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.     

CRYSTAL STRUCTURE OF Mo_2(u-S)_2(S_2P(OEt)_2)_4

<正> Mr=996.91, triclinic, P1, a=8.773(2), b=9.712(3), c=13.652(1) A; α=69.24(0), β=70.43(3), γ=66.87(l)°; Z=l, Dx=1.699 g/cm 3. Final R=0.053 for 3186 reflections with I≥3a(I). There is an interesting trans influence of μ-s bridge in this binuclear cluster. Mo-Mo distance is 2.752(1) A.     

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.     

CRYSTAL STRUCTURE OF ORGANOLANTHANIDE COMPLEX [Li~+(DME)_3]_2[(CpNd)_4(μ_2-CH_3)_2(μ_4-O)(μ_2-Cl)_6]~(2-)

<正> The crystal and molecular structure of [Li+(DME)3]2[(CpNd)4 (μ2-CH3)2(μ4-O) (μ2-Cl)6]2~was determined from single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P21/n with lattice parameters a= 14. 614(5), b= 18. 683 (5),c= 24. 595 (6) A, β = ,91-85(2)°, V = 6712(3) A3,2 = 4,DC = 1. 63g/cm3,F(000) = 3256,Mr=1650. 85. The structure was solved by direct methods and Fourier techniques and refined by least-squares to a final R=0. 047,RW = 0. 049 for 3761 with I>3σ(I). The result revealed that the anion [(CpNd)4(μ4-O) (μ2-Cl)6(μ2-CH3)2]2- is composed of four neodymium (Ⅲ) atoms bridged by six Cl atoms, two methyl groups and one oxygen atom, and every Nd is bonded to a cyclopentadienyl group. The four Nd atoms form a distorted tetrahedron. The cations are composed of two Li+(DME)3 with average Li-O distance of 2. 120(40) A.     

SYNTHESIS AND MOLECULAR STRUCTURE OF AN ION PAIR COMPOUND [YCl_2(THF)_5]~+[YCl_4(THF)_2]~-

<正> [YC12(THF)5][YC14(THF)2], MT = 895. 2, monoclinic, space group C2/c, a = 12. 568(4), b = 11. 538(3), c=27. 354(3)A,β=91. 46(2)°, V = 3965. 3A3, Z = 4, Dc= 1. 500gcm-3,λ(MoKa) = 0. 71073A , F(000) = 3680, R = 0. 057 for 1663 observed reflections. The average Cl-O distance is 2. 570 A in the cation, 2. 607A in the anion. The average Y-O distance of 2. 391A in the cation is slightly longer than that of 2. 318 A in the anion.     

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.     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER (η~5-C_5H_5)_2W_2Fe_2(μ_3-S)_2(CO)_8

<正> (η5-C5H5)W2Fe2(μ3-S)2(CO)8,Mr = 897. 80,monoclinic,C2/c,a= 18. 019 (2),b = 8. 330(1),c= 16. 043(2) A ,β= 114. 30(1)°,v = 2194. 7(6)A3,z= 4, Dx = 2. 717g/cm3, A(MoKa) = 0. 71037 A , μ= 122. 01cm-1, F (000) = 1656, T = 295K,R=0.056,Rw = 0. 059 for 1250 observed reflections. The crystals of the title compound are isomorphous with the analog (η5-C5H5)2Mo2Fe2(μ3-S)2(CO)8.     

THE CRYSTAL STRUCTURE OF BIS(TETRAETHYLAMMONIUM)(μ-OXO)BIS[TRIPHENYL-THIOLATO-IRON(Ⅲ)],(Et_4N)_2[Fe_2O(SPh)_6]

<正> Fe_2OSsN_2C_(52)H_(70),Mr=1043.23,monoclinic, P21/a, a=18.121(3), b=15.249(3), c=20.369(4)A,β=102.49(8)°,V=5495(1)A3, Z=4, Dc=1.261g.cm-3,MoKα(λ =0.710691), μ=17.816mm-1, F(000)=2208. R=0.073 for 4374 observed reflections with I≥3.0σ(I). The structure of the anion contains a linear Fe-O-Fe unit, with mean Fe-O distance of 1.766(2)A. The coordination geometry about each iron atom is close to tetrahedral with the angles O-Fe-S and S-Fe-S being 115.3° and 103.1°, respectively.     

