X=Cl,Br)

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     

A CLUSTER COMPOUND WITH DI-ENDOXYGEN LIGANDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF [Fe(MOS_4O)_2][N(C_2H_5)_4]3

[Fe(MoS_4O)_2] [N(C_2H_3)_4]_3 cluster compound with di-end-oxygen ligands has been prepared and characterized by the X-ray diffraction method. The compound crystallizes in a monoclinic space group P2_1/n with lattice parameters a=13.019(4), b=16.959(5), c=18.234(5), β=97.34(2)(°), Z=4. The final agreement factors are R=0.0740, Rw=0.0598. The terminal bond length, Mo-S_t and bridged one, MO-S_b for the compound are much longer than the counterpart without end-oxygen ligand. It possibly suggests that low valence of molybdenum and smaller electronegativity of sulphur than oxygen lead to the charge transfer as S→Mo→O.     

THE STUDY OF SPECTRA AND X-RAY CRYSTAL STRUCTURE OF A NOVEL BIONICS INSECTICIDE——(CH_3)_2NHCH(CH_2S_2O_3)_2Na·H_2O

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.     

Synthesis and structure of the cluster μ_3-sulfido-μ-(diethylphosphorodithioato-S,S''''-)-allylthioureo-cyclo-tris-[(μ-sulfido)-x-(diethylphosphorodi-thioato-S,S'''')-molybdenum(IV)],Mo_3S_4(C_4H_(10)O_2S_2P)_4(C_4H_8N_2S)

Title compound,Mr=1273.16,was synthesized by a substitution reaction and its crystal'is triclinic belonging to space group P1 with cell parameters:a=13.944(2),b=14.143(7),c=14.233(3),A,a=77.35(3)°,β=69.94(2)°,γ=63.50(3)°,V=2351(1)A~3,Z=2,D_c=1.799g cm~(-3).Room tem-perature,graphite-filtered Mo K_α,radiation(λ=0.71073A)was used for data collection.μ=14.988cm~(-1),F(000)=1280,R=0.051 for 7025 observed reflections.The crystal consists of decrete clustermolecules containing a duster core[Mo_3(μ_3-S)]~(10+)with three μ-S,one μ-dtp(dtp=[S_2P(OC_2H_5)]~(2-),three x-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom.Thebónds of cluster skeleton[Mo_3(μ_3-S)(μ-S)_3]~(4+),Mo—Mo 2.744～2.766,Mo—(μ_3-S)2.340～2.342 andMo—(μ-S)2.272～2.296 A,are comparable with those found in the related analogues.     

STUDIES OF SYNTHESIS, STRUCTURE AND PROPERTIES OF CLUSTER COMPOUND [Fe_6S_9(SCH_2CH_2OH)Cl]~(4-)

By mixing appropriate quantity of FeCl_2, (NH_4)_2MoS_4 ano HSCH_2CH_2OH in MeOH--MeONa, the crystal [(C_2H_5)_4N]_4[Fe_6S_9(SCH_2CH_2OH)Cl] was obtained. The cluster compound crystallizes in triclinic, space gtoup, P1, and crystal cell constants:a = 12.818(4)A, b = 13.632(3)A, c = 18.328(7)A, α = 106.09(2)°, β = 100.75(2)°, γ = 102.69(2)°, Z = 2. On the basis of 7517 unique data (I>3σ(I)) the structure has been refined toR = 0.0818 by the block-diagonal least-squares. The result of structure analysis shows thatthe cluster compound [Fe_6S_9(SCH_2CH_2OH)CI]~(4-) includes doubly bridging μ_2-S, triply bridgingμ_3-S and quadruply bridging μ_4-S. The [Fe_6S_9]~(2-) core of [Fe_6S_9(SCH_2CH_2OH)CI]~(4-) consistsof eight nonplanar Fe_2S_3 rhombs that are fused edge-sharing to give four Fe(μ_2-S)(μ_3-S)Fe,two Fe(μ_2--S)(μ_4-S)Fe and two Fe(μ_3-S) (μ_4-S)Fe subunits. The quantum chemical calcu-lation of EHMO method was carried out for this cluster compound. The structure analysisgives a rule wit     

SYNTHESIS AND CRYSTAL STRUCTURE OF TWO TRINUCLEAR MOLYBDENUM CLUSTERS CONTAINING A LOOSE COORDINATION SITE, {Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4-(C_3H_3ON)}·CH_3CN (Ⅰ) AND {Mo_3-(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4-(C_3H_3ON)}(Ⅱ)

The synthesis and crystal structure of two trinuclear molybdenum clusters containing a loosecoordination site, {Mo_3(μ_3-S)(μ-S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}· CH_3CN (Ⅰ) and {Mo_3(μ_3- O)-(μ- S)_3[S_2P(OEt)_2]_4(C_3H_3ON)} (Ⅱ), are reported. Cluster (Ⅰ) belongs to the monoclinic spacegroup p2_1/n, a = 16.579 (3), b = 16.959 (2), c = 16.867 (2) A, β= 94.44 (1)°, V = 4728A~3,Z = 4, D_c = 1.778g·cm~(-3). The crystal structure was solved by the Patterson method with afina1 R value of 0.045. Cluster (Ⅱ) belongs to the triclinic space group Pi, a = 13.175 (4),b = 13.372(6), c = 16.656(3)A, α= 117.87(4), β= 60.09(3), γ= 109.03(3)°, ν= 2231A~3,Z = 2, D_3 = 1.798g·cm~(-3). Direct methods were used to solve the crystal structure with afinal R value of 0.066. Both clusters are monocapped trinuclear ones having an oxazoleoccupied coordination site as their main structural characteristic. The difference in cappingatoms results in the difference in their skeletons, Mo_S_4 in cluster (Ⅰ) vs. Mo_3OS_3     

