SYNTHESIS AND STRUCTURE OF A NEW LINEAR TETRANUCLEAR Mo-Fe-S CLUSTER (Et_4N)_2[(Et_2NCSSMoS_2)_2O_3Fe_2S_2]·DMF

(Et4N)2[Et2NCSSMoS2)2O3Fe2S2]·DMF(1) ,Mr= 1174. 10,mono-clinic,space group P21/n,a = 9. 608(3),b=17. 962(2),c=15. 312(3) A ,β=95. 03 (3)°,V=2632. 4 A3,Dc= 1. 48 g/cm3 and Z=2. The structure was solved from 2499 reflections with I>3σ(Ⅰ) and refined by full-matrix least squares method to R(Rw) = 0. 073(0. 087). The anion of 1 has linear Mo -Fe -Fe-Mo array. The oxidation states of metal atoms in this cluster are 2Mo(Ⅵ) + 2Fe(Ⅲ).

SYNTHESIS AND CRYSTAL STRUCTURE OF A PLATINUM (Ⅱ) COMPLEX WITH MIXED DIPHOSPHINE AND THIOLATE LIG-ANDS, Pt(dppm)(SPh)_2

The reaction of H2PtC14, Ph2PCH2PPh2(dppm) , NaSPh, and element selenium in DMF gives rise to a mononuclear complex Pt (dppm ) (SPh)2, PtS2P2C37H32, Mr = 797. 83, triclinic, space group P1, a = 10. 051(2), b = 11. 805 (3), c=15. 499(4)(?). α=109.41(3), β=90. 94(3), γ=107. 80°, V = 1636.3 (?)3. Z = 2, Dc= 1. 619gcm-3, * = 45. 749cm-1, and F(000) = 788. The final structural refinement converged with unweighted and weighted R factors of 0. 029 and 0. 044, respectively, for 4832 observed unique reflections with I>3σ(I). The complex is an asymmetric molecule with a four-coordinated Pt atom. The average of Pt -S and Pt-P bond distances are 2. 334(3) and 2. 260(3) (?), respectively.

STUDY ON TETRANUCLEAR TRANSITION METAL CLUSTER WITH μ_3-O BRIDGES I . SYNTHESIS AND CRYSTAL STRUCTURE OF [Fe_4O_2(O_2CCH_3)_7(2,2'-bipy)_2]Cl

[Fe4O2(O2CCH3)7(2,2’-bipy)2]Cl,Mr=1016.5,monoclinic,C2/c,a=27.628(5),b=11.882(3),c=16.587(3)A,β=119.03(1)°,V=4761.4A3,Z=4,Dc=1.418 g/cm3,λ(MoKa)=0.71069A,μ=13.13 cm-1,F(000)=2088,R=0.062 and Rw=0.077 for 3116 reflections with I≥3σ(I).The title compound contains a [Fe4O2]8+core with bridging CH3COO-and terminal bipy groups giving the structure with a C2 symmetry.The arrangement of the four metal atoms is not planar but has a butterfly-like structure with a dihedral angle of 141.58°.

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

(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.

SYNTHESIS AND STRUCTURE OF THE PEROXOVANADIUM (V) COMPLEX CONTAINING NITRILOTRIACETATE Na_2[VO (O_2) N-(CH_2COO)_3]·5H_2O

Na2[VO(O2)N(CH2COO)3] · 5H2O, Mr= 423. 11, monoclinic, space group P21/c, a = 6. 283(3), b = 20. 378(6), c=12. 056(4)(?) , β=102. 96 (3)°, V = 1507. 9(?)3, Z = 4, Dc= 1. 864 g/cm3. λ(MoKα) = 0. 71069A , F(000) = 864. Final R = 0. 037 and Rw = 0. 046 for 1658 observed reflections with I>10σ (I). The structure of the anion of the title complex shows that the vanadium atom is coordinated by one vanadyl oxygen atom, two oxygen atoms of the peroxp-group, three oxygen atoms and one nitrogen atom from the NTA ligand to form a distorted pentagonal bipyramid.

SYNTHESIS AND CRYSTAL STRUCTURE OF A TRITUNGSTEN CLU-STER COMPOUND H[W_3O_2(O_2CCH_3)_9]·5H_2O

In this paper we report the structure of another new W3 cluster compound H[W3O2(O2CCH3)9]·5H2O prepared by the method reported previously. The title compound crystal lizes in monoctinic system, space group P21 with cell dimensions: a = 8. 237(3),6=13. 273(2),c=14.508(4)A,β=92.97°(3),V=1584A3.Z=2,and Dc=2. 529g/cm3.The average W - W, W -U_3-O,W -Oac and W -Ot distances are 2. 775, 2. 01,2. 09 and 2. 04 A, respectively.

