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1.
A pair of structurally similar dinuclear oxovanadium(V) complexes, [VO2L1]2 (I) and [VO2L2]2 (II), where L1 and L2 are the mono-anionic form of 2-[(2-isopropylaminoethylimino)methyl]-4-methylphenol (HL1) and 4-fluoro-2-[(2-isopropylaminoethylimino)methyl]phenol (HL2), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P21/c, a = 12.528(1), b = 12.266(1), c = 9.432(1) Å, β = 104.814(3)°, V = 1401.2(3) Å3, Z = 2. The crystal of I is monoclinic: space group P21/n, a = 12.3128(5), b = 6.5124(3), c = 17.1272(7) Å, β = 105.863(1)°, V = 1321.1(1) Å3, Z = 2. The V…V distances are 3.210(1) Å in I and 3.219(1) Å in II. The V atoms in the complexes are in octahedral coordination. Biological assay indicates that complex II, bearing fluoro-substitute groups, has stronger antimicrobial activity against most bacteria than complex I which bearing methyl-substitute groups.  相似文献   

2.
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   

3.
The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L2+) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L2+: [L0.5CuCl2] (I), [L0.5CuCl0.72Br1.28] (II), and [L0.5CuBr2] (III). The crystal structures of complexes I–III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P21/n, Z = 4. For I: a = 7.632(4) Å, b = 11.318(5) Å, c = 10.635(5) Å, β = 98.551(7)°, V = 908.4(7) Å3. For II: a = 7.7415(7) Å, b = 11.4652(9) Å, c = 10.7267(10) Å, β = 98.351(4)°, V = 942.0(2) Å3. The organic cation L2+ acts as a bridge linking a pair of separate cuprous halide fragments Cu2X4. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P21/c, a = 6.519(2) Å, b = 9.060(3) Å, c = 16.284(6) Å, β = 97.219(4)°, V = 954.2(6) Å3, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr 2 ? ) n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I–III are stabilized by hydrogen bonds (C)H…X (2.6–2.9 Å).  相似文献   

4.
The reaction of K2[Ru(NO)Cl5] with pyridine in aqueous ethanol at pH ~ 7–8 affords a nitrosoruthenium hydroxocomplex mer-[Ru(NO)Py3Cl(OH)]Cl·1.5H2O (I) (yield ~55%). Treatment of hydroxocomplex I with hydrochloric acid at room temperature gives the aqua complex mer-[Ru(NO)Py3Cl(H2O)]Cl2·2H2O·0.5HCl (II). The structures of the compounds are determined by X-ray crystallography: I, space group P21/n, a = 9.2292(4) Å, b = 11.7781(4) Å, c = 17.4915(7) Å, β = 90.9560(10)°, R = 4.84%; II, space group P-1, a = 7.3528(9) Å, b = 11.5793(11) Å, c = 13.6961(16) Å, α = 84.558(3)°, β = 87.668(4)°, γ = 74.146(4)°, R = 6.22%. Compounds I and II are characterized by powder XRD, 1H and 13C NMR, and IR spectroscopy. The thermal decomposition of compound II in the inert atmosphere is examined by thermal analysis.  相似文献   

