STRUCTURE OF {Mo4S4（μ—OAc）2[S2P（OC2H5）2]4H}

<正> {Mo4S4(μ-OAc)2(dtp)4H}3,(dtp=S2P(OEt)2),Mr=1371.60,Or-thorhombic, space group Pcab, a = 18. 90 (2) ,b = 21. 678 (4 ) , c = 24. 491 (4 ) A , V = 10031(7)A3,Z=8,Dc=1.818g/cm-3,F(000)=5464,λ(MoKa)=0.71073A,finalR= 0. 069 for 3738 independent reflections. This is a successful example of the formation of [Mo4S4]5+ from[3+1] reaction mode. The results of the structure determination indicate that the configuration of the title compound exhibits a tetranuclear cubane-type core [Mo4S4]5+ with six Mo - Mo distances in the range 2. 685~2. 969A and is very similar to that of the previously characterized compound {Mo4S4(μ-OAc)2(dtp)4}2, [Mo4S4]6+, which was obtained directly by the reaction of MoCl3·3H2O with dtp. Some notable differences, however, can be found when six Mo - Mo bond distances and bonding parameters of the four terminal bidentate ligands (dtp) are compared between these two compounds , That can be attributed to the difference in the oxidation state of these two clusters .     

The Molybdenum（0）Complex [Et4N]2[Mo2（CO）6（pys）2]（pys=Pyrindine—2—thiol

The title compound tetraethylammonium hexacarbonylbis(μ-pyridine-2-thiolato-S∶S) dimolybdenum [Et4N]2[Mo2(CO)6(pys)2] crystallizes in the monoclinic, space group, P21/c with a=13.217(2), b=21.648(2), c=27.193(6)(), β=82.52(2)°, V=7714.6()3, Z=8, Mr=840.77, Dc=1.45 g/cm3, μ=7.8 cm-1, R=0.038 and Rw=0.040 for 6082 reflections with I≥3σ(I). X-ray crystal structure study reveals that the asymmetric unit of the title compound is comprised of two independent formulations of the molecular formula. Each dianion has approximate C2 symmetry and the dimetallic Mo2S2 core adopts a "butterfly" conformation with a dihedral angle between the halves of 139.3(1)° for the first independent anion and 142.8(1)° for the second one. The two pyridine rings lie on the same side of the molecule in a cis arrangement and the Mo...Mo separations are 3.76(1) and 3.838(1)().     

REACTIVITY OF METAL(O) DITHIOCARBAMATO CARBONYL COMPLEXES [Mo(CO)_4(S_2CNEt_2)]~- (M=Mo, W): SYNTHESIS AND STRUCTURE OF A NEW MIXED-VALENCE DINUCLEAR MOLYBDENUM-SULFUR COMPLEX, [Et_4N]_2[(CO)_4MoS_2MoS_2]

<正> The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

Synthesis and Crystal Structure of a Decanuclear Silver(Ⅰ)-thiolate Compound Ag_(10)S[S_2P(OEt)_2]_8

Introduction Polynuclear Ag(I)-thiolate compounds are of interests due to their unique molecular structures and metal-metal interactions. There were some such compounds reported in literatures, including Ag8(6-S)(dtp)6 [dtp=S2P(OEt)2] with [Ag8] cube,1 {Ag[S2P(OC3H7)2]}6 with a [Ag6] distorted octahedron,2 Ag11S(Et2dtc)9 [Et2dtc=S2CN(C2H5)2] with a [Ag11] cage of a 3-fold axis,3 and Ag14(6-S)(SPh)12(PPh3)8 4CH3OH13H2O with a [Ag14S12] cage composed of a staggered [Ag6] octahedr…     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

CRYSTAL AND MOLECULAR STRUCTURE OF A NEW ISOMER OF THE COMPLEX W2S4[S2P（OEt）2]2

<正> C8H20O4P2S8W2, Mr = 866. 37, monoclinic, space group P21/ n, α= 10. 122(2),b=12. 813(3),c=18. 267(3) A ;β=90. 25(1)°;7 = 2639(2) A3;Z=4; Dc=2. 43gcm-3;λ(Mo Kα) = 0. 71069A ,μ= 110. 80cm-1,F(000) = 1624,final R = 0. 039 for 2906 observed reflections with I≥3σ(I). The tungsten atom in W2S4[S2P (OEt)2]2 is coordinated by five sulfur atoms,forming a square pyramid. Two WS5 units are linked together by sharing a S-S edge.     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

SYNTHESIS AND STRUCTURE OF （Me4N）[Mo（OC6H4S—o）3]

