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1.
Treatment of RuCl2(PPh3)3 with 6-dimethylaminopentafulvene in THF in the presence of water produced(η5-C5H4CHO) RuCl(PPh3)2, which was reduced by NaBH4 to give the Ru–H···HO dihydrogen bonded complex(η5-C5H4CH2OH) RuH(PPh3)2. The dihydrogen bonded complex(η5-C5H4CH2OH)RuH(PPh3)2 could also be synthesized by the reduction of complex(η5-C5H4CHO)RuH(PPh3)2, which was obtained by the reaction of RuHCl(PPh3)3 with 6-dimethylaminopentafulvene in the presence of water. The analogous dihydrogen bonded osmium complex(η5-C5H4CH2OH)OsH(PPh3)2 was similarly prepared. Single crystal structures and DFT calculations support the presence of intra-molecular H···H interaction, with separations of around 1.9 to 2.0 .  相似文献   

2.
The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.  相似文献   

3.
Tris)(η 5-cyclopentadienyl-μ-carbonyl-iron)-μ3-nitrosyl cluster was obtained from the reaction of cyclopentadienyl dicarbonyliron dimer with nitrogen monoxide in xylene. The cluster was characterized by elemental analyses, IR, MS and 1H NMR. The crystal structure of [(η5-C5H5)(μ-CO)Fe]3(μ3-NO).C4H8O was determined by X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pnma, a=9.053(2), 6=10.545(2), c=22.525(4) A, V=2150.3(7) A3, Z=4,Dc=1.68 g.cm-3; structure solution and refinement based on 1141 reflections with I > 3.0 (I) (MoKa, A=0.71073 A) converged at R=0.0540. The infrared absorption band at 1325 cm-1 of the μ3-NO in the cluster, which is red shifted, shows that μ3-NO is activated.  相似文献   

4.
A novel complex [Zn(FcCOO)2(2,2'-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) A, α = 90, β = 97.7420(10), γ = 90o, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) A3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I > 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.  相似文献   

5.
The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.  相似文献   

6.
All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori  相似文献   

7.
Treatment of tricarbonyl cyclopentadienyl metal (molybdenum or tungsten) chloride with equal molar amounts of tricarbonyl nitrosyl iron sodium at room temperature yielded the following complexes: orange (η5-C5H5)M(CO)2NO, violet [(η5-C5H5)M(CO)3]2 and black (η5-C5H5)M(μ3-NH)(μ2-NO)(μ2-CO)Fe2(CO)6. These were separated and purified by column chromatography. The last black complexes have a new cluster-type structure with a face-bridging imido(μ3-NH) ligand which was obtained by reducing the nitrosyl (NO) group. In this paper, synthesis and characterization of the title complexes are reported along with their crystal structures which are of two types.  相似文献   

8.
<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.  相似文献   

9.
<正> Complexes [(η8-C8H8)LnCl(OC4H8)2]2, (Ln = Pr(1), Nd(2)) both crystallize in monoclinic space group P21/n with cell dimensions for 1: a = 11. 860(3), b=12. 697(3), c=12. 161(2)(?), β=111. 88(2)°, V= 1699. 50(69) (?)3, Dc=1. 66gcm-3,Z==2 (4 monomers), μc=30. 2cm-1, F (000) = 848, the final R = 0. 031, Rw = 0. 032 for 2303 independent reflections with I≥ 3σ(I) ; and for 2: a=11. 834(4), b = 12. 666(5), c=12. 166(3)(?), β=111. 73(2)°, V= 1694. 03 (99)(?)3, Dc= 1. 68g. cm-3, Z = 2 (4 monomers), μc=32. 3cm-1, F(000) = 852, R=Rw = 0. 035 for 3487 independent reflections with I≥3σ(I). In each complex, there are two Ln atoms in a dimeric unit which are bridged asymmetrically by two chloride ions with Ln - Cl bond lengths of 2. 847(2) and 2. 924(2)(?) for 1, or 2. 836(1) and 2. 919(2)(?) for 2. The cyclooctatetraene COT dianion ring is planar with eightfold molecular symmetry and an average C -C bond length of 1. 392(?). It is symmetrically coordinated to the Ln atom with an average Ln - C distance of  相似文献   

10.
<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  相似文献   

11.
HU Jiu-Rong  LIANG Fu-Pei   《结构化学》2007,26(7):793-796
A novel complex [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2′-bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) (A), α = 90, β = 97.7420(10), γ = 90°, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) (A)3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I > 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.  相似文献   

12.
<正> The title complex crystallizes in the orthorhombic space group Pna21 with Mr = 570. 8, a = 16. 927(6), b = 18.942(7), c=10. 618(5)(?) and Z = 4. The structure was solved by Patterson and Fourier techniques and refined by block-diagonal least squares techniques to R = 0. 090 and Rw = 0. 093 for 1553 reflections with I>1. 5σ(I). The Pr3+ ion is bonded to five carbon atoms of cyclopentadi-enyl ring, four μ-chlorine atoms and one oxygen atom of THF in an octahedral geometry with the Pr-C distances in the range 2. 6.7 - 2. 79(?)(av. 2. 76(?)) , the Pr-Cl distances in the range 2. 81 - 2. 92(?) (av. 2. 86(?)) and the Pr -O distance of 2. 51 (?). Each Li+ ion is coordinated by two μ-chlorine atoms and two oxygen atoms from THF in a tetrahedral geometry with the Li-Cl distances in the range 2. 24 - 2. 61(?) (av. 2. 43(?)) and the Li -O distances in the range 1. 86-1. 94(?)(av. 1. 91(?)). The Pr atom and the two Li atoms are bridged asymmetrically by the chlorine atoms.  相似文献   