Preparation and Structure of (Ph_3PCH_2Ph)[Ni(OSNC_5H_3)_2]DMF

Compound (Ph3PCH2Ph)[Ni (OSNC5H3)2] . DMF was obtained from the reaction.of NiCl2,Na2(OSNC5H3)and Ph3PCH2PhCl. Mr = 735. 53,monoclinic,P21/ c,a=9. 857(6),b=17. 594(9),c=21. 369(10) A,β=102. 85(4)°,V=3613. 1A3,Z = 4,Dc=1. 35g/cm3,λ(Mo-Ka) = 0.71073A.μ=7. 3cm-1,F(000) = 1532,The nickel (Ⅲ) ion is coordinated by two 2-mercapto-3-pyridinolate ligands to give an approximate square-plannar configuration with cis-geometry.

CRYSTAL STRUCTURE OF Pt(dppe)(SPh)_2

Anaerobic reaction of Pt (dppe)Cl2 (dppe = Ph2PCH2CH2PPh2) with NaSPh and elemental selenium affords complex Pt(dppe)(SPh)2,which crystallizes in the monoclinic system space group C2/c with a=14. 392(7) ,b=16. 380(7) ,c=14. 266(5) A ,β=86. 44(4)°,V=3342(5) A3,Z = 4,Dc=1. 613g/cm3,and μ(MoKa) = 44. 813 cm-1. The final structural refinement converged with unweighted and weighted R factors of 0. 041 and 0. 057 for 2206 observed reflections (I>3σ(I)). X-ray analysis shows that the Pt atom in Pt(dppe)(SPh)2 is at the center of the approximately planar tetragon of two P atoms and two S atoms.

CRYSTAL STRUCTURES OF TWO DITHIOLATO-COPPER COMPLEXES (Ph_4P)Cu(BDT)_2 AND (Ph_4P)Cu(TDT)_2

[(C6H5)4P]Cu(S2C6H4)2(Ⅰ),Mr = 683. 39,monoclinic,space group C2/c,a=16. 099 (4),b= 11. 913(3) ,c = 16: 715(9) A ,β=97. 13(4)°, v = 3180. 7 A3,z=4.MoKa radiation,λ= 0. 71069A ,Dc= 1. 427g/cm3,μ= 10. 1cm-1,F(000) = 1400,R=0. 061 and Rw = 0. 068 for 2189 reflections with Ⅰ>3σ(Ⅰ). [(C6H5)4P]Cu (S2C7H6)2(Ⅰ),Mr = 711. 45,monoclinic,space group C2/c,a=16. 501(6),b = 37. 461 (15),c=16. 684(4)A,β=96. 70(4)°, v= 10248. 8(46) A3,z= 12. MoKa radiation, λ= 0. 71069A,Dc=1.383g/cm3,μ=9. 45cm-1,F(000).= 4416,R= 0. 074 and Rw= 0. 078 for 2085 reflections with I>2σ(I)(1). The copper atom in the complexes is surrounded by four sulfur atoms from two dithiolato ligands in an approximate, square-plane. The average Cu-S distances of the copmplexes(Ⅰ) and (Ⅱ) are 2. 179 and 2. 178 A, respectively.

SYNTHESIS AND CRYSTAL STRUCTURE OF DINUCLEAR IRON CARBONYL DERIVATIVE (μ-SC_6H_5) (μ-P (SC_6H_5)_2) Fe_2 (CO)_5 (P-(SC_6H_5)_3)

The reaction of Fe3(CO)12 with P(SPh)3 yields the tile compound. C41H30Fe2O5P2S6, Mr = 968. 65, monoclinic, space group, P21/n, a = 14. 449(9), b = 18. 046(11), c=16.871(10)(?), β=98. 76°, V = 4348(?)3, Z = 4, Dc=1. 480g/ cm3, λ(MoKα) = 0. 71073(?) The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares procedure to R = 0.084, Rw = 0.144 for 4059 reflections. Fe(1)-Fe(2) = 2. 576(6), Fe(2)-P(2) = 2.194(9)(?). The dihedral angle between the Fe(l)SFe(2) and Fe(1)PFe(2) planes is 81. 9°. The other one (dihedral angle between SFe(1)P and SFe(2)P planes) is 75. 2°.

