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.     

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.     

Crystal Structure of a Three-dimensional Coordination Polymer {[Ca_3(μ_5-OOCCH_2OCH_2COO)_3(H_2O)_4]·4H_2O}_n

A novel three-dimensional coordination polymer, {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]- 4H2O}n, has been synthesized with oxydiacetate as bridge ligand and structurally determined by X-ray crystallography. The crystal belongs to monoclinic, space group C2/c with a = 17.805(2), b = 9.3923(12), c = 17.255(2) A, β = 107.838(5)°, V = 2746.8(6) A3, Mr = 660.58, C12H28Ca3O23, Dc = 1.597 g/cm3, μ = 0.695 mm-1, Z = 4, F(000) = 1376, GOOF = 1.027, R = 0.0303 and wR = 0.0660. In the complex there are two coordination modes for Ca(II) ions, one coordinated by three μ5-OOCCH2OCH2COO2- bridge ligands together with two H2O molecules, and the other by five μ-5-OOCCH2OCH2COO2 bridge ligands. In both coordination modes each Ca(II) ion assumes a distorted dipentapyramidal CaO7 geometry; whereas each oxydiacetate is coordinated with five Ca(II) ions and acts as a pentdentates bridge ligand.     

STUDIES OF RARE EARTH METAL COMPLEXES OF AMINO ACIDS AND PEPTIDES. SYNTHESES AND CRYSTAL STRUCTURES OF TRIAQUO TRIS (N-ACETYLGLYCINE) LANTHANIDE Ln(CH_3CONHCH_2COO)_3(H_2O)_3(Ln = Nd~(3+),Eu~(3+) and Er~(3+))

<正> The title complexes were synthesized and their crystal structures were determined. These complexes crystallize in trigonal space group R3 with 3 molecules in a unit cell and are isostructural to each other. Crystallographic data: complex 1, Nd(CH3CONHCH2COO)3(H2O)3, Mr = 546. 6, a= 16. 582(4), c = 5. 982(2)(?), V= 1424. 5(8)(?)3, Dc=1. 91gcm-3, F (000) = 819, μ = 28.06cm-1, R(Rw) = 0. 048(0. 061); complex 2, Eu (CH3CONHCH2COO)3 (H2O)3, Mr = 554.3, a = 16.564(10), c=5.974(3)(?), V = 1418(2)(?)3,Dc= 1. 95gcm-3, R (Rw) = 0. 018 (0. 025), F (000) = 828, μ= 33. 83cm-1; complex 3, Er-(CH3CONHCH2COO)3(H2O)3, Mr = 569. 6, a = 16. 476(7), c=5. 946(6)(?), V = 1398(2) (?)3, D, = 2. 03gcm-3, R (Rw ) = 0. 020 (0. 027) , F (000) = 843, μ= 46. 25cm-1. These complexes adopt mononuclear structure, in which Ln(Ⅲ) ion is coordinated to six oxygen atoms from three ligands and three oxygen atoms from water molecules with the polyhedron of 4,4,4-tricapped triangular prism. The carboxy-lato group of the ligand bonds to Ln     

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.     

SYNTHESIS AND STRUCTURE OF A TRITHIOCARBONATO Mo(Et_4 N)_2 [(S_2)Mo_2O_2(μ-S)_2(CS_3)]

A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from asystem containing MoO_4~(2-),S_x~(2-),and CS_2 and characterized by IR and X-ray structural analysis.The complex crystallizes in the (?)onoclinic space group P2_1/c with a=9.539(3)(?),b=20.745(2)(?),c=15.452(2)(?),β=94.58(2)°,and Z=4.The structure was solved by direct anddifference Fourier synthesis methods.Least squares refinement using 2910 reflections withI>3σ(I)converged to R=0.054.The CS_3~(2-) iigand in the complex chelates to Mo atom andvalues of the C-S bond distances in the CS_3~(2-) ligend indicate a substantial contribution ofthree resonance forms.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3[Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]

