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.     

CRYSTAL STRUCTURE OF (Et_4N)_4[Mo_2Fe_7S_8(SPh)_(12)]

<正> (Et4N)4[Mo2Fe7S8(SPh)12] : Mw=2670.3, triclinic, p1, a=12.775(4), b=13.076(3), c=20.576(4)A, α=80.00(2), β=81.39(2), γ=61.51(2)°, V=2966.3(14) A3, Z=1, D=1.494 gcm-3, R=0.077 for 4031 observed reflections. The complex was prepared by reactions of (Et4N)2[Fe4(SPh) 10] with (Et4N)2MoS4 in an ace-tonitrile solution. The structure of [Mo2Fe7S8(SPh)12]4- anion is a double-cubane-like configuration bridged by a Fe(SPh)6 group.     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE TRI-(μ2-METHOXY)-BRIDGED 'DOUBLE-CUBANE' CLUSTER COMPLEX (Et_4N)_3[Mo_2Fe_6S_8(OMe)_3(SPh)_6]

<正> The title compound was synthesized and crystal structure was solved. (Et4N)3[Mo2Fe6S8(OMe)3(SPh)6], Mr=1922.39, hexagonal, PGs/m, a = 17.750(3), c=15.880(2) A, V=4332.7(26) A3, Z-2, Dx=1.477 g/cm3, MoKα, λ= 0.71069 A, R = 0.059, Rw = 0.065, for 814 observed reflexions. The complex anion contains two Fe3MoS4 cubane-like units linked throug their molybdenum atoms by three ,μ2-methoxy-groups, and the overall structure of the anion has C3b symmetry.     

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.     

SYNTHESIS AND STRUCTURE OF (Et_4N)_2[Ni_2(OSC_5H_4)_2(μ-SC_6H_4OH)_2]

<正> The synthesis and structure of cluster compound(Et4N)2[Ni2-(OSC6H4)2(u-SC6H4OH)2] are reported. Mr = 876.54,space group P21/n, a = 9.179(4), b = 17.487(6), c = 12.840(4) A;B=92.87(3)°;V=2058.6(2)A3; Z = 2; DC = 1.182g·cm-3.     

CRYSTAL STRUCTURE OF {Mo_3(μ_3-S)(μ-S)_3 [S_2P(OEt}_2]_4·PhCH_2CN}

<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively.     

CRYSTAL AND MOLECULAR STRUCTURE OF A OINUCLEAR MOLYBDENUM(O) CARBONYL COMPLEX WITH THIOLATO-BRIDGES,[Et_4N]_2(Mo_2(CO)_8(SC_sH_4OH)_2-C~2]

<正> The structure of a dinuclear Mo(0) carbonyl complex with thiolato bridges, [Et4N]2 [Mo2 (CO)8(SC6H4OH)2-CR](1), Mr =926.82, was determined from three-dimensional X-ray data.1 crystallizes in the triclinic,space group P1,a= 9.534(1),b=10.094(1),c= 11.954(1)A;α=80.93(38),β=68.62 (31),γ= 83.06(33)°;Z=1; V = 1055.4A3,Dc=1.46 gcm-3;A = 0.035, R2= 0.046,F(000)=476. The configuration of planar MoS2Mo core center of 1 with Mo-S distance of 2.617A and No...Mo distance of 4.0722 A is nearly the same as that of the Sph-analog. This provides an example to demonstrate the ineffectiveness of electrophilic feature of R ligand on the MoS2Mo core in a series of dinuclear Mo(0) complexes with thiolato-bridges.     

The Crystal and Electronic Structure of A Reticular Type Mo-Fe-S Cluster Compound [Et_4N]_4[Mo2Fe_4S_9(SCH_2CH_2S)_2]

