杂多化合物K_2HPMo_8W_4O_(40)·8H_2O的合成和结构

合成了Keggin结构的杂多化合物K2HPMo8W4O40·8H2O，并测定了其单晶结构。晶胞参数为：四方晶系，空间群92871073。该化合物是由和水分子组成。该阴离子属Keggin结构，其中的12个金属原子是Mo，W的统计分布。M-M（M=2／3Mo＋1／3W）的键长为3．54。     

Synthesis and Crystal Structure of 〔Na(N-(p-chlorophenyl)aza-15-crown-5)-(Et_2O)〕_2 (Na_2W_(0.5)Mo_(7.5)O_(26))

1mThODUCnONThestudyofsupermolecularcomplexesofcrownetherringhasthrivedforyearsrecentlybecauseoftheirprobabilityprospectinmaterialscienceandlifescience,andtheirinterestingstereochemistrywhentheradiusofcavityofringischanged"'.Inthecourseofourinvestigationontherelationshipbetweenthesizeofthecrownetherringandthepolymerizationofpolyoxometalate,anovel'crystalofsupermolecularcomplexof[Na(N--(p--chlorophenyl)aza--15--crown--5)(Et,O)j2(Na,W,.5Mo,.5O,,)wasobtained.2EXPERIMENTALToasolutionofequ…     

Synthesis and Structure Characterization of Oxo Complex of Molybdenum(Ⅵ): MoO_2(C_9H_6NO)_2

1mThODU~NOxocomplexesofmolybdenumandtungstenareimPOrtantascatalystsfortheolefinmetathesisreactiontl),molybdenumoxocomplexesarealsoactivecatalystsfortheoxidationoforganicsubstrates(2).Sofar,synthesisofthesecomplexesarePrO-oecdedinsolution,wereportherethesynthesisofthetitlecompoundonthesolidstate,whichischaracterizedbyX--raycrystaldiffractionmethod.2EXPERimENTALAwellgroundmixtureofMoCI,.3H,O(0.1mmol)withC,H,NO(0.2mmol)inanagatemortarwastransferredintoareactiontubeandheatedinasandbatha…     

Synthesis and Structure of Tungsten Carbonyl Compound with 2-Mercapto Pyrimidine [Et_4N] [W (CO)_4(SC_4H_3,N_2) ]

1INTR0DUCTI0NLowva1encemolybdenum/tungstencomp1exeswiththiolatoligandsareusefulforthestudiesonsyntheticandstructuralchemistry.Inrecentyearswehavesynthe-sizedandcharacterizedaseriesofdinuclearMo-SRc0mpoundscontainingaplanarMoSzMocorewithamon0dentatethiolatoligand"-"anda"butterfly"M0S2Mocorewithabidentatethi0latoligand"=."H0wdoesmultidentateliganddo"hasnaturallyattracted0urinterest-2-mercaptoPyrimidine(PymS)wasusedasamultidentateligandtocarry0utsynthesisexperiment.unexpectedly,whichgavea…     

［Vmo_3O_4（O_2CEt）_8］_2Na_2的合成与结构

［ＶＭｏ３Ｏ４（Ｏ２ＣＥｔ）８］２Ｎａ２（１），三斜晶系，Ｐ１空间群，ａ＝１２．９７７（７），ｂ＝１４．０７０（６），ｃ＝１２．３３８（８），α＝１０９．８１（４），β＝１１７．２０（４），γ＝９０．５１（５）°，Ｖ＝１８４８．８３，Ｍｒ＝２０２０．６，Ｄｃ＝１．８１ｇ／ｃｍ３，Ｚ＝１，Ｆ（０００），μ＝１２．９ｃｍ１（ＭｏＫα）对３７４２个可观测反射点（Ｉ＞３σ（Ｉ））最终一致性因子为Ｒ＝０．０１８，Ｒω＝０．０５４。单晶结构分析表明，簇阴离子中两个［Ｍｏ３Ｏ４］４＋单元通过两个＂桥＂金属Ｖ原子连接成一个奇特的环状结构，Ｍｏ－Ｍｏ平均键长为２．５１９（１），Ｍｏ…Ｖ间平均距离为３．６５４。簇阴离子通过Ｎａ＋连成一个一维长链，Ｎａ原子与氧原子形成一个少见的五配位三角双锥结构，Ｎａ－Ｏ距离仅为２．３１２，Ｎａ－Ｏ间较强的相互作用以及无限长链的晶体结构很好地解释了簇合物（１）的稳定性和不溶性。     

