[Tb(CH_3COO)_3(H_2O)_2]_2的合成及其结构测定

2-羟基吡啶、希土高氯酸盐和乙酸钴在乙腈中反应,制备了九配位化合物[Tb(CH_3COO)_3·2H_2O]_2该晶体为三斜晶系,P~(?)空间群,其晶胞参数为a=8.870(4)(?),b=9.247(1)(?),c=10.586(1)(?),α=65.13(1)°,β=64.43(2)°,γ=62.16(4)°,V=665.97(?)~3,Z=1,F(000)=394。测定了配合物的红外光谱。讨论了它的生成机制。     

四核钼簇合物的配体取代反应及产物Mo_4S_4(μ-OAc)_2(dtp)_4的晶体结构

标题化合物(Ⅰ)经由Mo_4S_4(μ-dtp)_4(Ⅱ)[dtp=S_2P(OEt)_2]和Ni(OAc)_2反应而得。(Ⅰ)晶体属单斜晶系,空间群P2/c,a=13.176(4),b=11.699(3),c=18.526(4)(?),β=116.11(3)°,V=2564(3)(?)~3,Z=2,D_c=1.776g·cm~(-3)。晶体结构由直接法解出,最终偏离因子R=0.085。本文结果表明,可由已知的四核钼簇合物经过配体置换反应,合成得到其簇骼中心[Mo_4S_4]保持不变并具有-OAc作为桥式配体和-dtp作为端基配体的混合配体类立方烷[Mo_4S_4]簇合物。     

SYNTHESIS AND CRYSTAL STRUCTURE OF TWO TRINUCLEAR MOLYBDENUM CLUSTERS CONTAINING A LOOSE COORDINATION SITE, {Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4-(C_3H_3ON)}·CH_3CN (Ⅰ) AND {Mo_3-(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4-(C_3H_3ON)}(Ⅱ)

The synthesis and crystal structure of two trinuclear molybdenum clusters containing a loosecoordination site, {Mo_3(μ_3-S)(μ-S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}· CH_3CN (Ⅰ) and {Mo_3(μ_3- O)-(μ- S)_3[S_2P(OEt)_2]_4(C_3H_3ON)} (Ⅱ), are reported. Cluster (Ⅰ) belongs to the monoclinic spacegroup p2_1/n, a = 16.579 (3), b = 16.959 (2), c = 16.867 (2) A, β= 94.44 (1)°, V = 4728A~3,Z = 4, D_c = 1.778g·cm~(-3). The crystal structure was solved by the Patterson method with afina1 R value of 0.045. Cluster (Ⅱ) belongs to the triclinic space group Pi, a = 13.175 (4),b = 13.372(6), c = 16.656(3)A, α= 117.87(4), β= 60.09(3), γ= 109.03(3)°, ν= 2231A~3,Z = 2, D_3 = 1.798g·cm~(-3). Direct methods were used to solve the crystal structure with afinal R value of 0.066. Both clusters are monocapped trinuclear ones having an oxazoleoccupied coordination site as their main structural characteristic. The difference in cappingatoms results in the difference in their skeletons, Mo_S_4 in cluster (Ⅰ) vs. Mo_3OS_3     

STUDY ON THE REACTION PERFORMANCE OF CLUSTER COMPOUND——A REACTION OF Cu(+2) CAPTURING LIGANDS FROM MOLYBDENUM CLUSTER AND THE CRYSTAL STRUCTURE OF ITS PRODUCT Cu_8Cl_2[S_2P(OEt)_2]_6

The oxidation-reduction reaction of the molybdenum cluster compound Mo_3(μ_3-S)(μ-S)_2-[μ-SOP(OEt)_2] [S_2P(OEt)_2]_3(O)_2 with CuCl_2·2H_2O has been investigated and the chemical components of its product, Cu_8Cl_2[S_2P(OEt)_2]_6, were confirmed. The crystal belongs to the triclinic system and the space group is P with the following unit cell parameters: a=11.578 (5), b=12.663 (3), c=14.317 (4); α=55.54 (2)°, β=57.35 (3)°, γ=72.23 (3)°; Z=1; D_(calc)=1.926 g·cm~(-3). Final discrepancy factor of R is 0.075 for 3573 unique reflections with I≥3σ(I). The results of investigation show that the crystal structure consists of molecular chains with Cu_8Cl_2[S_2P(OEt)_2]_6 as structural unit, in which eight Cu atoms form a cube-shaped cage. The coordination sphere of each Cu atom is a tetrahedron configuration. The distances between Cu atoms are 3.018-3.437, which indicates that there are no metal-metal bonds between Cu atoms. It is worthwhile to study further the phenomenon how Cu(+2) captures the     