CRYSTAL AND MOLECULAR STRUCTURE OF ISOMORPHOUS Cp_2Cr_2(CO)_4(μ-η2-P_2)[M(CO)_5]_2(M=Mo,W)

<正> Cp_2Cr_2(CO)_4(μ-η~2-P_2)C(M(CO)_5]_2(M=Mo(3),W(4)) are isostruc-tural to Cp2Cr2 (CO)4 (μ-η2-P2) [Cr (CO)5]2 (2) and crystallize in space group C2/c (No. 15) with a=18. 553(5),b=10. 462,c=16. 786(2)(2)A ,β=109. 84(1)°,V= 3064. 5(8)A3,Z=4,Mr = 880. 16,F(000) = 1712,and Dc=1.907 g/cm3 for 3,and a -18. 552(6),b= 10. 471 (2),c= 16. 768(2) A, β=109. 77(2)°,V = 3065(1) A3,Z = 4,Mr= 1055. 98,F(000) = 1968,and Dc = 2. 288g/cm3 for 4. This series of complexes share a virtually invariant Cr2(μ-η2-P2) central core with their parent complex Cp2Cr2-(CO)4(μ-η2-P2)(1).The Mo-P (2. 506(1) A) and W-P (2. 511(3) A) distances are longer than the corresponding Cr - P distance (2. 397(1)A) in complex 2 in accordance with the increase in covalent radii of the M atoms.     

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.     

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)).     

CRYSTAL STRUCTURE OF TRINUCLEAR MOLYBDENUM CLUS-TER Mo_3(μ_3-S)(μ_2-S_2)_3(Et_2dtc)_3I SYNTHESIZED BY SOLID STATE REACTION

<正> The title cluster compound was synthesized by solid state reaction at low heating temperature. C15H30IMo3N3S13, Mr=1083. 93, monoclinic, P21/n, a = 14.396(3), b = 13. 116(3), c=18. 142(8)A;β= 91. 36(3)°; V =3425(2)A3, Z = 4. Dc = 2. 10g/cm3, F(000) = 2112,μ(MoKa) = 27. 29cm-1, final R = 0. 034, Rw = 0. 051 for 1845 unique observed reflections (I≥3σ(I)). The three Mo atoms form an equilateral triangle with an average side length of 2. 714 A. Each Mo atom is coordinated with seven S atoms forming a distorted pentagonal bipyramid. The iodine atom connects with three S atoms (out of the CMo3] plane) with an average distance of 3. 205 A.The title compound has similar cubane-like cluster core [Mo3S7I] as the compound Mo3(μ3-S)(μ2-S2)3(dtp)3I(dtp= (EtO)2PS2).     

CRYSTAL STRUCTURE OF Mo_3(μ_3-O) (μ-S_2)_ 3 [S_2P(OEt)_2]_3I

<正> Mr=1178.9, monoclinic, P21/n, a=16.570(2), b=12.370(1), c=20.007(2) A,β=99.97(1)°, V=4039.0A3, Z=4, Dx=1.938 Mgm-3, λ(MoKα)=0.7107A, μ(MoKα)=23.96 F(000)=2296, room temperature. Final R value=0.047 for 4387 unique observed reflections. It consists of neutral mono-oxo-capped trinuclear molybdenum cluster molecules with an average Mo-Mo bond length of 2.626(4)A and an average Mo-0 bond length of 2.036(2)8.     

SYNTHESIS AND CRYSTAL STRUCTURE OF {C(η~5-C_5H_5)_4Nd_4(μ_4-O) (μ_2-Cl)_8)]·[Li(dme)_2THF]_2

<正> The reaction of (η5-C5H5)3Nd·THF and NdCl3·2LiCl·nTHF in solution at room temperature gave rise to[(η5-C5H5)4Nd4(μ4-O)(μ2-Cl)8][Li(dme)2THF]2 (Mr = 1654.44). Crystals of the compound were obtained at about - 10℃. The intensity data were collected under nitrogen atmosphere at-60℃. The crystal belongs to the rhombic system with space group Pna21 and the unit cell parameters : a=19. 010(7),b = 23. 231(6) ,c= 14. 180(4) A ;V = 6261. 91 (A3) , DC= 1. 67 (g/cm3), λ(MoKa) = 0. 71069A,F(000) = 3240,μ(mm-1) = 3. 660;Z = 4. Least-squares refinement with anisotropic temperature factors for all non-hydrogen atoms led to the final R=0. 054, Rw = 0. 056. The molecule is made up of the anion group and the cation. The oxygen atom links four Nd3+together as μ4-bridge. The eight chlorine atoms form the eight chlorine-bridge bonds among four Nd3+ions. The average bond length is : Nd-O=2. 374,Nd-Cl = 2. 811,Nd-C=2. 777,Nd(a)- Nd(b) = 3. 872A.The bond angles of Nd(a) -Nd (b)-Nd(c) fall in the range of 62~63°,th     