The space group of the title crystal is Pnam. The unit cell parameters are: a=17.226(4), b=14.306(7), c=15.074(4); z=4, Dobs=2.03g·cm~(-3), D_(calc)=2.063g·cm~(-3). The crystal structure was solved by the heavy atom method and refined by the full-matrix least-squares until the final conventional discrepancy factor was reduced to 0.068. The results of the investigation show that the crystal consists of trinuclear Mo cluster anions [Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]~(3-) together with planar (C_5H_7S_2)~ monocations, surrounding the cluster anions. In the cluster anion three Mo atoms, forming a nearly equilateral triangle (2.755(1), 2.755(1), 2.743(1)), are bound by a μ_3-S bridging atom, while each pair of Mo atoms is bridged further by a μ_2-S_2 ligand. Besides, each Mo atom is coordinated to two terminal Cl atoms, so that the coordination sphere of each Mo atom approaches closely a pentagonal bipyramid. In addition, a single Gl atom, not at all involved in the coordination spheres of the three Mo atom     

STUDY ON STRUCTURE OF SULFUR-BRIDGED TRANSITION METAL CLUSTERS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3 [Mo_3(μ_3-S)_2 (μ_2-Cl)_3Cl_6]

The compound (C_5H_7S_2)_3[Mo_3 (μ_3--S)_2 (μ_2--Cl)_3 Cl_6] forms dark black octahedralcrystals with the following crystallographic parameters: a=22.885(10)A, c=25.407(7)A. Thespace group is I4_1/α, Z=16, ρ_(obs.)=2.073g/cm~3, ρ_(calc.)=2.126g/cm~3. The 1621 independentreflections with I≥3σ were collected on a CAD-4 four-circle diffractometer by means of MoK_αradiation. The structure was solved by three-dimensional Patterson synthesis and refined byleast squares technique to a final discrepancy factor of R=0.056. The results of our investiga-tion reveal that the molecule consists of a trinuclear Mo cluster anion and three planar mono-cations.surrounding the cluster anion. As the core of the anion the triad of Mo atoms, possessing anequilateral triangular configuration, is linked by two μ3--S bridging atoms and three μ2--Clatoms. Besides, two terminal Cl atoms are attached to each Mo atom to form an octahedralconfiguration. The diamagnetism and the short Mo-Mo distances (2.556 A, 2.641 A, 2.653 A)clearly indicate the existence of Mo-Mo bonds. The anion as a whole has an idealized D_(3h) localsymmetry.     

THE SYNTHESIS AND STRUCTURE OF THE IMIDAZOLATE-BRIDGED HETEROTRINUCLEAR COMPLEX (en)_2Ni[(Im)Co-(NH_3)_5]_2(CIO_4)_6·5H_2O

<正> (H2NC2H4NH2)2Ni [(C3H3N2) Co (NH3)5]2 (CIO4)6 · 5H2O,NiCo2Cl6O29N18C10H62, Mr = 1288. 00, monoclinic, C2/c, a = 31. 832(4), b = 9. 691 (1), c=15. 425(4)(?),β=90. 71(2)°, Z = 4, V = 4758. 0(?)3, Dc=1. 798g/cm3, μ (MoKa) = 15. 22cm-1, F(000)=2656. The three metal nuclei, one Ni( Ⅱ ) and two Co( Ⅲ ), bridged by two imidazolyl anions (Im = C3H3N2), form an isosceles triangle. The Ni( Ⅱ ) atom is situated on the two-fold axis and coordinated by six nitrogen atoms to form a distorted octahedron with two nitrogen atoms from two Im in cis-positions. The two Co( Ⅲ ) atoms are related by C2 symmetry and each Co( Ⅲ ) is coordinated by six nitrogen atoms to form an octahedral configuration.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF (Et_4N)_2[Mo_3(μ_3-O)(μ_3-Cl)(μ_2-Cl)_3Cl_6]·EtOH

The title crystal belongs to the monoclinic system. The space group is P2_1/c with unit cell parameters: a=11.379(3), b=20.766(2), c=14.487(3), β=91.49(2)°, V=3519(2)~3Z=4, D_c=1.819g.cm~(-3), D_0=1.81g.cm~(-3). The crystal structure was solved by the heavy atom method and difference Fourier synthesis and refined by the full-matrix least-squares to a final R factor of 0.040 based on 3261 unique reflections with intensities I≥3σ(I). The structure consists of two sots of tetraethylammonium cations and trinuclear Me cluster anions. In the cluster anion the three Mo atoms form an isosceles triangle with Mo-Mo distances of 2.601(1), 2.608(1), 2.642(1), respectively, showing a strong bonding interaction between the metal atoms. One μ_3-O atom and one μ_3-Cl atom are situated above and below the triangle respectively, binding the three Me atoms to form a triangular bipyramidal cluster core. Each pair of Mo atoms is bridged further by a μ_2-Cl atom situated on the Mo_3 triangular plane. In addition, each     

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

<正> 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(?).     