<正> (Me_4N)[Mo(OC_6H_4S-o)_3] ,Mr=542. 57,orthorhombic,space group Pnb21 with a = 22. 708(1),b = 9. 737(4),c=10. 486(2) A;V=2318. 6A3;Z=4,Dc = 1. 55g/cm3,final R=0. 064 and Rw=0. 074.μ=8. 3cm-1, F(000) = 1108,The atom Mo( V ) of the anion issix-coordinated to three oxygen and three sulfur atoms in a distorted octahedral geometry.     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A TUNGSTEN-COPPER-SULFUR CLUSTER [Et_4N]_2[WCU_3S_4(S_2CNEt_2)_3]

<正> [Et4N]2 [WCu3S4 (S2CNEt2)3], Mr = 1172. 01, orthorhombic, space group P212121 with a=12. 858(9),b=13. 204(5) ,c=29. 501(9) A ,V=5008. 7 A3, Z = 4, Dc = 1. 55gcm-3, μ(MoKa) = 40. 3cm-1. The final R and Rw are 0. 069 and 0. 075, respectively, for 3072 observed unique reflections. The anion contains a slightly distorted WS42~ tetrahedron coordinated by three CuS2 CNEt2 units,with four metal atoms lying in a plane.     

CRYSTAL STRUCTURE OF（Bu4N）2[Pt（C3S5）2]

<正> The title compound C38H72N2PtS10(Mr=1072.74)crystallizes in triclinic system,space group P1 with cell constants a=11.994(4),b=18.117(7),c=11.855(6)A,α=95.55(4),β=99.14(3),γ=75.71(3)°,V=2460.0A3,Z=2 and Dc=1.45 gcm-3.The structure is solved by direct methods and refined by full-matrix least-squares technique to final R=0.046 and Rw=0.045 based on 5919 independent reflections with I≥3.0(I).The anion [Pt(C3S5)2]2-is approximately planar,of which the platinum-sulfur coordination polyhedron takes a square form with mean Pt-S bond length of 2.310(4)A.     

Solid state synthesis and structure of two novel polyoxometalates [(n-Bu)_4N]_4[M_6o_(19)][Ag_21_4](M=Mo,W)

The reaction of [NH4]2[MO2S2],AgI and (n-Bu)4NBr in solid state produced the polyoxometalates [(n-Bu)4N]4[M6O19][Ag2l4] (1,M=Mo;2,M=W) which were structurally determined.The crystals of 1 and 2 are isomorphous,monoclinic,space group P221/c.1,a=1.6624(2),6=1.6699(3),c=1.7217(2) nm,(8=98.29(1)°,V =4.729(1) nm3,Z=2,R=0.040,Rw=0.037;2,a= 1.6636(3),6=1.6733(3),c=1.7190(3) nm,β=98.25(1)°,V=4.736(1) nm3,Z=2,R=0.038,Rw=0.047.The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag2I4]2-and [M6O19]2-The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster ion,heteropolymetalate and organic cations,while the latter is only composed of heteropolymetalate and organic cations.     

SYNTHESIS AND STRUCTURE OF[Et_4N]_3[FE_3(SPh)_3Br_3Cl_3]

<正> The title compound was synthesized and its structure solved. The formula is [Et4N]3[Fe3(SPh)3Br3Cl3]. M=1231.95, monoclinic, space group C2/c, a=24.569(4), b=13.504(2), c=18.348.(3)A, β=110.78(1)°, V=5691(3)A3, Z=4, Dm= 1.41, Dc=1.44-g/cm3. The flat structure of the anion has. a planar [Fe3S3] ring and three phenyl groups. Statistical distribution of chlorine and bromine atoms on two sides of the [Fe3S3] plane results in a C2 symmetry of the anion.     

Crystal Structure of [Et_4N][Sm(S_2CNEt_2)_4]

The crystal structure of .[Et4N][Sm(S2CNEt2)4] was determined by X-ray diffraction technique. The crystal crystallizes in monoclinic system, space group P21/n with a= 1. 1695(3), b=2.0821(6), c=1.7420(7) nm, β=99. 79(3)°? Z=4, Dc= 1. 39 g/ cm3, μ(Mo/KTσ) = 18. 4 cm-1, F(000) = 1812. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R of 0. 053 for 3116 (Ⅰ> 3σ- (Ⅰ)) reflections. Each asymmetric unit contains two ions [Sm (S2CNEt2)4]-1 and [Et4N] +1, having distance between central atoms N5 and Sm3+ to be 0. 6522 nm. The atom Sm is coordinated by eight sulphur atoms. The Sm-S distance lies in the range of 0. 285-0. 290 nm with an average of 0. 288 nm.     