5.
Mixed-ligand complexes of asymmetric gadolinium β-diketonates with 2,2′-bipyridyl (Bipy)—[Gd(Pa)3(Bipy)] (HPa is pivaloylacetone) (I) and [Gd(Pta)3(Bipy)] (HPta is pivaloyltrifluoroacetone) (II)-have been obtained by direct interaction of initial reagents and their structures have been studied by X-ray crystallography. Crystals of I are monoclinic: a = 9.536(1) Å, b = 15.037(1) Å, c = 13.280(1) Å, β = 109.56(1)°, V = 1798.7(3) Å3, Z = 2, space group P21. Crystals of II are triclinic: a = 9.6696(17) Å, b = 12.1348(9) Å, c = 18.243(3) Å, α = 100.257(12)°, β = 103.997(2)°, γ = 101.438(11)°, V = 1977.4(5), Z = 2, space group P $\bar 1$ . The coordination polyhedron of the central gadolinium atom in I and II is a distorted square antiprism formed by six oxygen atoms of the three β-diketonate ligands (av. Gd-O, 2.35(2) and 2.351(5) Å in I and II, respectively) and two nitrogen atoms of the Bipy ligand (av. Gd-N, 2.47(2) and 2.584(7) Å in I and II, respectively). Although the molecular structures of these complexes are similar, they have different crystal packings. In II, the planes of the Bipy ligands of neighboring molecules related by an inversion center are bound by stacking interaction (the distance between the Bipy planes is 3.45 Å). The structure and properties of these mixed-ligand complexes have been discussed based on the results of quantum-chemical density functional theory calculations (DFT/B3PW91). The nature of the substituents in the β-diketonate ligand has an effect on the structure and properties of the complexes. The correlation between the Gd-Dik and Gd (Dik)3-Bipy bond energies has been studied.  相似文献   

6.
Heating of an aqueous solution of [Pt(en)Py2Cl2]Cl2 · 2H2O (I) with KBr excess leads to the formation of [Pt(en)Py2Br2]Br2 · H2O (II). The interaction of a solution of II with bromine water results in the precipitation of polybromide ([Pt(en)Py2Br2]Br2 · Br2), which within a few days in the reaction solution partly transforms into oximide platinum(IV) complex, [Pt(HN-C(O)-C(O)-NH)Py2Br2] · H2O (III). Complex [Pt(en)PyBr3]Br · H2O (IV) with an impurity of II was prepared by reacting KBr excess and the product of [Pt(en)Py2]Cl2 oxidation with chlorine in 0.05 N HCl. The action of HNO3 on the solution of IV produced a nitrate derivative ([Pt(en)PyBr3]NO3, V). Complex IV, unlike II, does not react with bromine. The IR spectra of all the obtained compounds were recorded. Complexes II, III, and V were studied by X-ray crystallography. The crystals of II are monoclinic, space group P21/c, a = 15.640(2) Å, b = 9.345(1) Å, c = 14.167(2) Å, β = 102.63(1)°, V = 2020.5(5) Å3, Z = 4, R hkl = 0.033. The crystals of III are triclinic, space group P $\bar 1$ , a = 7.108(1) Å, b = 10.946(1) Å, c = 11.020(2) Å, α = 83.63(1)°, β = 80.31(1)°, γ = 75.02(1)°, V = 814.4(2) Å3, Z = 2, R hkl = 0.033. In the near-planar five-membered chelate ring (torsion angle NCCN is 7°), the C-O distances (1.23(1) Å) correspond to double bonds; the C-C (1.53(1) Å) and C-N (1.31(1) Å), distances correspond to ordinary bonds. The crystals of V are monoclinic, space group P21/c, a = 8.306(2) Å, b = 8.995(2) Å, c = 20.231(4) Å, β = 97.48(2)°, V = 1498.6(6) Å3, Z = 4, R hkl = 0.037.  相似文献   

7.
The phenolic azide bridged dinuclear nickel(II) complex, [Ni2(L1)2(N3)(H2O)(μ1,1-N3)] · EtOH (I), and the thiocyanate bridged dinuclear copper(II) complex, [Cu2(L2)21,1-NCS)2] (II), where L1 and L2 are the deprotonated forms of 2-mothoxy-6-[(2-piperidin-1-ylethylimino)methyl]phenol and 2,4-dichloro-6-[(2-methylaminoethylimino)methyl]phenol, respectively, were synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal of I is orthorhombic: space group Pbca, a = 12.172(1), b = 20.953(1), c = 29.779(2) Å, V = 7594.8(9) Å3, Z = 8. The crystal of II is monoclinic: space group P21/n, a = 8.7615(11), b = 19.672(2), c = 16.568(2) Å, β = 99.449(2)°, V = 2816.9(6) Å3, Z = 4. The Ni atoms in I are in octahedral coordinations, and the Cu atoms in II are in square-pyramidal coordinations.  相似文献   