两个具有松散配位的三核钼簇合物{Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}·CH_3CN(Ⅰ){Mo_3(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}(Ⅱ)的合成和晶体结构

本文报道了两个具有松散配位的三核钼簇合物{Mo_3(μ_3—S)(μ—S)_3[S_2P(OEt)_2]_4·(C_3H_3ON)}·CH_3GN(Ⅰ)、{Mo_3(μ_3—O)(μ—S)_3[S_2P(OEt)_2]_4(C_3H_3ON)}(Ⅱ)的合成和晶体结构。簇合物(Ⅰ)属单斜晶系,空间群为P2_2/n,晶胞参数为a=16.579(3),b=16.959(2),c=16.867(2);β=94.44(1)°;v=4728 3;Z=4;D_c=1.778g·cm~(-3),用Patterson法解出结构,最终偏离因子R=0.045。簇合物(Ⅱ)属三斜晶系,空间群为P1,晶胞参数为a=13.175(4),b=13.372(6),c=16.656(3);α=117.87(4)°,β=60.09(3)°,γ=109.03(3)°;ν=2231 3;Z=2;D_c=1.798g·cm~(-3),用直接法解出结构,最终偏离因子R=0.066。两个簇合物均为以具有一个松散配位为特征的单帽三核簇,而且松散配位上均被一嘿唑五员环所占据,其主要差别在于簇合物(Ⅰ)的簇胳为Mo_3S_4,而簇合物(Ⅱ)则为一Mo_3OS_3·文中对这一“松散”配位的三核钼簇合物的活泼性进行了讨论。     

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 structure of the cluster μ_3-sulfido-μ-(diethylphosphorodithioato-S,S''''-)-allylthioureo-cyclo-tris-[(μ-sulfido)-x-(diethylphosphorodi-thioato-S,S'''')-molybdenum(IV)],Mo_3S_4(C_4H_(10)O_2S_2P)_4(C_4H_8N_2S)

Title compound,Mr=1273.16,was synthesized by a substitution reaction and its crystal'is triclinic belonging to space group P1 with cell parameters:a=13.944(2),b=14.143(7),c=14.233(3),A,a=77.35(3)°,β=69.94(2)°,γ=63.50(3)°,V=2351(1)A~3,Z=2,D_c=1.799g cm~(-3).Room tem-perature,graphite-filtered Mo K_α,radiation(λ=0.71073A)was used for data collection.μ=14.988cm~(-1),F(000)=1280,R=0.051 for 7025 observed reflections.The crystal consists of decrete clustermolecules containing a duster core[Mo_3(μ_3-S)]~(10+)with three μ-S,one μ-dtp(dtp=[S_2P(OC_2H_5)]~(2-),three x-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom.Thebónds of cluster skeleton[Mo_3(μ_3-S)(μ-S)_3]~(4+),Mo—Mo 2.744～2.766,Mo—(μ_3-S)2.340～2.342 andMo—(μ-S)2.272～2.296 A,are comparable with those found in the related analogues.     

希夫碱配合物的研究——Ⅵ.K[Fe(acacen)(CN)_2]·2H_2O的合成及晶体结构

制备了K[Fe(acaccn)(CN)_2]·2H_2O,并测定了晶体结构.单胞中存在两种结构上不同的[Fc(acaccn)(CN)_2]~-,空间群为P3_1(＃144),晶胞参数为:a=b=11.873(3)(?),c=15.002(14)(?),V=2808(2)(?)~3,Z=6,D_c=1.44g/cm~3.     

SYNTHESIS AND STRUCTURE OF TETRANUCLEAR MOLYBDENUM CLUSTER COMPOUND[Mo_4S_4(μ-O_2CC_6H_5)_2(dtp)_4]

The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)wasobtained by the ligand substitution reaction of tetranuclear molybdenum cluster[Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in thepresence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c,Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4;Dc=1.78g/cm~3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]clustercore and t-(dtp)~(-1)ligands are retained and only μ-bridged(dtp)~(-1)ligands aresubstituted by(C_6H_5CO_2)~(-1)in the substitution reaction,thus producing the newtitle cluster compound,the structure of which contains two species of bidentateligand.     