含柠檬酸配体的钼硫簇合物的合成与晶体结构的测定

合成了含有Mo—S簇阴离子 [Mo2 O2 ( μ S) 2 (C6H5O7) (C6H4 O7) ]5-柠檬酸簇合物 ,并通过元素分析、红外光谱、紫外 可见光谱和X射线光电子能谱对配合物进行了表征 ,用X射线衍射法测定了该化合物的晶体结构 .结果表明 ,该簇合物属于单斜晶系 ,空间群P2 1/c,a =2 3 766( 5)nm ,b =1 3 2 74 ( 3 )nm ,c =2 2 4 71 ( 5)nm ,α=γ =90°,β=1 1 8 2 1°,V =6 2 4 7( 2 )nm3 ,Z =8,一致性因子R =0 0 83 1 ,R2 ,w=0 1 536.该簇合物阴离子中每一个Mo原子都采取扭曲的八面体结构 ,柠檬酸通过羟基、α 羧基、一个 β 羧基与Mo配位 .晶体结构表明在一个结晶学上不对称的结构单元内有两个结晶学上独立的分子 .     

一种新颖钒.钨异金属八核簇合物[VW~3~4(O~2CEt)~8]~2Na~2的合成与结构

本文报道了一种钒.钨异金属八核簇合物[VW~3~4(O~2CEt)~8]~2Na~2(1)在恒温液相条件下的合成与结构研究,晶体属三斜晶系,P1空间群,a=1.2973(4),b=1.4063(3),c=1.2396(5)nm,α=1.09.92(2),β=117.32(2),γ=90.53(2)°,V=1.8513nm^3,D~c=2.29g/cm^3,Z=1对5499个可观测反射点[I>3σ(I)] 最终一致性因子为R=0.030.单晶结构分析表明,簇阴离子中两个[W~3O~4]^4^+单元通过两个"桥"金属V原子联接成一个奇特的环状结构,W-W平均键长为0.25328(6)nm,W...V间平均距离为0.3654nm,簇阴离子通过Na^+联成一个一维长链.Na 原子具有少见的五配位,Na-O距离仅为0.2314nm,Na-O间教情的相互作用以及无限长链的晶体结构很好地解释乐簇合物1的稳定性和不溶性.     

Synthesis and Characterization of the Molybdenum－Tungsten Mixed－metal Oxopolymetalate（Et_4N）_2［Mo_（4．5）W_（1．5）O_（19）］

ＳｙｎｔｈｅｓｉｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆｔｈｅＭｏｌｙｂｄｅｎｕｍ－ＴｕｎｇｓｔｅｎＭｉｘｅｄ－ｍｅｔａｌＯｘｏｐｏｌｙｍｅｔａｌａｔｅ（Ｅｔ_４Ｎ）_２［Ｍｏ_（４．５）Ｗ_（１．５）Ｏ_（１９）］ＬｉｕＨｕａｎｇ；ＸｕＬｉ；Ｈｕａ?..     