8.
Heteroligand binuclear complexes of CuCl with triphenylphosphine and 5-pyridine-2-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L1) of the compositions [CuCl(PPh3)(L1)]2 (I) and [CuCiL1]2 (II) are synthesized and studied by X-ray diffraction method. Crystals I are monoclinic; space group P21/n, a=8.9520(18) Å, b=18.926(4) Å, c=16.841(3) Å, β=94.96(3)°, Z=2. The Cu(I) atom has a quasi-tetrahedral surrounding involving the tetraphenylphosphine P atom, the pyridyl N atom of the molecule L1, and two bridging Cl atoms. Crystals II are monoclinic; space group P21/c, a=9.3520(19) Å, b=8.1490(16) Å, c=18.660(4) A, β = 104.43(3)°, Z = 2. Both L1 ligands in complex II act as bridges. The Cu(I) atom also has a quasi-tetrahedral surrounding formed by the Cl atoms, the pyridyl N atoms and thiol S atom of one L1 ligand, and the thione S atom of the second L1 ligand. Similar binuclear complexes with the bridging function of the L1 ligand were also detected in a solution of II by the ESI method.  相似文献   

9.
Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C9H7N(C3H5)]2CuIICl2.86Br1.14 (I), [C9H7N(C3H5)]CuIBr2 · H2O (II), and [C9H7N(C3H5)]CuIBr2 (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P21/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) Å3, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) Å3, Z = 2. The crystals of complex III are monoclinic: space group P21/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) Å3, Z = 4. The structure of compound I is built of the CuIIX 4 2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C9H7(C3H5)]2 Cu 2 I Br4 forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C9H7(C3H5)]2Cu 2 I Br4} n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.  相似文献   

10.
The complexes with the formulae [Mn(L1)2] · 0.5H2O (I) and [Mn(L2)2] (II), where L1 and L2 are the dianionic form of 2,4-dichloro-6-[(2-hydroxyethylimino)methyl]phenol and 2-{[1-(3-ethoxy-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol, respectively, were obtained and characterized by elemental analysis and IR spectroscopy. The crystal structures of complexes I and II were determined using X-ray diffraction. The crystal of I is orthorhombic space group Fdd2: a = 24.170(2), b = 32.021(3), c = 11.352(2) Å, V = 8785.9(19) Å3, Z = 8. The crystal of II is monoclinic space group C2/c: a = 13.931(4), b = 18.381(5), c = 12.444(5) Å, β = 121.980(3)°, V = 2702.9(15) Å3, Z = 4. The Mn atom in each of the complexes is in an octahedral coordination.  相似文献   

11.
Four new fluorochromatouranylates, namely, K[UO2(CrO4)F] · 1.5H2O (I), Rb[UO2(CrO4)F] · 1.5H2O (II), Rb[UO2(CrO4)F] · 0.5H2O (III), and Cs[UO2(CrO4)F] · 0.5H2O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P21/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO2(CrO4)F] n n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT3M2 crystallochemical group, to which the studied compounds I–III also belong, is discussed.  相似文献   