A dinuclear molybdenum cluster containing i-mnt ligand: synthesis and crystal structure of [Mo_2S_4(i-mnt)_2] (Et_4N)_2

A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

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     

Synthesis and crystal structure of an ionic cluster {[Mo_3(μ_3-O)(μ-S)_3(dtp)_3(py)_3][CdI(dtp)_2]}

A new cluster compound {[Mo3(μ3-O)(μ-S)3(dtp)3(py)3][CdI(dtp)2]} (dtp=S2P(O-was obtained from the reaction of (Mo3OS3(dtp)4(H2O)] with a CdI2-Bu4NI mixture.The molecular structure is composed of a cluster cation [Mo3OS3(dtp)3(py)3]+ and the complex anion [CdI(dtp)2]-Crystal data:Triclinic,space group P1 with cell parameters a=1.4672(7),b=1.5356(5),c=1.6806(5) nm,α=74.59(3),β=67.89(4),7=78.86(3)°,V=3.364(2) nm3,and Z=2,least-squares refinement of 8941 reflections gives a final agreement factor of R=0.052,Rw=0.065.     

MOLYBDENUM-IRON MIXED METAL CLUSTERS (Ⅰ)——THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF (η~5-C_5H_5)_2Mo_2Fe_2(μ_4-Te)(μ_3-Te)_2(CO)_6

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)).     

Synthesis and crystal structure of [V_2(μ-S_2)_2(S_2CNEt_2)_4]·2CH_3Cl

[V_2(μ-S_2)_2(S_2CNEt_2)_4].2CH_3Cl was synthesized by the reaction of NaS_2CNEt_2,Li_2S andVOCl_3 at room temperature.Crystal data:M=1061.3,space group Pbca,with the orthorhombicparameters:a=20.123(3),b=20.485(4),c=10.911(3),V=4497.7,Z=4,D_c=1.57g/cm~3,Mo Kσradiation(λ=0.71069()?),μ=13.2 cm~(-1),F(000)=2168.Final R=0.041 and R_w=0.047 for 2288 ob-served reflections with I>3σ(1).The coordination sphere of each V atom in title compound is a dis-torted tetragonal prism composed of two bidentate dithiocarbamate and two S_(2~((2-)) ligands.The V—Vdistance is 2.890 while the V—S distances fall in the range of 2.422—2.505.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL TUNGSTEN-COPPER-SULFUR CUBANE-LIKE CLUSTER {W3CuS4[S2P(OC2H5)2]3(I)(μ-CH3COO)(C5H5N)}

<正> Within recent years, study work on trinuclear Mo clusters has attracted the attention of structural chemists. In particular, people have focussed their interest on trinuclear clusters with loose ligands, such as {Mo_3S_4[S_2P(OC_2H_5)_2]_4(H_2O)} and {W_3S_4[S_2P(OC_2H_5)_2]_4(H_2O)} , in which the H_2O     

A new route to prepare the mixed oxo-ethylidynecapped trinuclear tungsten(Ⅳ)cluster and the crystal structure of H_2Na_3[W_3O(CCH_3)(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5H_2O

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).     

STUDIES ON SYNTHESIS, STRUCTURE AND PROPERTIES OF THE CRYSTAL OF TRIADIC COMPLEX {Mo[S_2CN(C_2H_5)_2]_4}~( 1){FeCl_4}~(-1){C_6H_5CH_2SSCH_2C_6H_5}

In this paper, a new complex {Mo[S_2CN(C_2H_5)_2]_4}~( 1){FeCl}~(-1){C_6H_5CH_2SSCH_2C_6H_5} is syn-thesized by the reaction of MoCl_5, FeCl_3, PhCH_2SH and diethyldithiocarbamate (DTC)in MeOH. The complex is characterized by X-ray, IR, UV-visible, reflection spectra, themeasurements of magnetic susceptibility, differential thermal and elemental analyses. The crystal of triadic complex containing multi-bond species is quite stable and rare.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR COPPER (Ⅰ) CLUSTER COMPLEX, Cu_4(α-C_(10)H_7CSS_2)_4·1/2CS_2

The title compound has been synthesized by the reaction of sodium α-dithionaphthoatewith CuCl_2 in an alkaline aqueous solution or by the reaction of α-dithionaphthoic acid withCuCl_2 in an organic solvent, The crude product was recrystallized in a mixture of CS_2 andC_2H_5OH. The crystals obtained are red and stable in air. The structure of the title compound is determined by a single-crystal X-ray diffractionanalysis. The crystal belongs to monoclinic space group C_(2h)~5- P(2_1/a) with unit cell parameters:a= 16.453(3)A, b=12.651(4)A, c=23.182(7)A, β=100.5(2)°, V=4744.6A~3,Z=4. Thestructure was refined to R=0.06 for 4707 reflections. In the molecule, Cu_4 cluster has a distorted tetrahedral configuration. Surrounding thistetrahydron are four α-perthionaphthoate ligands, coordinated to copper through the sulfuratoms. One of the sulfur atoms in each ligand forms sulfur bridge with copper atoms,while the other is coordinated to only one copper. The three Cu--S bonds formed by thethree sulfur atoms with a given copper atom are approximately coplanar. Each group--C--S_2 with Cu atom on a vertex of the tetetrahedron forms a five-member ring. Thesefive-member rings are also approximately cooplanar. The molecule possesses an approachingS_4 point symmetry. The mechanism for the formation of the title compound involves a redox reaction.which is discussed in this paper.