The single crystal of [Et4N]4 [MO2Fe4S9(SCH2CH2S)2] was obtainedby reaction of (NH4)2HoS4, FeCl3 , HSCH2CH2SH and Et4 NBr in CH3CN and MeOH-MeONa. Cluster compound [Et4N]4 [Mo2Fe4S9(SCH2CH2S)2] crystal -Lized in the monoclinic space group C2/c with unit cell parameters:a = 17. 672(2)A, b = 33. 851(4)A, c = l3. 900(3)A, β=135.11(4)°, V=5868.8 (3.9)A3 and Z = 4. On the basis of 3514 unique data (I>2σ(I)) the structure was refined to R = 0.0575. The anion [Mo2Fe4S9(SCH2CH2S)2]4-of the cluster compound includes doubly bridging (μ2-S), triply bridging (μ3-S) and quadruply bridging (μ4 -S) . The structrue analysis gives a rule with bond lengths decreasing in the order of Fe-(μ4-S)> Fe-(μ3-s)> Fe-(μ2 -s) and EHMO calculation gives the other rule with bond order increasing in the order of Fe-(μ4-S)< Fe-(μ3-S)相似文献   

SYNTHESIS AND CRYSTAL STRUCTURE OF BIS (TETRAETHY-LAMMONIUM) BIS(TRITHIOCARBONATO) BIS(μ-PHENYLTHIO-LATO)-DI-NICKEL(Ⅱ), (Et_4N)_2[Ni_2(μ-SC_6H_5)_2(S_2CS)_2]

<正> (Et4N)[Ni2(SC6H5)2(S2CS)2],Mr= 844. 68; monoclinic P21/c, a = 16. 951(3), b = 11. 151(3), c=20. 428(2)(?) ,β=99. 03(2)°, V = 3813(3)(?)3, Z = 4, Dm = l. 48, Dx = 1. 471 gem-3, graphite-monochromated MoKa=0. 71073 (?), μ=14. 4cm-1, F(000) = 1776; T' = 295K, R = 0.061, Rw =0.072 for 5586 unique observed reflections, and 211 parameters. The structure of the complex consist of discrete [Ni2(μ-SC6H5)2(S2CS)2]2- complex anions and tetraethylammonium cations. In each anion nickel (Ⅱ) is distorted square planar coordinated with four atoms, two bridging atoms from the benzene-thiolato and two from the trithio-car-bonate, SCS22- ligand. The structure has the synendo conformation[1].     

SYNTHESIS AND STRUCTURE OF THE DINUCLEAR MANGANESE-SULFUR COMPLEX (Ph_4As)_2Mn_2(SC_3H_6S)_4

<正> (Ph4As)2[Mn2(SC3H8S)4] was obtained from the reaction of MnCl2-4H2O,Na2(1,2-pdt)(1,2-H2pdt=CH3CH(SH)CH2SH),and Ph4AsCl.C80H64As2Mn2S8, Mr =1301.41,orthorhombic,Pbca; a=10.854(2), b =22.562(6), c =24.545(6)A; V=6010.8A3;Z =4,Dc=1.44g/cm3. The centrosymmetic anion of title compound is a dimer of (Mn(pdt)2]- bridged by one sulfur atom each of the two bridging pdt2-, The atom Mo(Ⅲ) is in a distorted trigonal bipyramidal geometry.     

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)(?).     

SYNTHESIS AND STRUCTURE OF (Ph_4P)_2[Ni_3(μ-SC_3H_6S)_4]·2CH_3CN

<正> (Ph4P)2[Ni3(u-SC3H6S)4].2CH3CN was obtained from the reaction of NiCl2.6H2O,Na2(1,2-pdt)(pdtH2=CH3CH(SH)CH2SH) and Ph4PBr.Mr=1361. 80, P21/c,a=10.802(2),b=30.111 (7),c=9. 907(3) A ,B=93. 60(3) ;V= 3216. 0 A3;Z=2,Dc=1. 41g/cm3. The three Ni atoms of the anion are linearly arranged and bridged by four sulfur atoms from the four 1 ,2-propyldithiolato ligands.     

STRUCTURE OF A Fe-S CLUSTER COMPLEX [{(μ-PhCH_2S)Fe_2(CO)_6}_2(μ4-S)]

<正> [{(μ-PhCH2S)Fe2(CO)6}2(u4-S)], Mr = 837.95, triclinic, Pl,a=13.701(3),b=16.542(5), c=17.030(5)A,α=107.69(2),β=90.15(2),γ= 114.49(2)°,V=3309.3A3, Z=4, Dx=1.68 g/cm3,MoKa,λ=0.71069A μ=20.2 cm-1,F(000)=2008, room temperature, final R=0.035 for 4960 independent reflections. The molecule possesses approximate C2 symmetry with the pseudo-twofold axis passing through the unique sulfur atom u4-S(2) and the midpoint of the other two u2-sulfur atoms S(1) and S(3). The unique u4-sulfur atom has a tetrahedral geometry and donates its six valence electrons to the four iron atoms. The average Fe-(μ4-S) distance of 2.247 A is slightly shorter than the average Fe-(μ2-S) distance of 2.265A.     