12.
ZnPhen(EtOCS2)2 (I) and Zn(2,2′-Bipy)(n-BuOCS2)2 (II) mixed-ligand complexes have been synthesized. The structures were solved from X-ray diffraction data (CAD-4 and X8-APEX diffractometers, MoK α radiation, 1879 and 3637 F hkl , R = 0.0374 and 0.0315). Crystals I are monoclinic with parameters a = 11.678(3) Å, b = 19.215(3) Å, c = 9.655(1) Å; β = 101.23(1)°; V = 2125.0(7) Å3; Z = 4, space group P21/c; crystals II are triclinic with parameters a = 8.7875(3) Å, b = 11.833(1) Å, c = 13.3454(6) Å; α = 112.154(2)°, β = 108.503(1)°, γ = 92.787(2)°; V = 1196.2(1) Å3; Z = 2, space group 1 $P\bar 1$ . The structures are composed of discrete mononuclear molecules. The polyhedra of the Zn atoms are distorted trigonal bipyramids N2S3 formed by coordination of the N atoms of Phen or 2,2′-Bipy molecules and sulfur atoms of the monodentate and cyclic bidentate xanthogenate ligand. In structures I and II, dimer assemblies are formed by π-π interactions of Phen or 2,2′-Bipy molecules.  相似文献   

13.
Zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3 (HL) were synthesized. Crystals of [M(DMSO)2L2] · CHCl3, where M= Zn(II) (I) and Mn(II) (II), obtained from chloroform plus dimethyl sulfoxide (DMSO) mixture were found to be isostructural based on the similarity of their unit cell parameters and unit cell volumes. The crystals are triclinic, Z = 2, space group P \(\bar 1\); a = 10.422(1) Å, b = 11.929(1) Å, c = 20.429(1) Å, α = 73.616(1)°, β = 85.095(1)°, γ = 77.586(1)° for complex I; a = 10.436(1) Å, b = 12.297(1) Å, c = 19.924(2) Å, α = 78.138(2)°, β = 87.625(2)°, γ = 82.048(2)° for complex II. X-ray structural analysis of complex I was carried out. For complex II, the structure was not refined because all of its atoms are each disordered over three to five positions. The two DMSO molecules in complex I coordinate the central metal atoms in the monodentate mode via their donor oxygen atoms to occupy an axial position and an equatorial position in an octahedral polyhedron. The other four positions are occupied by the four oxygen atoms of the two deprotonated ligands L? coordinated in the bidentate-cyclic mode. The outer sphere of complex I contains the solvating chloroform molecule.  相似文献   

14.
[[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   

15.
A synthetic procedure was developed, and heteropolynuclear coordination compounds—the products of the interaction of germanium tetrachloride with xylaric (trihydroxyglutaric) acid HOOC-CH(OH)-CH(OH)-CH(OH)-COOH (H5L) and the acetates of the 3d metals Mn(II) and Co(II)—were prepared. The compounds were characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of the [M(H2O)6][Ge(μ3-L)2{M(H2O)2}2] · 4H2O · nCH3CN complexes, where M = Co, n = 0 (I) and M = Mn, n = 1 (II), was performed. The crystals of I are monoclinic, a = 10.752(2) Å, b = 11.830(2) Å, and c = 10.772(2) Å, β = 94.741(3)°, V = 1365.4(5) Å3, Z = 2, space group P21/n, R1 = 0.0309 for 3200 reflections with I > 2σ(I). The crystals of II are triclinic, a = 9.5330(17) Å, b = 9.7415(17) Å, and c = 10.3935(18) Å, α = 115.024(2)°, β = 97.580(3)°, γ = 111.535(3)°, V = 764.9(2)Å3, Z = 1, space group $P\bar 1$ , R1 = 0.0621 for 3028 reflections with I > 2σ(I). The bimetallic anions [Ge(μ3-L)2{M(H2O)2}2]2?, the cations [M(H2O)6]2+, and crystal water molecules form the basis of compounds I and II (the acetonitrile molecule is also a constituent of compound II). In the centrally symmetrical trinuclear complex anion, the Ge(1) atom is bound to two M(1) atoms through two completely deprotonated bridging ligands. The Ge(1) atom is coordinated to the six alcohol oxygen atoms of two ligands L5? at the apexes of a distorted octahedron (the average Ge(1)-O distances in I and II are 1.8858(14) and 1.892(3)Å, respectively). The coordination polyhedron of the M(1) atom in the complex anion is a strongly distorted octahedron. The base of the coordination polyhedron is formed by the two bridging alcohol oxygen atoms (the average M(1)-O distances in I and II are 2.1756(14) and 2.255(3) Å, respectively) of two L5? ligands and by the oxygen atoms of two water molecules (the average M(1)-O distances in I and II are 2.0693(17) and 2.175(4) Å, respectively). In the centrally symmetrical complex cation, the coordination polyhedron of the M(2) atom is a somewhat distorted octahedron. The M(2)-O(H2O) bond lengths in I and II vary in the ranges of 2.0137(17)-2.1555(17) and 2.140(5)-2.172(4) Å, respectively (the average lengths are 2.0375(17) and 2.166(4) Å, respectively). The cations and anions are joined by a branched system of hydrogen bonds.  相似文献   