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     

CRYSTAL AND MOLECULAR STRUCTURE OF GUANIDINIUM BIS (o-AMINOPHENYLARSENIC) HEXAMOLYBDATE (CN_3H_6)_4[(o NH_2C_6H_4 As)_2Mo_6O_(24)]

<正> Guanidinium bis (o - aminophenylarsenic) hexamolybdate belongs to monoclinic space group P21/c,with a=10. 217(2),b= 18. 870(2),c= 10. 939(2)A,β = 102. 82(3)°,Z = 2,V=2056. 4A3,and Dc=2. 477 g·cm-3. Each molecule contains one [(o-NH2C6H4As)2Mo6O24]4- anion and four CN3H6+ cations. In the anion,six distorted MoO6 octahedra are connected with edges-sharing to form a six-membered Mo ring which is capped above and below by two o - aminophenylarsenic groups. There is half a molecule in an asymmetric unit. It is interesting that both phenyl planes are almost perpendicular to the plane of the Mo atoms. The structure of the anion is similar to that of [ (CH3 As)2Mo6O24]4-,[(n-C3H7As)2Mo6O24]4- or [(C6H5CH2As)2Mo6O24]4-. This is the first example of this type of compounds in which the As atom is directly connected to a substituted phenyl group.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF Mo_3(μ_3-S)(μ_2-S_2)_3[S_2P(OEt)_2]_3Cl

The title crystal is straw-yellow in colour, belonging to the triclinic system. The space group is P with the following unit cell parameters:a=11.570(2), b=13.093(1), c=14.399(2), α=102.62(1), β=102.15(1), γ=111.87 (1)°, V=1870(1), Z=2, D_(calc)=1.960g·cm~(-3).The crystal structure was solved by the heavy atom method and refined by full-matrix least-squares to a final conventional R factor of 0.055. The results show that the crystal structure consists of neutral trinuclear Mo cluster molecules, in which three independent Mo atoms form an equilateral triangle with an average side length of 2.725(3), corresponding to a Me-Me single bond. On one side of the triangle one μ_3-S atom binds the three Mo atoms together to form a monoeapped trinuclear cluster. In addition, three S_2 radicals acting as μ_2 bridges are located between each two Mo atoms. Each Mo atom is also coordinated to two terminal S atoms of an [S_2P(OEt)_2]~- radical so as to complete a distorted pentagonal bipyramid configuration.     

CRYSTAL STRUCTURE OF GdCl_3(DIMETHOXYETHANK)_2

<正> C8H2oCl3GdO4,Mr=443.80,monoclinic, space group P21/c, a=11.442 (3),b= 8.849(2), c= 15.575(5)A,β=104.8l(2)° ,V=1521.9(7)A3,Z= 4, DC = 1.94 g/cm3,λ(MoKα) =0.71069A,F(000)=860. The structure was solved by Patterson and Fourier techniques and refined by least-squares nethod to a final conventional lvalue of 0.051 (Rw=0.054). The central ion Gd(III) is bonded to three chlorine atoms and four oxygen atoms froa two dimethoxye-thane molecules to form a distorted pentagonal bipyramid. The Qd-Cl distances are in the range of 2.460-2.628A (average 2.571A). The Gd-O distances are in the range of 2.408-2.493A (average 2.458A).     

STUDIES ON RARE EARTH METAL COMPLEXES OF AMINO ACIDS. THE SYNTHESIS AND CRYSTAL STRUCTURE OF TE-TRAKIS ( ALANINE ) OCTAAQUODILANTHANIDE HEXAPER-CHLORATE [Ln_2(Ala)_4(H_2O)_8]*(ClO_4)_6(Ln = Er~(3+)and Eu~(3+),Ala=CH_3CH(~+NH_3)COO~-)