铂氢化物trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2(tu=SC(NH_2)_2)的结构

制得含硫脲配体的铂氢化物单晶trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2,其结构测定结果为:C_(46)H_(55)N_4O_2P_2S_2ClPt M=1052.6,单斜晶系,空间群为 P2_1/c,a=12.103(1),b=21.619(3),c=20.189(4)(?),β=103.31(0)°,V=5140(2)(?)~3,Z=4,D_c=1.360g·cm~(-3),F(000)=2128,R=0.050,R_w=0.063.Pt(Ⅱ)与两个磷、一个硫脲分子的硫和一个氢相配合,形成四边形配位。     

STUDY ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF THE TWO TRINUCLEAR MOLYBDENUM CLUSTERS(C_5H_7S_2)[Mo_3(μ_3-O )(μ-X)_3(μ-OAc)_3Cl_3](X=Cl,Br)

The crystal structure of two isomorphic cluster compounds with formula (C_5H_7S_2)-[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (X=Cl for compound (Ⅰ) and compound (Ⅱ)) has been investigated by X-ray diffraction method. The parameters of two crystals are: a=10.423(1),b=17.095(4), c=14.062(7), β=97.54(4)(°); Dc=2.20gcm~(-3), D_o=2.17g cm~(-3) for compound (Ⅰ). and a=10.511(3), b=11.213(2), c=14.053(3), β=96.12(2)(°); D_c=2.52g cm~(-3), D_o=2.53gcm~(-3) for compound (Ⅱ). The space groups are P2_1/C. Z=4. The 2621 and 2548 independent reflections with I>3σ(I) were collected on a CAD-4 four-circle diffractometer by means of MoKα radiation. The crystal structures were solved by heavy atom method and refined by full-matrix least-squares technique to a final discrepancy factors of R=0.061 and 0.051 respectively. The results of investigation show that the molecule consists of the cation (C_5H_7S_2)+ and the trinuclear Mo cluster anion, the configuration of which is similar to that of (Et_4N)_2[Mo_3(μ_3-O)(μ     

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.     

1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(HPMBP)的金属离子配合物的结构研究——Ⅰ.HPMBP及其配合物Cu(PMBP)_2的晶体结构

本文研究了Cu(PMBP)_2和HPMBP的单晶体结构,晶体学参数为:(1)HPMBP,C_(17)H_(14)0_2N_2,M=278.31,单斜晶系,空间群P2_1/a,a=11.406(5),b=9.087(1),c=13.467(3)(?),β=90.76(3)°,V=1395.7(?)~3,Z=4,D_c=1.324g cm~(-3),μ=0.95cm~(-1).(2)Cu(PMBP)_2,C_(34)H_(26)O_4N_4Cu,M=618.16,单斜晶系,空间群P_2_1/c,a=6.809(3),b=23.722(8),c=9.102(3)(?),β=108.94(4)°,V=1390.7(?)~3,Z=2,D_c=1.476g cm~(-3) μ=8.67cm~(-1).结果表明,HPMBP具有烯醇式结构,其中两个给体氧原子处于有利于形成六元螯合环的几何位置;在配合物Cu(PMBP)_2中,Cu原子为对称中心,两个配体中的四个氧原子形成以Cu为中心的近似平面正方形的配位结构,Cu-O距离分别为1.906和1.896(?).     

THE MOLECULAR AND CRYSTAL STRUCTURE OF [Et4N]2[Fe2S2（NO）4]

<正> The compound [Et_4N]_2[Fe_2S_2(NO)_4] (M_r=556.36) crystallizes in the monoclinic,space group P 2_1/n with a=9. 688(3), b=10. 882(2), c=12. 625(2), β=97. 86(3)°, Z=2, V=1318. 4, D_c=1. 40g/cm~3, ;μ(MoK_a)=12. 8cm~(-1) and F(000)=588. The final R=0. 028 and R_w=0. 029 for 2041 reflections (I≥3σ(I)).The crystals of [Et_4N]_2[Fe_2S_2(NO)_4] consist of discrete cations [Et_4N]~+ and anions     

Synthesis,structure and electrochemistry of dithiocarbamato phenthiolate oxo-molybdenum(Ⅳ)complexes[MoO(SΦ)_2(S_2CNEt_2)]

The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]~- with phenthiolate [Et_4N]SΦin acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com-plex [MoO(SΦ)_2(S_2CNEt_2)]~-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2(S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo-noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V=2989~3,Z=4,D_c=1.35 g/cm~3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes inthe monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27(2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm~3 and R=0.051 for 2852 independeut reflections [I>3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]~- contains asingle oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atomis a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linkedto oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance(1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 wasdiscussed also.     

含氧桥的笼状化合物[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)-[H_3O]~+·1/2(CH_3)_2NCHo·1/2H_2O的合成和结构

[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O(DMF=(CH_3)_2NC-HO)(M_r=1204.67)的晶体属三斜晶系,空间群P,晶胞参数a=16.438(6);b=22.22(1);c=11.325(5),α=104.25(4);β=108.97(3);γ=97.68(4)°,V=3688(3),Z=4,D_c=2.17gcm~(-1),R=0.056,R_w=0.074,晶胞中每个不对称单元含有两个[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O,阴离子[Mo_5P_2O_(23)]~(6-)中的Mo、P原子成一个畸变五角双锥构型。有一个阴离子的所有原子(Mo、P、O)位置完全确定,而另一个阴离子有一个磷酸根的三个氧原子位置出现二重位置统计分布。化合物的阳离子为二甲胺阳离子和水合氢离子。     