16.
Tetraamminecobalt hydrogen hexamolybdoferrate [Co(NH3)4] · H[FeMo6O18(OH)6] · 6H2O (I) and tetraamminecobalt hydrogen hexamolybdogallate(III) [Co(NH3)4] · H[GaMo6O18(OH)6] · 6H2O (II) were synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I and II are monoclinic; a = 16.21 Å, b = 5.43 Å, c = 12.32 Å, β = 119.63°, V = 1092.11 Å3, ρcalcd = 2.21 g/cm3, and Z = 1 for I; a = 16.24 Å, b = 5.59 Å, c = 12.29 Å, β = 119.79°, V = 1064.05 Å3, ρcalcd = 2.15 g/cm3, and Z = 1 for II. Compounds I and II were used as catalysts for soft oxidation of natural gas.  相似文献   

17.
New heteroligand Cu(II) and Zn(II) complexes with the α-naphthylacetic acid anion (NAA) and monoethanolamine (MEA), [M(NAA)2(MEA)2] (M = Cu2+, (I), Zn2+ (II)), are synthesized. The crystal structures of the obtained complexes are determined by X-ray diffraction analysis (CIF files CCDC 984097 (I) and 930946 (II)). The crystals are monoclinic, for I: a = 18.8140(9) Å, b = 4.82500(14) Å, c = 16.0360(7) Å, β = 115.135(6)°, V = 1317.87(11) Å3, space group P21/c, Z = 2; for II: a = 32.9760(14) Å, b = 5.0911(3) Å, c = 15.7994(10) Å, β = 94.418(5)°, V = 2644.6(3) Å3, space group C2/c, Z = 4. In the structure of complex I, the Cu2+ ion arranged in the symmetry center is coordinated at the vertices of the distorted octahedron by the oxygen atoms of two NAA molecules (Cu-O(2) 2.019(4) Å) and two MEA molecules. The latter is the bidentate-chelating ligand and coordinates the metal through the O and N atoms to form the five-membered metallocycle (Cu-O(3) 2.457(5), Cu-N(1) 1.986(5) Å). In complex II, the Zn atom (on axis 2) is coordinated at the vertices of the distorted tetrahedron by the oxygen atoms of two NAA molecules (Zn-O(2) 1.976(4) Å) and the nitrogen atoms of two MEA molecules (Zn-N 2.034(6) Å). The character of the interaction of coordinated NAA and MEA ligands and methods for packing complexes I and II are considered on the basis of the structural data.  相似文献   