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 STRUCTURE OF (Br(μ-Met)(μ-Gly)(H_2O)_4]_2[Er(μ-Net)_2(H_2O)_4]_2(ClO_4)_(12)

<正> [Er(u-Met)(u-Gly)(H2O)4]2[Er(u-Met)2(HaO)4]2(ClO4)12(NMet=CH3S-(CH2)2CH(NH2)COOH,Gly=NH2CH2COOH), Mr=3194, trilinic, space group P1, a = 12.375(6),b= 14.041(13), c=19.074(13)A,α=80.85(6),β=80.72(6).γ=62.82(6)° ,Z=1,V= 2896A3,Dc=1.83 g/cm3,R=0.091. The carboxyl groups of Met and Gly in the title complex are bonded to Er atoms as bidentate bridging ligands.There are two different cations located at crystallographic symmetry centers in one unit cell.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_3 (μ-C_2H_5COO)(dtp)_3Py

<正> C20H40Mo3NO8P3S10, Mr=1123.93, triclinic, P1,a=12.972(3), b=13.763(2), c= 14.515(7)A,α=66.22(3),β=101.72(3),γ=118.90(1)° , V= 2076(2) A3, Z=2,Dc=1.798 g.cm-3, MoKa radiation, final R= 0.040 and Rw=0.056 for 5645 observed reflections. The molecule contains three Mo atoms arranged in a triangle with one capping-S atom, three (μ-S) atoms, one (μ-EtCOO) ligand, one chelate ligand dtp on each Mo atom, and one terminal Py on atom Mo(1). The coordination of Mo atoms is of distorted octahedron.     

MOLECULAR STRUCTURE OF ORGANOLANTHANIDE COMPLEX [Li(THF)_4]_2[{ (η~5-CH_3C_5H_4)NdCl(μ_2-Cl)NdCl_2(η~5-CH_3C_5H_4)}_2(μ_4-O)]

<正> The crystal structure of the complex [Li(THF)4]2[{(η5-CH3C5H4)Nd-Cl(μ2-Cl)NdCl2(η5-CH3C5H4)}2(μ4-O)] has been determined by X-ray diffraction technique. The crystal is monoclinic of space group C2/c with a = 22. 740(7) ,b= 18. 319 (6),c=18. 330(6) A,β=93. 04(3)°,V = 7624. 93A3,Dc= 1. 55g/cm3,Z = 4,F(000) = 2800,μ=15. 02cm-1. The complex is consisted of two [Li(THF)4]+cations and one [{(η5-CH3C5H4)NdCl(μ2-Cl)NdCl2(η5-CH3C5H4)}2(μ4-O)]2-dianion. The two units [Cη5-CH3C5H4)NdCl(μ2-Cl)NdCl2(η5-CH3C5H4)] in the tetra nnclear-neodymium dianion are connected by a μ4-O bridge with the average Nd -μ4-O 2. 36(1) A ,Nd -C(ring) 2. 76(3)A,Nd-Cl 2. 823(7)A and Nd-μ2-Cl 2. 798(7)A.     

SYNTHESIS AND CRYSTAL STRUCTURE OFμ-TEREPHTHALATO BINUCLEAR COBALT(Ⅱ) COMPLEX [Co_2(tpha)(bpy)_4](ClO_4)_2

<正> The structure of μ-terephthalato binuclear cobalt (Ⅱ) complex CCo2(tpha)(bpy)4](ClO4)2(tpha=μ-terephthalato, bpy=2,2' -bipyridine) has been determined by X-ray method. Crystals of title complex are monoelinic, space group P21/c, with a = 13. 086(2), b = 9. 428(2), c=20. 237(4) A. β= 108. 83(1)°, Mr = 1105.61, Z = 2, Dx = 1. 55g/cm3, μ= 8. 09cm-1 and F(000)= 1128. The structure has been solved by direct methods and refined to R=0. 053, The title cation has Ct symmetry in which the terephthalato group acts as bridging ligand between the two metal atoms. Each cobalt(Ⅱ)ion is in a distorted octahedral environment. The Co.....Co distance is 10. 35A.     

SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)(μ-S)_3[S_2P(OEt)_2]_4(C_3H_3N_2)

<正> Mr=1164, space group C2/c, a=14.954(13)A,b=22.323(6)A,c=27.003(18)A,β=98.23(7)°,V=8920 A3, Z=8. Final R=0.069 for 2818 unique diffraction data with I≥30(I). The title cluster compound is of Ml configuration with a triple bridging atom O and with a 'loosely coordinated site' occupied by an imidazole ligand. Three Mo-Mo bond lengths are 2.657 (2), 2.649(2),and 2.646(2)A,respectively. The average bond length of Mo-(μ3-O) bonds is 2.052 A.