Synthesis, Structure and Secondorder Nonlinear Optical Activities of a New Tungsten（0） Compound with Pyridine-2-thiolato Ligand, [Et4N][W（pyS）（CO）4] （pys = C5H4NS^-）

The reaction of W(CO)6 with pyOSNa (C5-H4NOSNa) and Et4NCl in MeCN affords a new tungsten(0) complex [Et4N][W(pyS)(CO)4] 1 (Mr.= 536.29).The crystal and molecular structures have been determined by X-ray single-crystal diffraction.Complex 1 crystallizes in the orthorhombic system,space group P212121 with a = 8.2429(5),b = 9.1045(4),c =26.8851(14) (A),β = 90.00°,V= 2017.66(18) (A)3,Z = 4,Dc.= 1.765 g/cm3,μ = 58.51 cm-1,F(000) =1048,the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I ＞ 2σ(I).X-ray structure analysis revealed that the molecule is acentric and has large first-order hyperpolarizability (7.2 × 10-30 esu),so it could be an IR second-order nonlinear optical candidate material.     

钼(钨)/铜/硫三核簇合物[A]2[MS4(CuCN)2] (M=Mo,W;A=Et4N,PPh4)的合成及晶体结构

合成了四个三核簇合物[A]2[MS4(CuCN)2](1A＝Et4N,M＝Mo;2A＝PPh4,M＝W;3A＝Et4N,M＝W;4A＝PPh4,M＝Mo),测定了[Et4N]2[MoS4(CuCN)2]*H2O(1*H2O)和[PPh4]2[WS4(CuCN)2]*0.5DMF*H2O(2*0.5DMF*H2O)的晶体结构.1和2的簇阴离子[MS4(CuCN)2]2-(M＝Mo,W)均具有一个双齿配体MS42-和两个CuCN形成的近似D2d对称性结构.     

CRYSTAL STRUCTURE AND REACTIVITY OF (Et_4N) [Mo_3(μ_6-O)-(μ-Cl)_3(μ-OAc)_3Cl_3]

<正> (Et4N)[Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3], C14H29Cl6Mo3NO7, Mr = 823.92, triclinic, P1, a = 17. 508(4), b = 19. 602(3), c=8. 091(2)A, α=91. 25(2)°, β= 96. 56(2)°,γ= 83. 61(2)°, V = 2741(1)A3, Z = 4, Dc = 2.00g/cm3, MoKa (λ=0. 71069A), μ= 19. 44cm-1, F(000) = 1616, T = 23℃, final R = 0. 055, Rw = 0. 068 for 5728 unique intensity data (I≥3σ(I)).The molecule consists of cluster aniorn [Mo3(μ3-O) (μ-Cl)3(μ-OAc)3Cl3]- and cation (Et4N) + . There are two independent molecules in an asymmetric unit whose cluster anions A and B have the same configuration except for some bonding parameters. The cluster core may be described as an equilateral {Mo3} triangle with a capping O atom and three bridging Cl atoms below and above it respectively. In addition, each pair of Mo atoms is bridged by an acetate group and each Mo atom is further coordinated to a terminal chlorine atom. The three Mo - Mo bonds are 2. 587 (2), 2.587(2), 2. 582(2) A for cluster anion A and 2. 587(2), 2.595(2), 2.577 (2) A for cluster a     

Studies on solid state reactions of coordination compounds——XLⅦ.Solid state syntheses and crystal structures of cluster compounds {Cu_3MoS_3I}(PPh_3)_3S and {Cu_3WS_3Br} (PPh_3)_3S

Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state producedfour mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which(1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic,space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°,Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c=20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observedreflections).The results of the structure determination showed that the central units of the two cubane-like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter-nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions andfrom solution reactions are discussed.     

THE MOLECULAR AND CRYSTAL STRUCTURE OF [Et4N]2[Fe2S2（NO）4]

<正> The compound [Et_4N]_2[Fe_2S_2(NO)_4] (M_r=556.36) crystallizes in the monoclinic,space group P 2_1/n with a=9. 688(3), b=10. 882(2), c=12. 625(2), β=97. 86(3)°, Z=2, V=1318. 4, D_c=1. 40g/cm~3, ;μ(MoK_a)=12. 8cm~(-1) and F(000)=588. The final R=0. 028 and R_w=0. 029 for 2041 reflections (I≥3σ(I)).The crystals of [Et_4N]_2[Fe_2S_2(NO)_4] consist of discrete cations [Et_4N]~+ and anions