A bi-butterfly W-Cu-S cluster compound:Synthesis and crystal structure of(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]

The compound(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]was obtained by the reaction of Bu_4NBr,(NH_4)_2WS_4,NaS_2NCC_4H_8 and CuCl in CH_3CN and CH_3OH.It crystallizes in the monoclinicspace group P2_1/c with unit cell parameters:a=21.875(5),b=16.843(4),c=17.745(5),β=101.69(6)°,V=6402(6)~3,Z=4,D_o=1.718 g·cm~(-3).The final R and R_w values converged to 0.055and 0.060 respectively.The structure consists of two‘butterfly’units[WS_4Cu_2]linked togetherby two weak Cu—S bonds and two bridging S_2CNC_4H_8 ligands.Infrared spectra gave charac-teristic absorptions at 495 cm~(-1) for W=S and 450,435,412 cm~(-1) for W—μ-S.     

钼簇合物反应性能的研究: {Mo3S4[S2P(OEt)2]4H2O}的加硫反应以及产物{Mo3(μ3-S)(μ-S2)3[S2P(OEt2]3I}的晶体结构

由贫硫化合物{Mo_3S_4[S_2P(OEt)_2]_4·H_2O}通过加硫获得了富硫化合物{Mo_3S_7[S_2P(OEt)_2]_3·I}(CH_8C_6H_5).化合物属三斜晶系,空间群PI,晶胞参数为a=10.350(1)A,b=13.931(4)A,c=16.369(3)A,α=103.69(2),β=86.62(1),γ=111.99(2)°,V=2183A~3;z=2,D_c=1.817g·cm~(-3).最终结构偏离因子R为0.042. 簇分子{Mo_3(μ_3-S)(μ-S_2)_3[S_2P(OEt)_2]3·I}属{Mo_3(μ3一Y)(μ-S_2)_3[S_2P(OEt)_2]_3·X}(Y=O,S;X=Cl,I)系列构型.{Mo_3}基本上是一个正三角形,Mo—Mo键长分别为2.721(1),2.724(1),2.725(1)A,Mo的配位多面体为七个硫原子组成的畸变五角双锥,有一个I原子联结着三个(S_2)~(2-)桥基的三个不与Mo共平面的S原子,I—S距离平均为3.169A,比相应的Van der Waals距离(～4.00A)明显地短,显示一定程度的成键作用,簇分子的这一构型是一种较为稳定的结构类型.     

A NOVEL REACTION BETWEEN [μ-PhC(O)S]-(μ-RS)Fe_2(CO)_6 AND (μ-R~1S)(μ-XMgS)Fe_2(CO)_6——THE SYNTHESIS, CHARACTERIZATION AND FORMATION MECHANISM OF TWIN CLUSTER COMPLEXES [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]

The reaction of (μ-RS)(μ-XMgS)Fe_2(CO)_6 with PhC(O)Cl gave four new benzoyl complexes [μ-PhC(O)S](μ-RS)Fe_2(CO)_6(R=Me, Et, n-Bu, CH_2=CHCH_2), which further reacted with (μ-R~1S)(μ-XMgS)Fe_2(CO)_6 to afford eight new twin cluster complexes with the general formula of [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]. The single crystal X-ray analysis for one of these complexes (R=n-Bu, R~1=Ph) showed that it consists of two different moieties PhSFe_2(CO)_6 and n-BuSFe_2(CO)_6 joined together through the spiran type of μ_4-S., The complex belongs to space group P-1; cell parameters are a=9.028(3), b=10.386(1), c=16.723 (5); α=87.70(2)°,β=75.67(2)°, r=82.26(2)°; z=2, Dx=1.743 g/cm~3. Final deviation factor R=0.031.     

CRYSTAL STRUCTURE OF DI - NITRATOBIS(ETHYLCAPROLACTAM)URANYL(Ⅱ) UO_2[CH_2(CH_2)_4CONC_2H_5]_2(NO_3)_2

The crystal structure of Di-nitratobis(ethylcaprolactam)uranyl(Ⅱ) UO_2[CH_2(CH_2)_4CONC_2H_5]_2(NO_3)_2 was established by a single-crystal X-ray diffraction study.It is triclinie, space group P1, with a=7.171(2), b=8.655(3), c=10.182(5)A, α=78.27(3), β=70.63(3), γ=81.76(3)°, V=581.7(4)A~3, Z=l, Dc=1.94 g.cm~(-3).Final R value is 0.0218.The result reveals that uranyl ion is coordinated to six oxygen atoms, two of them are from two carbonyl groups of ethylcaprolactam and the other four are from two nitrate groups.