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1.
2.
Compounds p-HOOCC6F4COOH · H2O (H2L · H2O), [Tb2(H2O)4(L)3 · 2H2O] n (I), and Tb2(Phen)2(L)3 · 2H2O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H2L · H2O is built of centrosymmetric molecules H2L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb2(H2O)4(L)3] n and molecules of water of crystallization. The ligands are the L2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO9 is a distorted three-capped trigonal prism. Acid H2L manifests photoluminescence in the UV region (??max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb3+ ions, and the band with ??max = 545 nm (transition 5 D 4?? 7 F 5) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.  相似文献   

3.
The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.  相似文献   

4.
Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.  相似文献   

5.
6.
Alkylation of ethylenediamine with allyl bromide in the presence of NaHCO3 in benzene-ethanol and acetone-ethanol gave N,N,N′,N′-tetraallylethylenediamine L4 and N,N,N,N′,N′-pentaallylethylenediaminium bromide (L5(H+)Br2), respectively. The ac electrochemical synthesis at copper wire electrodes in solutions of copper(II) halide and an appropriate ligand yielded single crystals of Cu(I) complexes with ethylenediaminium ([L0(H+)2]0.5CuCl2 (I) and [L0(H+)2]0.5CuBr1.67Cl0.33 (II)) and its N-allyl derivatives N,N,N′,N′-tetraallylethylenediaminium ([{L4(H+)2}0.5Cu2Cl3] (III)) and N,N,N,N′,N′-pentaallylethylenediaminium ([L5(H+)Cu4Br6] (IV)). The crystal structures of complexes I–IV were determined by X-ray diffraction. The isostructural crystals of complexes I and II are triclinic, space group P $ \bar 1 $ , Z = 2. For I: a = 5.936(3), b = 6.387(3), c = 7.126(4) Å, α = 67.82(4)°, β = 72.98(4)°, γ = 67.55(4)°, V = 227.7(2) Å3. For II a = 6.110(3), b = 6.657(3), c = 7.309(3) Å, α = 68.40(3)°, β = 72.38(3)°, γ = 67.23(3)°, V = 250.4(2) Å3. In structures I and II, the organic cations are between infinite anionic chains (Cu 2 ? ) n . The crystals of π-complex III are triclinic, space group P $ \bar 1 $ , a = 6.851(4), b = 8.729(4), c = 9.960(4) Å, α = 98.25(3)°, β = 102.29(3)°, γ = 107.30(3)°, V = 541.8(5) Å3, Z = 2. In structure III, all the four allyl groups are π-coordinated by the metal atoms of four discrete anions Cu4Cl 6 2? . The crystals of π-complex IV are monoclinic, space group C2/c, a = 15.228(5), b = 17.095(6), c = 20.182(6) Å, β = 92.43(4)°, V = 5249(3) Å3, Z = 8. Only two of five allyl groups at the same N atom are coordinated by copper(I) atoms. Structure IV contains a complex inorganic fragment of the formula (Cu4Br 6 2? ) n .  相似文献   

7.
The syntheses and crystal structures of the closely related but non-isostructural Cd2(C19H21N3O3F)4(H2O)2?·?4H2O (1) and Pb2(C19H21N3O3F)4?·?4H2O (2) are described, where C19H21N3O3F? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M2O2 (M?=?Cd, Pb) structural unit. The Cd2+ coordination polyhedron in 1 is a CdO6 trigonal prism, including one coordinated water. The Pb2+ coordination polyhedron in 2 can be described as a very distorted square-based PbO5 pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C76H96Cd2F4N12O18, M r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?Å3, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F 2)?=?0.079. 2: C76H88F4N12O16Pb2, M r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?Å3, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F 2)?=?0.049.  相似文献   

8.
From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO3 in acetic acid solution, a new compound, [Mo22-O)2(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P21/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρc = 1.665 g/cm3, μ(MoK α) = 0.84 mm?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.  相似文献   