18.
Two complexes, namely, (18-crown-6)bis(perchlorato-O,O′)strontium (I) and (18-crown-6)bis(perchlorato-O,O′)barium (II), are synthesized. Their crystal structures are determined by X-ray diffraction analysis. The structures of I (space group P21/c, a = 15.266 Å, b = 11.080 Å, c = 13.235 Å, β = 109.20°, Z = 4) and II (space group P21/n, a = 8.330 Å, b = 11.202 Å, c = 11.752 Å, β = 98.38°, Z = 2) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.077 (I) and 0.041 (II) against 3714 (I) and 2478 (II) independent reflections (CAD-4 diffractometer, λMoK α radiation). Complex molecules [Sr(18C6)(ClO4)2] in the structure of I and [Ba(18C6)(ClO4)2] in II (in the inversion center)—are of the host-guest type. The Sr2+ or Ba2+ cation is localized in the center of a cavity of the 18-crown-6 ligand and coordinated by its all six O atoms. In compounds I and II, the coordination polyhedron of the Sr2+ and Ba2+ cations (coordination number 10) can be described as a distorted hexagonal bipyramid with two bifurcated vertices at two O atoms of two ClO 4 ? ligands, which are disordered in I and II and each of them has two orientations.  相似文献   

19.
The first order rate constants for the tautomerization of the hydrio(alkynyl) clusters Ru3Pt(μ-H){μ42-C ≡ C1Bu}(CO)9(L2);1a: L2 = dppe,1b; L2 = dppet,1c; L2 = dppp and1d; L2 =S,S-dppb to the corresponding vinylidene clusters Ru3Pt{μ42-C = C(H)tBu}(CO)9(L2)2 have been measured, and they follow the orser1d <1a <1b1c. The reactions involving1a and1d exhibit an inverse kinetic deuterium isotope effect. The structures of1b, 2b, 2c, and2d were determined by X-ray crystallography, and are compared with those of1a and2a which have been previously reported. Crystal data for1b, space groupPbca,a = 13.338(4) Å,b = 17.771(6) Å,c = 36.092(8) Å,Z = 8,R(R w) = 0.059(0.058) for 2342 absorption corrected, observed data; for2b, space group P21/n,a = 10.566(2) Å,b = 20.234(5) Å,c = 20.270(3) Å,β = 96.11(1)°,Z = 4,R(R w) = 0.043(0.053) for 5865 absorption corrected, observed data; for2c, space group P21/n,a = 14.211(5) Å,b = 19.534(2) Å,c = 15.870(2) Å,β = 100.81(2)°,Z = 4,R(R w) = 0.055(0.031) for 6566 absorption corrected, observed data: for2d, space group P212121,a = 12.309(4) Å,b = 19.047(6) Å,c = 19.206(4) Å,Z = 4,R(R w) = 0.055(0.053) fpr 2151 absorption corrected, observed data. The fluxional behavior of1d and1e (which consists of two interconverting isomers) has been examined by variable temperature13C NMR spectroscopy and by31P EXSY.  相似文献   

20.
The crystal structures of bis(2-thiobarbiturato-O)tetraaquamagnesium Mg(H2O)4(HTBA-O)2 I and catena-[(μ2-2-thiobarbiturato-O,O)(2-thiobarbiturato-O)bis(μ2-aqua)diaquastrontium] monohydrate catena-[Sr(μ2-H2O)2(H2O)22-HTBA-O,O)(HBTA-O)] n · nH2O (II), where H2TBA is 2-thiobarbituric acid C4H4N2O2S, have been determined. Crystal data for a=6.7598(2) Å, b = 7.6060(2) Å, c = 8.5797(2) Å, α = 79.822(2)°, β = 76.622(1)°, γ = 69.124(1)°, V = 398.82(2) Å3, space group P $\bar 1$ , Z = 1; for II: a = 20.8499(4) Å, b = 19.2649(5) Å, c = 4.14007(9) Å, β = 92.023(2)°, V = 1661.91(7) Å3, space group P21/n, Z = 4. The Mg2+ ion in I is bonded to six O atoms of two HTBA? ions and four water molecules that form a nearly regular octahedron. Each Sr2+ ion in II is coordinated to three oxygen atoms of three HTBA? ions and six water molecules that form an almost ideal tricapped trigonal prism. These polyhedra share edges to form infinite chains. Intermolecular hydrogen bonds create layered structures of I and II.  相似文献   

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