STRUCTURE OF NOVEL DICOPPER(Ⅱ) COMPLEX Cu_2 (oxpn) (NCS)_2 (H_2O)(oxpn=N,N''''-bis(3-aminopropyl) oxamido)

<正> C10H10Cu2N6O4S2,Mr = 475. 41,monoclinic,space group P2/c,a = 8. 531 (2),b= 6. 870(1) ,c= 14. 463(2) A ,β=93. 84 (2), V= 845. 7 A3,Z=2,D = 1. 866 g·cm-3,μ=27. 799cm-1,F(000) = 484,R=0. 071. The molecules possesse basically a planar structure ,with the two aquamolecules displaced 2. 75 A to opposite sides of this plane and being at the apexpositions of the square pyramidal coordination of the two Cu atoms, respectively, the two carbonyls of the oxamide show the "trans-form".     

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 Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

CRYSTAL STRUCTURE OF W_4(μ_(3-)S)_4[S_2P(OEt)_2]_6

<正> W4S4 [S2P (OEt)2]6, Mr= 1974. 94, triclinic, P1, a = 14. 063 (5) , b = 16. 289(4), c= 13. 377(3) A ,α=92. 06 (2), β=95. 24(3), γ= 73. 06(2)°, V= 2919(3)A3,Z=2,DC=2. 18g/cm3, Moka radiation,λ =0. 71069A ,μ = 90. 64cm-1, F(000) = 1764,R=0. 053 and Rw = 0. 069 for 5422 reflections with I≥3σ(I).The title compound is comprised of a cubane-like cluster core [W4S4] in which every W atom is coordinated by six S atoms to form a distorted octahedron.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_2[S_2P(OEt)_2]_3][SOP(OEt)_2](0)_2

<正> M=1140.85, monoclinic, P21/c. a=12.748(2), b=14.320(2), c=23.118 (3)A,β=101.07(1)°, V=4141(2)A3, Z=4, Dc=1.830 g.cm-3. Final R=0.039 for 4160 reflections.The title compound is a rather irregular trinuclear molybdenum cluster having only two M-M bonds with two shorter Mo-Mo distances of 2.808(1), 2.839(1), and one longer Mo-Mo distance of 3.337(1)8. The existence of two Mo-Mo bonds is coincident with the electron counting for {Mo3} cluster core, and may be regarded as a result of the oxidation of a compound Mo3(μ3-S)(μ-S)2 (μ-L)[S2P(OEt)2]4(L') (L'=neutral ligands)1 characterized by us previously.     

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.     

CRYSTAL STRUCTURE OF TRIS(2-THENOYLTRIFLUOROACETONATO)BIS(TRIPHENYLPHOSPHINE OXIDE)EUROPIUM(Ⅲ), Eu(TTA)_3.(Ph_3PO)_2

<正> C60H42O8F9S3P2Eu,Mr=1372.07 triclinic, space group Pl,a = 11.191(1), b = 12.121(2), c = 23.529(3) A,α=80.08(1),β=76.51(1),γ=70.46(1)°,V=2909.3(6)A3, Dm(flotation in CCl4/BrCH2CH2Br) = 1.566, Dx(Z=2) = 1.562 g cm-3,λ(MoKα) =0.71073 A,μ=13.16 cm-1, F(OOO)=1376, T =295 °K, final RF=0.033 for 9104 observed reflections with |Fσ|>3σ(|Fσ|).The compound is isostructural with the known neodymium(Ⅲ) complex. The metal atom in the monomeric molecule is coordinated dodecahedrally by the eight 0 atoms of the surrounding ligands with Eu-0 bond distances in the range 2.361(2)-2.457(3) A.