9.
Two Cu(II) hydroxo succinates [Cu3(H2O)2(OH)2(C4H4O4)2]?·?4H2O (1) and [Cu4(H2O)2(OH)4(C4H4O4)2]?·?5H2O (2) and one Cu(II) hydroxo glutarate [Cu5(OH)6(C5H6O4)2]?·?4H2O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO6} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO6} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H2O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO6} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H2O molecules. The {CuO6} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H2O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.  相似文献   

10.
The crystal structure determination of the title compounds showed that they are isomorphous, revealing the general formula [M(H2O)4(py)2](sac)2·4H2O. Their structures are built up of [M(H2O)4(py)2]2+ cations, saccharinato anions and non-coordinated water molecules. The metal atom lies on the inversion center and is octahedrally coordinated by four water oxygens and two pyridine nitrogen atoms. The crystal structure packing is achieved through the hydrogen bonds of Ow⋯Ow, Ow⋯O and Ow⋯N type. Coordinated water molecules are hydrogen bonded to non-coordinated ones at the same time participating in hydrogen bonding with carbonyl oxygen and nitrogen atom from the saccharinato anions. Non-coordinated water molecules participate in hydrogen bonding with the oxygen atoms belonging to the saccharinato CO and SO2 groups. The hydrogen bond network between the oxygen atoms belonging to the SO2 group of the saccharinato anions and one of the non-coordinated water molecules (OW3) constructs the centrosymmetric cavity in the structure.  相似文献   

11.
The title compound (C6N3H18)2Ti4O4(C2O4)7(4H2O 1 (C13H22N3O18Ti2, Mr = 604.14) was synthesized by the reaction of Ti(SO4)2, H2C2O4(2H2O and N-(2-ammonioethyl)- piperazinium (AEPP) in aqueous solution. The single-crystal X-ray analysis has revealed that 1 crystallizes in the triclinic system, space group Pī with a = 9.1437(6), b = 11.4991(10), c = 11.6975(8)A, α = 96.2915(18), β = 107.998(3), γ = 104.276(4)°, V = 1110.35(14)A3, Z = 2, Dc = 1.807 g/cm3, F(000) = 618, μ = 0.815 mm-1, the final R = 0.0463 and wR = 0.1264 for 3718 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Ti4O4(C2O4)7]6- anion and two protonated N-(2-ammonioethyl)piperazinium cations. The anions are linked into an infinite chain through Ti4O4(C2O4)8 by sharing the oxalates as bridging ligands.  相似文献   

12.
Qualitative single crystals of ??-complexes Cu(H+L)(ClO4)]ClO4 · H2O (I), Cu(H+L)(BF4)]BF4 · H2O (II), and [Cu(H+L)(H2O)]SiF6 · H2O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO4)2 · 6H2O, Cu(BF4)2 · 6H2O, and CuSiF6 · 4H2O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P21/n, Z = 4. For compound III, space group P21/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?3; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?3. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H+L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO 4 ? or BF 4 ? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF 6 2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).  相似文献   

13.
Two fumarato-bridged Co(II) coordination polymers Co(H2O)4L 1 and [Co3(H2O)4(OH)2L2]·2H2O 2 with H2LHOOCCH CHCOOH were prepared. Complex 1 consists of polymeric chains 1[Co(H2O)4(C4H2O4)2/2], which result from octahedrally coordinated Co atoms bridged by bis-monodentate fumarate anions and are assembled by interchain hydrogen bonds. Within 2, the edge-shared Co2O10 bi-octahedra are connected to the CoO6 octahedra to form 1D cobalt oxide chains and 3D open framework generated from the chains inter-linked by bis-bidentate fumarate anions displays rhombic tunnels, which are filled with the lattice H2O molecules. Thermal and magnetic behaviors of both the title coordination polymers are discussed. Crystal data: (1) monoclinic, P21/c, Z=4, a=7.493(1) Å, b=14.377(1) Å, c=7.708(1) Å, β=99.54(1)°, V=818.9(2) Å3, R1=0.0304, and wR2=0.0669 for 1487 observed reflections (I⩾2σ(I)) out of 1877 unique reflections; (2) monoclinic, P21/c, Z=2, a=6.618(1) Å, b=8.172(2) Å, c=15.578(3) Å, β=96.30(3)°, V=837.4(3) Å3, R1=0.0360 and wR2=0.0663 for 1442 observed reflections (I⩾2σ(I)) out of 1927 unique reflections.  相似文献   