Na_3H_2[PMo_(10)V_2O_(40)]·16H_2O的合成与晶体结构

标题化合物的晶体属P2_1/m空间群,α=13.821(2),b=15.355(3),c=11.597(2),β=107.50(2)°,V=2347.2~3,M_r=2091.46,Z=2,D_c=2.959 g·cm~(-3),μ(MoK_o)=30.77cm~(-1),F(000)=1992。用4049个独立可观测衍射精修结构,R=0.033。杂多酸阴离子[PMo_(10)V_2O_(40)]~(5-)具有准Keggin结构,12个金属原子呈无序分布,中心原子P与两个齿顶原子M(Mo/V)在对称面上。P—O平均键长1.541(2),M—O键长1.671(2)-2.432(2)。除一个Na—O配位多面体为畸变三方锥外,其余四个Na—O配位体均为六配位。讨论了Na~+离子呈无序分布的晶体结构特征并初步总结[PMo_(10)V_2O_(40)]~(5-)在不同晶相中的构型。     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

Structure of 〔Na(DB18C6) (CH_3OH)〕_2W_6O_(19)·(DB18C6)·(CH_3OH)

1INrnODUCTIoNlnthepreviouspapers,wehavereportedthesynthesisandcrystalstructureofseveralcrownetherpolyoxometalates"-",nowwestudythestructureofthetitlecomplexandcompareitwithsomeothercrownetherpolyoxometalatecomplexes.2EXPERmENTALToal5OmLaqueoussolutioncontaining32g(1OOmol)Na,WO#.2H,Opre-justedtopH=3.5withchloricacid,14g(4Ommol)(n-Bu)'NBrwasadded,thenwhitepowderwasformed.ThewhiteprecipitateobtainedwithafiltrationwaskeptasthenewmaterialAinnextstep.AmixtureoflgAandO.3g(O.8mmol)DB18…     

十一钼硅钴杂多蓝H_8[SiMo_(11)Co(H_2O)O_(39)]·20H_2O的合成与晶体结构

采用电解法制备了未见文献报道的杂多蓝H8[SiMo11Co（H2O）O39]·20H2O，通过X-射线衍射测定了其晶体结构，该晶体属单斜晶系，空间群P21；。晶胞参数全矩阵最小二乘法修正至中心原子Si与4个氧形成四面体结构，配原子M（M＝11／12Mo＋1／12Co）与O形成12个MO6八面体结构3个MO6共边形成4个M3O13三金属簇，4个三金属簇与SiO4四面体共角相连形成阴离子结构。     

STRUCTURE OF（C6H5COCHCOC6H5）SmI2（THF）3

<正> (C6H5COCHCOC6H5)SmI2(THF)3,Mr= 843. 75,triclinic space group P1,a=13. 274(3),b=9. 886(3),c= 12. 526(4)A,a= 110. 89(3),B=93. 98(2),y=85. 16(2) ,V=1528. 9(8)A3,Z=2,Dc=1. 83g/cm3, (MoKa) = 0. 71069A,u= 40. 3cm-1,F(000) - 810. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R value of 0.082(Rw= 0. 083). The central Sm(III) ion is coordinated by two iodine ions, two oxygen atoms from C6H5COCHCOC6H5 and three oxygen atoms from three THF molecules to form a distorted pentagonal bipyramid. The Sm-I distances are 3. 103 and 3. 092 A ,The Sm-O (O atom from C6H5COCHCOC6H5) distances are 2. 273 and 2. 307 A and the average Sm -O(THF) distance is 2. 500A.     

Synthesis and Structural Characterization of a Salt{[Co(Phen)3][Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O)(Phen = 1,10-Phenanthroline,edt = Ethane-1,2-dithiolate)

Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2(6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) (A), β = 92.835°, V = 9829.3(3) (A)3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co-N and Mo…Mo bond distances are 2.139 and 2.872 (A), respectively.     