<正> Complex [Er2(Ala)4(H2O)8]·(ClO4)6, 1, Mr = 1431. 8, mono-clinic, space group C2/c with cell parameters a= 18. 21(1), 6 = 14. 67(2), c=17. 19(3)(?), β=101. 60(8)°, V = 4495(4)(?)3, Dc=2.11g/cm3, Do = 2. 09g/cm3, Z = 4, F (000) = 2808, μ= 42. 30cm-1; Complex [Eu2(Ala)4(H2O)8]·(ClO4)6, 2, Mr = 1401.4, monoclinic, space group C2/c, a = 18. 16(4) , b = 14.52(2), c=17. 35(1)(?), β=102. 3(1)°, Z = 4, V= 4468(11)(?)3. The structure of complex 1 is refined by full-matrix least - squares method with 3348 observed reflections (I≥3σ (I)) to R = 0. 048 and Rw= 0.060. The two erbium ions in the dimeric complex cation [Er2(Ala)4(H2O)8]]6+ are connected by four bridging carboxylato groups, each pair of the carboxylato groups is coplanar with the two Er(III) ions and the dihedral angle between the two planes is 91. 42*. Each Er3+ion is coordinated by four carboxylato oxygen atoms and four water oxygen atoms, assuming a square antiprism arrangment. The alanine exists in the form of CH3CH (+NH3) COO- , and the mo     

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.     

CRYSTAL STRUCTURE OF 2, 4-DITHIONE-3-AMINO-1, 3, 2-OX-AZAPHOSPHORINEBENZO-2-THIONO PYRIDINIUM

<正> The structure of title compound [C7H6N2OPS3]-·[HNC5H5]+ was determined by x-ray diffraction. It belongs to monoclinic system with space group P21/a, a = 16.745(2), b= 8.563(2), c=21. 050(5)(?), β=93.32(1)°, V= 3013. 6(?)3, Z = 8, Mr = 341. 4, F (000) = 1536, Dc=1. 504 g. cm-3,μ= 53. 0 cm-1. The crystal is composed of discrete cations C5H5NH+ and anions CrH6N2OPS3-. There are two pairs of the cations and the anions in each asymmetric unit. The stability of the anion is increased by the formation of (d-p)π bonding involving the 3d orbital of the P atom and the lone electron pairs of the S atoms.     

THE CRYSTAL STRUCTURE OF TR1S (μ-SULFJDO)-(U3-SULFJDO)-TETRAKTS (O,O-DIETHYLPHOSPHORODITHIOATO-S,S)-OXAZOLE-TRI-MOLYBDENUM-ANTIMONOUSCHLORID {Mo_3(U3-S)[u-S)_3·SbCl_3][S_2P(OEt)_2]_4·(C_3H_3ON)}

<正> Mr = 1445.67, triclinic. The space group is P1 with the unit cell parameters: a = 10.342(3), b = 11.994(3), c = 21.352(4) A; (?)= 76.27(2), β - 88.55(2)°, r = 73.26(2)°; V = 246lA3, Z = 2, DC = 1.959 g.cm-3. The final R factor is 0.068 based on 4053 reflectioons with I≥3(?)(Ⅰ). The title compound may be regarded as the result of that a molecule of trinuclear Mo cluster {Mo3S4[S2P(OEt)2]4·(C3H3ON)}[1] connects with a molecule of SbCl3 by three bridging S atoms. The skeleton {Mo3SbS4} is a distorted cube. The distances of Mo-Mo bonds are 2.728(2), 2,743(2) and 2.751(2) A, respectively, and the distances between Sb and Mo atoms are 3.814(2), 3.815(2) and 3.847(2) A, respectively.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURES OF (Et_4N)_2[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_2Cl_5]

The title compound forms black crystals shaped like pseudo-octahedrons, which belong to the orthorhombic system The space group is Pna 2_1 with unit cell parametrs of a=17.815(1), b=16.629(2), c=12.003(1), and with Z=4, D_(obs)=1.80g·cm~(-3), and D_(calc)=1.804g·cm~(-3). The crystal structure was solved by the heavy atom method and refiened by fullmatrix least-squares to a final conventional R factor of 0.048 for 2584 unique reflections with I≥σ(Ⅰ). The investigation confirms that the crystal structure consists of tetraethylammonium cations and trinuclear Mo cluster anions. The anion is a μ_3-O monocapped trinuclear cluster with an average Mo-Mo bond length of 2.60 (2). On the side of the Mo_3 triangular plane opposite to the μ_3-O atom, each two Mo atoms are bridged by a Cl atom with the result that these seven atoms (3 Me, 1 O and 3 Cl atoms)form an apex-deficient quasicubane configuration. In addition, each Mo atom is coordinated to three additional atoms resulting in a pseudo-octahedral geome