13.
The title compound of Cu(C14H9O3)2(C5H5N)2(C2H5OH)2(1) was synthesized via the hy- drothermal reaction of CuCl2·2H2O and 9-hydroxy-fluorene-9-carboxylic acid(HHF) with pyridine, and characterized by elemental analysis and infrared spectra. The crystal belongs to triclinic, space group P1 with a = 8.8302(12), b = 10.1625(14), c = 12.2708(17), α = 86.207(2), β = 69.562(2), γ = 64.932(2)o, V = 930.3(2) 3, Z = 1, Mr = 764.30, Dc = 1.364 g/cm3, F(000) = 399, S = 1.059 and μ(MoKα) = 0.644 mm-1. The final R = 0.0459 and wR = 0.1274 for 3414 observed reflections with I 2σ(I). The copper atom is six-coordinated by two oxygen atoms from two different 9-hydroxy-fluorene-9-carboxylate ligands, two pyridine nitrogen atoms and two ethanol oxygen atoms, forming a distorted octahedral coordination geometry. The extensive O–H···O hydrogen bonding connects the molecules to form a one-dimensional chain structure. Between adjacent one-dimensional chains, a two-dimensional layered structure was formed by fluorene ring π-π packing interaction. Between the layers, a three-dimensional structure was formed through the π-π packing interaction of the pyridine ring. Moreover, the thermal stability and photoluminescent property of the complex has been investigated.  相似文献   

14.
<正> The title complex Co2 (η5-C5H5 )2 [(μ-NtC4H9 )2SO2 ] (1) was isolated from the reaction of CpCo (COD) with tC4H9N = S = NC4H9t and characterized by mass spectral,IR,1HNMR and X-ray diffraction measurements. Co2SO2N2C18H28 Mr = 454. 4, tetragonal,space group P41212 (#92) ,a=9. 212(1) ,c=22. 899(4) A ,V=1943. 0(8) A3,Z= 4,Dc= 1. 55g/cm3 ,F(000)=944,μ(MoKa) = 18.21cm-1 ,R= 0. 048 and Rw = 0. 055 for 682 (I>3σ(Ⅰ))observed unique reflections. G. O. F. = 1. 25. This molecule contains Co-Co bond (2. 335 (2) A ) with two doubly bridging N atoms of the (tC4H9N)2SO2 ligand.  相似文献   

15.
仪晓凤  杨环  王义  王璐璐  桑瑞利  徐立 《结构化学》2014,33(11):1697-1702
A new mixed-valence heterometal cluster Mo8VW2VIO26(C5H5N)8·2H2O has been synthesized under solvothermal conditions and characterized by X-ray single-crystal diffraction, IR, UV-vis and XPS spectroscopy. The title compound crystallizes in the triclinic system, space group P1 with a = 11.708(3), b = 12.018(4), c = 13.316(4) , a = 112.184(4), β = 97.844(4), r = 110.043(3)o, V = 1551.9(8) 3 and Z = 1 at 293(2) K. The final full-matrix least-squares refinement converged to R = 0.0414 for 4460 observed unique reflections with I 2σ(I) and w R = 0.1290 for all data(5352) and S = 1.015. In addition, its thermal stability and fluorescent property have also been investigated.  相似文献   

16.
Under suitable reactant ratios without sublimation or reerystallization, single crystals of(η~5-C_5,H_5)_3 Ln-OC_4H_8(In = La, Pr, Nd) could be prepared by the reaction of cyclopentadienylsodium with respective lanthanide trichlorides in THF. Using low temperature technique wehave collected the X-ray data of single crystals of the title compounds at -60℃ under N_2and determined crystal structures. (η~5-C_5H_5)_3 Pr·OC_4H_8, [(η_5-C_5H_5)_3 Nd·OC_4H_8] recrystallizesin the monoclinic space group P2_1/n[P2_1/n] with unit cell parameters a = 8.406(3) [8.364(3)],b = 24. 510(9) [24.467(9)], c = 8. 284(3) [8.254(3)] A, β= 101.60(3) [101.42 (3)], D_c = 1. 62 [1.65]gem~(-3) for z = 4 [4]. Least-square refinement has led to a final R value of 0.056 [0.063],R_W = 0.049 [0.062]. The THF molecule is coordinated to the Pr [Nd] atom at a Pr-O [Nd-O]bond length of 2.16(1) [2.54(1)], A. The Pr-C (Cp) [Nd-C(Cp)] bond distances average 2.80(2) [2.78(2)] A. The title compounds are isostructaral with (η~5-C_5H_5)_3  相似文献   

17.
<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.  相似文献   

18.
The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) , β = 109.187(2)o, V = 1482.6(2) 3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with I > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.  相似文献   

19.
A new mononuclear Co(II) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) , β = 117.532(4)o, V = 1123.9(8) 3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm–1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (I > 2σ(I)). The Co(II) is six-coordinated by two nitrogen atoms from two hmz–1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).  相似文献   

20.
The reaction of Co(OAc)2·4H2O with the Schiff base H2L in a methanol solution affords the red crystals of {[CoIIIL2]·[CoII(H2O)6]0.5·2.25H2O}4 1 (H2L = N-(2-hydroxyphenyl) sali-cylidenimine). The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n, C104H114Co6N8O37, Mr = 2421.61, a = 10.625(3), b = 16.335(4), c = 15.265(4) , β = 102.990(4)o, V = 2581.6(11) 3, Z = 1, Dc = 1.558 g/cm3, μ = 1.034 mm-1, F(000) = 1252, R = 0.0414 and wR = 0.1167 for 5889 reflections. The Co(III) atom is six-coordinated by two nitrogen atoms and four oxygen atoms of two tridentate L ligands. The abundant hydrogen bonding interactions extend the complex into a one-dimensional supra-molecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.  相似文献   

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