CRYSTAL STRUCTURE OF (NH_4)_(11)[Na(H_2O)_2P_4W_(14)O_(58)] ·12H_2O

<正> (NH4)11[Na(H2O)2P4W14O58)·12H2O, Mr = 4099. 39, triclinic, space group P1, a = 14. 376(2), b = 19.861(9), c=13. 010(3)(?) , α=104. 68(2), β=91. 37(1), γ= 104. 05(2)°, V = 3471. 1 (?)3, Z = 2, Dc=3. 922g/cm3, μ (MoKα) = 238. 274cm-1, F(000) = 3664, R = 0.0510, Rw = 0. 0665 for 9260 observed reflections with I> 3σ(I). The polyanion [Na(H2O)2P4W14O58]11- consists of two PW7O29 subunits anisostructurally, two linkage phosphorous atoms and one sodium ion with two water ligands as well. The geometries of tungsten atoms within these two subunits are almost the same as those in K12P4W14O58· 21H2O[2]. The four phosphorous atoms are in PO4 coordinations. The sodium ion locates nearly at the center of the polyanion, and is coordinated by two water molecules, five oxygen atoms of the anion and one phosphorous atom with Na-P = 3. 053(3) (?). Due to the presence of the sodium atom, the interactions between oxygen and tungsten atoms in the polyanion are somewhat weakened.     

Redox chemistry of the acetato-bridged clusters [M3(mu3-O)n(mu-O2CCH3)6(H2O)3]2+ (M = Mo, W, n = 1, 2): reversible redox between mono-micro3-oxo d8 M(III)2M(IV) and d9 M(III)3 forms

A cyclic voltammogram of aqueous 0.1 mol dm(-3) triflic acid solutions of the d6 bioxo-capped M-M bonded cluster [Mo3(mu3-O)2(O2CCH3)6(H2O)3]2+ at a glassy carbon electrode at 25 degrees C gives rise to an irreversible 3e- cathodic wave to a d9 Mo(III)3 species at -0.8 V vs. SCE which on the return scan gives rise to two anodic waves at +0.05 V vs. SCE (E(1/2), 1e- reversible to d8 Mo(III)2Mo(IV)) and +0.48 V vs. SCE (2e- irreversible back to d6 Mo(IV)3). The number of electrons passed at each redox wave has been confirmed by redox titration and controlled potential electrolysis which resulted in 90% recovery of [Mo3(mu3-O)2(O2CCH3)6(H2O)3]2+ following electrochemical re-oxidation at +0.8 V. A corresponding CV study of the d8 monoxo-capped W(III)2W(IV) cluster [W3(mu3-O)(O2CCH3)6(H2O)3]2+ gives rise to a reversible 1e- cathodic process at -0.92 V vs. SCE to give the d9 W(III)3 species [W3(mu3-O)(O2CCH3)6(H2O)3]+; the first authentic example of a W(III) complex with coordinated water ligands. However the cluster is too unstable (O2/water sensitive) to allow isolation. Comparisons with the cv study on [Mo3(mu3-O)2(O2CCH3)6(H2O)3]2+ suggest irreversible reduction of this complex to monoxo-capped [Mo(III)3(mu3-O)(O2CCH3)6(H2O)3]+ followed by reversible oxidation to its d8 counterpart [Mo3(mu3-O)(O2CCH3)6(H2O)3]2+ (Mo(III)2Mo(IV)) and finally irreversible oxidation back to the starting bioxo-capped cluster. Exposing the d9 Mo(III)3 cluster to air (O2) however gives a different final product with evidence of break up of the acetate bridged framework. Corresponding redox processes on d6 [W3(mu3-O)2(O2CCH3)6(H2O)3]2+ are too cathodic to allow similar generation of the monoxo-capped W(III)3 and W(III)2W(IV) clusters at the electrode surface.     

