STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS XXXXV. SOLID STATE SYNTHESIS AND CRYSTAL STRUCTURE OF [MoAg_3BrS_4I_3][(n-Bu)_4N]_3

<正> C48H108Ag3BrI3MoN3S4, Mr=1735. 84, cubic, F43c, a = b = c = 24. 577(4) A.V= 14845. 2A3, Z = 8, Dc=1. 553g/cm3, Dv = 1. 560g/cm3. Final R = 0. 061 for 307 unique diffraction data with I≥3σ(I). The anion of the title cluster compound can be viewed as a cubane like structure situated at specific equivalent positions in the unit cell with Td symmetry. One Mo and three Ag atoms, one Br and three Sb atoms, one S, and three I atoms are statistically distributed, individually. The distances of Mo....Ag (or Ag....Ag), Mo-Sb(or Ag -Sb, Ag -Br), and Mo-St(or Ag-I) are 3. 303(3), 2. 701(4) and 2. 741(3) A , respectively.     

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, structure and characterization of the trinuclear copper (Ⅰ) complex [Cu_3(μ_3Br)_2(dppm)_3]Br

The novel trinuelear copper(I) complex [Cu3(μ3-Br)2(dppm)3]Br has been obtained by reaction of bis(diphenyl-phosphino)methane (dppm) with cupric bromide. The title complex was characterized by single-crystal X-ray analysis, elemental analysis, molecular weight determination, 31P NMR and its conductivity was also measured. The [Cu3(dppm)3Br2] cation consists of a triangular array of copper atoms, with dppm ligands (Ph2PCH2PPh2) bridging each edge of the triangle and two triply bridging Br groups bound to the two faces of the Cu3 unit. Crystallographic data: monoclinic, space group P21/c, a = 1.4739(4) , b = 1.7708(5), c = 2.8395(8) nm, β= 97.16(3)°, V = 7.353nm3, Z = 4,F(000)= 3296, Dcalc = 1.472 g/cm3, μ= 26.478 cm-1, R = 0.06, Rw = 0.08, 4654 reflections observed with I > 3σ(I).     

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     

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [CrMo_3 (μ_3-O)_3(μ-O)(μ-O_2CCH_3)_5(O_2CCH_3)_3]Na2 · H_2O

<正> The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=2890 (3) A3, Z=2, A = 2. 08 g/cm3, F(000) -1780, Final R = 0. 049, Rw = 0. 058 for 2622 independent reflectons with I>3σ(I). The complex anion contains two Mo3O4 cores which connect two chromium atoms through four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atoms and the Mo atoms is coordinated by six oxygen atoms. The anions are linked by Na cations to form one-dimensional infinite chain structure.     

CRYSTAL STRUCTURE OF (C_5H_9C_5H_4)_3Er_4(μ_2-Cl)_6(μ_3-Cl)(μ_4-O)-(THF)_3

<正> The crystal of (C5H9C5H4)Er4(μ2-Cl)6(μ3-Cl)(μ4-O)(THF)3 belongs to triclinic space group P1, with a = 11. 909(4), b = 15.343(5), c=15. 619 (4)(?), α=104. 18(2), β=98. 81(3), γ= 111. 06(2)°, V = 2486(1)(?)3, Z = 2, Dc = 2. 07g/cm3, λ(MoKα) = 0.71073(?), μ= 73. 4cm-1, F(000) = 1476, Mr=1549. 25. The structure was solved by Patterson and Fourier techniques and refined by block diagonel least-squares method to final R = 0. 078 and Rw = 0. 084 for 5594 reflections with I≥1. 5σ(I). The results revealed that the complex is composed of four Er atoms bridged by seven Cl and one oxygen atoms with three of the Er atoms bonded each to a cyclopentylcyclopentadienyl group, and one Er atom, bonded to three THF. The Er atoms constitute a pseudo-tetrahedron.     