14.
Two new Cd(II) coordination polymers, [Cd(C4H6N2)2(C4H2O4)(H2O)2] n (1) (where C4H6N2?=?2-methylimidazole, C4H2O4?=?fumarate), and [Cd(C4H6N2)(H2O)(C4H4O4)] n ?·?nH2O (2), (where C4H4O4?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.  相似文献   

15.
[[UO2(L)(OH)] (I), (CN3H6)2[(UO2)2CrO4(L)4] · 2H2O (II), and [UO2(H2O)5][(UO2)2Cr2O7(L)4] (III) crystals, where L is picolinate ion C5H4NCOO?, have been synthesized and studied by X-ray diffraction and IR spectroscopy. Complex I crystallizes in triclinic system with the unit cell parameters a = 6.2858(5) Å, b = 7.9522(5) Å, c = 8.3598(6) Å, α = 79.527(6)°, β = 87.760(6)°, γ = 79.126(6)°, space group P $\bar 1$ , Z = 2, R = 0.0306, and complexes II and III crystalize in monoclinic system with a = 8.8630(9) Å, b = 13.4540(13) Å, c = 31.266(3) Å, β = 93.118(3)°, space group C2/c, Z = 4, R = 0.0187 (II), and a = 7.3172(4) Å, b = 15.4719(8) Å, c = 16.6534(10) Å, β = 98.943(4)°, space group P21/m, Z = 2, R = 0.0588 (III). The structure of complex I is built of electronegative [UO2(L)(OH)] chains, which belong to the AT11M2 crystallochemical group (A = UO 2 2+ , T11 = L, M2 = OH?) of uranyl complexes. The structure of complexes II and III contains [(UO2)2(L′)(L)4]2? dimers (L′ = CrO 4 2? or Cr2O 7 2? ), which belong to the A2B2B 4 01 group (A = UO 2 2+ ,B2 = L′, B01 = L). The specifics of intermolecular interactions in the structures of complexes I–III and some their analogues have been considered using molecular Voronoi-Dirichlet polyhedra.  相似文献   

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17.

Reaction of a freshly prepared Ni(OH)2?2 x (CO3) x ·yH2O with maleic acid in H2O at room temperature afforded [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O, which consists of [Ni(H2O)6]2+ cations, [Ni(H2O)2(C4H2O4)]2? anions and lattice H2O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.  相似文献   

18.
Fourteen bis(citrato)germanates(IV) and bis(citrato)stannates(IV) were prepared, in particular, [M(H2O)6][Ge(HCit)2] · 4H2O (M = Mg (I), Mn (II), Fe (III), Co (IV), Ni (V), Cu (VI), Zn (VII)) and [M(H2O)6][Sn(HCit)2] · nH2O (M = Mg, n = 4 (VIII); Mn, n = 2 (IX); Fe, n = 4 (X); Co, n = 4 (XI); Ni, n = 4 (XII); Cu, n = 4 (XIII); Zn, n = 3 (XIV)) (H4Cit is citric acid). The purity and the composition of the products were determined by a set of physicochemical methods including elemental analysis, thermogravimetry, and IR spectroscopy. The structures of I, II, IV, VI, VII, VIII, XI, and XII were determined by X-ray diffractometry. All eight crystals composed of centrosymmetrical octahederal [M(H2O)6]2+ cations, [Ge(HCit)2]2? (or [Sn(HCit)2]2?) anions, and crystal water molecules are isostructural. The structural units in I, II, IV, VI, VII, VIII, XI, and XII are connected by systems of hydrogen bonds to form a three-dimensional framework.  相似文献   

19.
Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...  相似文献   

20.
Abstract

The title complex, Cu2(C10H2O8)(C3H4O2)6(H2O)4 · 4H2O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.  相似文献   

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