Crystal Structure of Dimer Complex of 〔K (dndb)(H_2O)(NCS)〕_2

1INtrODUCTIONThecrownethercomPOundsandtheirderivativeshavecontinuouslyattractedconsiderableattentioneversincetheywerefirstreportedin1967illbecauseoftheirexcellentcapacitytoattachmetalatomstoformcomplexes.Nowadaystheyareappliedextensivelyinchemistry,biology,medicine,agriculture,metallurgyandmanyotherfields.Manypapersonsynthesesofnewcrownethers,theirstructuredeterminationandcharactersareoftenpublished.Inthestudiesthenitrifiedreactionofcrownetherisknownasasignificantwaybywhichfunctionalgroup…     

CRYSTAL STRUCTURE OF [Ni((C)_6H_(11)O)_2PS_2)·(C_4H_9NH_2)_4]-(C_6H_(11)O)_2PS_2

<正> [Ni((C6H11O)2PS2)·(C4H9NH2)4](C6H11O)2PS2,Mr-=938. 05, triclinic,P1,a=13. 513(6),b=16. 040 (7), c= 12. 891(6) A , α= 95. 66 (4),β= 90. 23(4),γ= 75. 46(3)°,V = 2691 A3,Z=2,Dc= 1. 16 g·cm3.μ=6. 07cm-1,MoKa radiation, λ=0. 71069 A ,F(000) = 1020,R=0. 100 for 4595 reflections with I≥3σ(I). The title compound molecule consists of a complex cation [Ni((C6H11O)2PS2)(C4H9-NH2)4]+ and a complex anion (C6H11O)2PS2- . The Ni (Ⅱ) atom in the cation is octahedrally coordinated by four nitrogen atoms from four w-butylamine ligands and two sulfur atoms from one (C6H11O)2PS2 group.     

一个新的超大铈锑钨酸盐阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4

合成了一超大铈锑钨酸盐[Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O,用X射线单晶衍射法及元素分析确定了其结构。其晶胞参数为：a=1.8908(6)nm,b=2.0032(14)nm,c=2.8653(12)nm,α=86.95(6)°,β=75.68(3)°,γ=67.52(5)°,V=9.706(9)nm^3,空间群P1。在杂多阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4中,四个β-B-(SbW~9O~3~3)^9^-是通过一个大的中心集团[Ce~3Sb~4W~2O~8(H~2O)~1~0]^1^7^+连接起来的,中心集团中含有两个桥连{WO~2(H~2O)}基,三个Ce(Ⅲ)离子和一个{Sb~4O~4}基团。三个Ce(Ⅲ)离子的配位数均为9,Ce(1)和Ce(3)的配位环境相同,但不同于Ce(2)的配位环境,四个{SbW~9O~3~3}中的三个参与了向Ce(Ⅲ)的配位。两个{SbW~9O~3~3}中的四个氧,三个水分子中的三个氧,{Sb~4O~4}中的一个氧及一个桥连{WO~2(H~2O)}中的一个氧向Ce(1)[或Ce(3)]配位;两个{SbW~9O~3~3}中的四个氧,两个水分子中的两个氧,{Sb~4O~4}中的一个氧及两个桥连{WO~2(H~2O)}中的两个氧向Ce(2)配位。在{Sb~4O~4}中,四个Sb原子的中心构成了一四面体。该离子属C~s点群,Sb(5),Sb(8)和Ce(2)所在的平面是其对称面。     

CRYSTAL STRUCTURE OF CK(C_(12)H_(24)O_6)]_2Pd(SCN)_4(H_2O)

<正> [K(C_12H_24O_6)]_2Pd(SCN)_4(H_2O),MT=963.59,monoclinic, P21/n,a= 11. 075(1),b= 12. 231(1),c= 15. 863(2) A ,β=93. 25(1)°,V=2145. 3A3,Z=2, Dc=1. 492gcm-3,λ(MoKa) = 0. 71073A μ=8. 64cm-1,F(000) = 996,final R=0. 045 for 1835 observable reflections. The Pd2+ ion coordinates with four S atoms from SCN- groups forming a regular square planar configuration. The K+ ion is surrounded by six ether oxygen atoms,one O atom from water molecule coordinated to two K+ions and one N atom from SCN- group to form a distorted hexagonal bipyramid. Two K atoms are linked with one Pd atom by two bridging SCN- groups forming a chain molecular array in the crystal.