CRYSTAL AND MOLECULAR STRUCTURE OF [Cu_2(α-C_(10)H_7-CH_2CO_2)_4(DMF)_2](DMF)_2· H_2O

The title complex crystallizes in the triclinic system, space group P1, a =11. 912(4), b = 13. 626(2), c=10. 040(3)(?), a=95. 03(2) ,β= 114. 8 (3), γ = 73. 58(3)°, V = 1418.0(?)3, Z = 1, D,= 1. 37g/cm3, F(000) = 612, R = 0. 064 for 4860 independent reflections [I>3σ(I)]. Each Cu atom is coordinated by the oxygen atoms from the C10H7CH2COO groups and DMF in a square pyramid geometry.

CRYSTAL STRUCTURE OF A TRINUCLEAR COBALT COMPLEX Co_3(bdt)_3(PBu_3~n)_3 · ~2CH_2C1 (bdt = S_2C_6H_4~2- ) WITH MIXED o-BEN-ZENEDITHIOLATE AND TRIBUTYLPHOSPHINE LIGANDS

Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.

SYNTHESIS AND CRYSTAL STRUCTURE OF A TRITUNGSTEN CLUS-TER COMPOUND [W_3O_2(O_2CCH_3)_6(H_2O)_3]ZnBr_4·8H_2O

C12H40O25Br4W3Zn, Mr = 1520. 71, monoclinic, space group P1, a = 10. 470(4) b=17. 669(6),c=14. 477(2) A ,α=99. 80(2),αB=101. 51(2),γ=99. 78 (4)°,V=1829A3,Z = 2,DX = 2. 66g/cm3,λ(MoKa) = 0. 71073A,μU= 146. 9cm-1,F (000) = 1408. Final R=0. 038,Rw = 0. 049 for 4088 independent observable reflections.

SYNTHESIS AND CRYSTAL STRUCTURE OF TRINUCLEAR CLUSTER [M_3O_2(O_2CCH_3)_6(H_2O)_3]ZnBr_4·8H_2O(M=0. 33Mo+0. 67W)

C12H40O25Br4MoW2Zn, Mr=1432. 75,Monoclinic,Space group C2/c,a= 13. 239(2),b= 16. 215(3),c= 17. 670(3) A ,β= 105. 53(2) ,V=3654 A3,Z= 4,μ= 64. 0cm-1,λ(MoKa) = 0. 71073 A , F (000) = 2688, Dc = 2. 605g/cm3. Final R = 0. 042,Rw = 0. 057 for 2688 observed independent reflections.

SYNTHESIS AND STRUCTURE OF (Me_4N)[Mo(OC_6H_4S-o)_3]

(Me4N)[Mo(OC6H4S-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.

SYNTHESIS AND STRUCTURE OF Ni_2(PBu_3~n)_2(SC_7H_6S)_2

The nickel(Ⅱ) complex Ni2(PBu3n)2(tdt)2(tdt = SC7H6S2-) containing dithiolato and phosphino ligands has been prepared and characterized by X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a = 14. 423(4), b = 15. 053(3), c=10. 648(3)(?), α=93.,95(2), β=100. 31(3), γ = 84. 16(2)°; V =2259.6 (?)3; Z = 2, Dc= 1. 22 gem-3, Mr = 830. 57; μ = 11. 076cm-1, F (000) = 888. In the complex, the Nickel atoms are linked by two bridging sulfur atoms from the two tdt ligands with the Ni-Ni distance of 2. 679 (?) . and each nickel atom is four coordinated by one phosphorus and three sulfur atoms with a square-planar geometry, the average length of Ni -S bond is 2. 193(?) and that of Ni-P bond 2.186(?).

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]

(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].

CRYSTAL STRUCTURE OF [PdCl_2 (DMAF)_2]·C_7H_8

C33H42 Fe2PdCl2N2 (dichloro-bis (dimethylaminomethylferrocene) pal-ladium(Ⅰ) toluene solvate) ,Mr = 755. 72,monoclinic,P21/c,a=7. 521(1),b= 11. 128 (2),c=19. 260(7) A ,β=91. 77(2)°,V=1611. 1A3,Z=2,Dc = 1. 56g·cm-3,D0 = 1. 58g·cm-3,μ=76. 3cm-1, The least-squares refinement gave a final R value of 0. 062 for 2192 observed reflections. The Pd atom is of squareplanar coordination. The ferrocene ligand of in DMAF has an approximately eclipsed conformation.