SYNTHESIS AND STRUCTURE OF THE CLUSTER COMPOUND {[Mo_3(μ_3-S)(μ-S_2)_3(dtp)_3]_2Cl}·FeCl_4, (dtp=S_2P(OC_2H_5)_2)

<正> The title compound, C24H6oCl5O12P6S26FeMo6,Mr = 2369. 00,crystallized in monoclinic,space group P21/n with cell parameters a= 17. 378(9) ,b=19. 752 (6),c=23. 845(A),β=84. 50(4)°,V = 8133. 4A3,Z=4,Z)c=1.931gcm-3,F(000) = 4676. 00. MoKa radiation (λ=0. 71073A),R=0. 070 for 8403 reflections with I≥3σ(I). The structure was solved by direct methods and showed to consist of an anion Fe-Cl4- and a cluster cation {[Mo3(μ3-S) (S2)3 (dtp)3]2Cl} + which is a double-trinuclear molybdenum cluster formed by sharing a chlorine atom with six weak Cl -S bonds of about 2.936-3. 145A.     

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.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-PhS) (μ-σ,π-CH_3CH = CH)Fe_2(CO)_6

<正> The crystal and molecular structure of (μ-PhS) (μ-σ, n-CH3CH = CH)-Fe2(CO)6 has been determined by X - ray diffraction technique. The complex has chemical formula of C15H10O6SFe2 and Mr=129. 99. The crystals are monoclinic,space group P21/c,with α=11. 789(2),b= 7. 159(1),c = 20. 890(4) A ;β = 100. 89(2);V = 1731. 32 A3;Z=4,Dc=1. 65g·cm-3;F(000) = 863. 86. The final R and Rw equal 0. 0315 and 0. 0405 respectively for 2527 observed unique reflections.     

MOLECULAR AND CRYSTAL STRUCTURE OF (μ-HOCH_2 CH_2 S)_2 Fe_2 (CO)_4(PPh_3)_2

<正> The molecular and crystal structure of the complex (μ-HOCH2CH2-S)2 Fe2(CO)4(PPh3)2 synthesized by reaction of ethylene epoxide with (μ-Lis)2Fe2(CO)6, followed by EtOH alcoholysis and PPh3 substitution,was determined by X-ray diffraction technique. The crystals are triclinic,space group P 1,with a= 10. 902(2),b=12. 106 (2),c=16. 123(4) A ,V= 2079. 36A3,α=78. 13(1),β=89. 37(2),γ=87. 93(1)°, Z = 2,Dx=1. 44 g/cm3.μ(MoKa) = 9. 149cm-1, F(000) = 940. The final R and Rw equal to 0. 055 and 0. 068,respectively,for 3598 observed independent reflections. In this molecule two PPh3 ligands are trans to the Fe - Fe bond and axially coordinated to two iron atoms. In addition,two hydroxylethyl groups are attached to bridging sulfur atoms by e-type of bond and thus this molecule is an ee conformer.     

SYNTHESIS AND CRYSTAL STRUCTURE OF Pr(NO_3)_3(Me_2-16-C-5)

<正> The complex Pr (NO3)3 (Me2-16-C-5) (Me2-16-C-5 = 3, 3-dimethyl-1,5,8,11,14-pentaoxacyclohexadecane) crystallizes in the hexagonal space group P65with a = b = 13. 145(2), c=25. 611(5) A ; Z = 6; V = 3832(1)A3; Dc = 1. 53gcm-3; F (000) = 1776;μ= 19. 7cm-1 (MoKa). The final refinement converged with R = 0. 049 and Rw = 0. 051 for 2005 observed reflections. The Pr(Ⅲ) ion is 11-coordinated to three bidentate nitrate groups and five oxygen atoms of a crown ether. The average Pr -O(crown) and Pr -O(NO3-) bond lengths are 2. 68 and 2. 57A , respectively.     

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     

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)}.     

Synthesis and Crystal Structure of a Tetranuclear Cu(Ⅰ) Complex with Vinyfidenebis(diphenylphosphine)

The vinylidenebis(diphenylphosphine) (vdpp) reacts with CuBr to give a tetranuclear complex, [Cu4(μ3-Br)2(μ2-Br)2(μ2-vdpp)2(CH3CN)2]·(CH3CN)2 1. The title complex has crystallo-graphically imposed centrosymmetry and presents a Cu4Br4 core with distorted stair-like structure. All copper(Ⅰ) atoms in 1 assume distorted tetrahedral coordination geometry. The distance of 2.7745(11) A between the two copper centers indicates the presence of ligand-supported Cu…Cu interactions. Crystal data for 1: C60H56Br4Cu4N4P4, Mr = 1530.77, triclinic, space group P1, a = 11.6593(9), b = 11.7181(9), c = 13.8711(11) A, α = 110.1020(10), ,β = 102.0050(10), γ = 109.8040(10)°, V = 1557.5(2) A3, Z = 1, Dc = 1.632 g/cm3, F(000) = 760, λ = 0.71073 A, T = 298(2) K, 2θmax = 50.04°,μ = 4.056 mm-1, S = 1.181, R = 0.0507 and wR = 0.1025.     

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.     

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.     

THE SYNTHESIS AND STRUCTURE OF Mo_3(μ_3-O)(μ-S)_3(μ-O_2CC_6H_5)_2(dtp)_2(Py)

<正> The title compound was prepared by reaction of Mo3(μ3-O) (μ-S)3-(dtp)4 (H2O) with C6H5COONa and pyridine. C27 H35 Mo3NO9P2S7, Mr = 1091.76, monoclinic, space group P21/c, a = 15. 057(5), b = 13. 052(5), c = 21. 662(6)(?), β=105.97(2)°, V = 4093(2) (?)3, Z = 4, Dc= 1. 77gcm-3, F(000) = 2176, μ(MoKα)=13.50cm-1, final R =0. 068 for 2835 observations. The molecular configuration is new and of approximate C, symmetry, and there are two C6H5COO bridging groups in the structure. The three Mo atoms form an isosceles triangle with three sides of 2. 567(3), 2. 576(3), and 2. 649(3)(?), where the two Mo-Mo bonds bridged by C6H5COO group are much shorter than that without. Something about the reactivity of Mo clusters is discussed.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRANUCLEAR MOLYBDENUM CLUSTER Mo_4(μ_3-O)_2Cl_2(o-CH_3C_6H_4COO)_6

<正> Cluster compound [Mo4(μ3-O)2O4Cl2(o-CH3C6H4COO)6] has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid. It crystllizes in the orthorhombic space group Praia with cell parameters:Mr= 1361. 6,a=13. 792(4), b=17. 957(3),c= 20. 974(9) A ,V=5194(2) A3,Z= 4,Dc= 1. 74g/cm3,F(000) = 2704,μ(MoKa) = 11. 0/cm. The final R=0. 061 and Rw=0. 064 for 1441(I>3oooooooooo(I)) observed unique reflections. The tetranuclear complex molecule, where the molybdenum atoms are bridged by two μ3-O atoms and six bidentate o-methylbenzoato ligands,is located at crystallographic two-fold axis(x,-1/4,1/4) with one Mo-Mo bond of 2. 610A     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)-(μ-S)_3(μ-OOCCH_3)(dtp)_3(Py)

<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one.     

TRINUCLEAR BASIC CARBOXYLATE COMPOUNDS OF TRANSITION METALS PART 2. SYNTHESIS AND CRYSTAL STRUCTURE OF [Fe_3O (EtCO_2)_3(MeCO_2)_3(H_2O)_3]NO3·H_2O

<正> The title complex crystallizes in monoclinic system,space group C 2/m with α=19. 870(5),b=13. 070(2),c=18. 246(4)A ,β=134. 32(1)°,Mr = 707. 88, V=3390. 0A3.Z = 4,DC=1. 387g/cm3,F(000) = 1468,final R=0. 066 for 2244 independent reflections with Ⅰ >3σ(Ⅰ). The cation was shown to contain three Fe (Ⅲ) atoms at the apices of an equilateral triangle with a 3-O bridge.The Fe (1)-(μ3-O)and Fe(2)-(μ3-O) distances are 1. 907(6) and 1. 87(1) A , respectively. And mixed ligands of acetato and propionyloxy lato are bridged to each pair of the Fe(Ⅲ) atoms.