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1.
The structure of the title compound features mononuclear octahedral CoII cations, trans-[Co(H2O)2(MeCN)4]2+, and trinuclear anions, trans-[Co(H2O)2(MeCN)2(CoCl4)2]2–; the latter centrosymmetric units contain a central octahedral Co(H2O)2(MeCN)2 moiety with two tetrahedral [CoCl4]2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.  相似文献   

2.
《Polyhedron》1986,5(10):1547-1551
The trans-[Co(en)2(malH)2]ClO4·H2O complex was prepared by the reaction of sodium hydrogen malonate with [Co(en)2(H2O2](ClO4)3 in the presence of a large concentration of perchlorate ion. It showed a three-band visible spectrum (γγmax 357, 448 and 542.6 nm), diagnostic of a trans-MA4B2 system and gave characteristic IR bands as expected for a trans-bisethylenediamine cobalt(III) complex. The 1H NMR spectrum in DMSO-d6 revealed a broad band at 5.8 ppm assignable to the amino hydrogen and a single band at 2.68 for the ethylene group of the chelate ring. The
group of the hydrogen malonate ion appeared as a sharp singlet at 2.95 ppm and integration showed the presence of two bimalonate groups. The reactive methylene protons were found to be exchangeable. Ion association by counter ions of the complex ion in DMSO-d6 showed no preference among amino protons. This is as expected for trans complexes with D2h-symmetry.  相似文献   

3.
In treatment of trans-[Ru(NO)(NH3)4(OH)]Cl2 with concentrated sulfuric acid on heating trans-[Ru(NO)(NH3)4(SO4)](HSO4)·H2O (I) is obtained with a yield close to quantitative. In the interaction of the saturated solution of I with a saturated NaNO3 solution a trans-[Ru(NO)(NH3)4(SO4)]NO3·H2O (II) precipitate forms whose structure is determined by single crystal XRD: space group P212121, a = 6.8406(3) Å, b = 12.6581(5) Å, c = 13.3291(5) Å. A monodentately coordinated sulfate ion is in the trans-position to the nitroso group. Compound II is characterized by IR spectroscopy, powder XRD, and diffuse reflectance spectroscopy. The process of its thermolysis is studied; by differential scanning calorimetry the thermal effect of the dehydration reaction occurring on heating to 120°C (ΔH = 58.9 ± 1.5 kJ/mol) is estimated. The final product of the thermolysis of II is a mixture of Ru and RuO2.  相似文献   

4.
5.
Summary Crystals of Co2(X 2O7)·2H2O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P21/n,R=0.032/0.046,R w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO4 tetrahedra connected via a common corner to anX 2O7 group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.
Vergleich der Kristallstrukturen von Co2(X 2O7)·2H2O,X=P und As
Zusammenfassung Kristalle von Co2(X 2O7)·2H2O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P21/n,R=0.032/0.046,R w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX 2O7-Gruppen verknüpftenXO4-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.
  相似文献   

6.
Reaction of Na2[PdCl4] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl2-(LH)2] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl2(2-ampyH)2] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl2(2-acmpyH)2] with NEt3 affords the cyclometalated complex, trans-[Pd(κ2-2-acmpy)2], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl2(LH)2] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)2(LH)2], in which the saccharinate anions are coordinated via the amide nitrogen atom.  相似文献   

7.
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) (A), β = 117.532(4)°, V = 1123.9(8) (A)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   

8.
The results of an investigation concerning there action between 1,2-propanediol and Co(NO3)2⋅ 6H2O, leading to a complex containing the lactate anion (L) as ligand are presented. The obtained solid homopolynuclear coordination compound[Co2(OH)2L2(H2O)2⋅0.5H2O]n, has been investigated by thermal analysis, electronic and IR spectroscopy and magnetic methods. Cobalt oxide obtained by thermal decomposition of this coordinative compound was characterized by IR and X-ray spectroscopy. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

9.
Quantum chemical calculations at the DFT level have been carried out for model complexes [Mo(P)(NH2)3] (1), [Mo(N)(NH2)3] (2), [Mo(PO)(NH2)3] (3), [Mo(NO)(NH2)3] (4), [Mo(CO)5(PO)]+ (5), and [Mo(CO)5(NO)]+ (6). The equilibrium geometries and the vibration frequencies are in good agreement with experimental and previous theoretical results. The nature of the Mo–PO, Mo–NO, Mo–PO+, Mo–NO+, Mo–P, and Mo–N bond has been investigated by means of the AIM, NBO and EDA methods. The NBO and EDA data complement each other in the interpretation of the interatomic interactions while the numerical AIM results must be interpreted with caution. The terminal Mo–P and Mo–N bonds in 1 and 2 are clearly electron-sharing triple bonds. The terminal Mo–PO and Mo–NO bonds in 3 and 4 have also three bonding contributions from a σ and a degenerate π orbital where the σ components are more polarized toward the ligand end and the π orbitals are more polarized toward the metal end than in 1 and 2. The EDA calculations show that the π bonding contributions to the Mo–PO and Mo–NO bonds in 3 and 4 are much more important than the σ contributions while σ and π bonding have nearly equal strength in the terminal Mo–P and Mo–N bonds in 1 and 2. The total (NH2)3Mo–PO binding interactions are stronger than for (NH2)3Mo–P which is in agreement with the shorter Mo–PO bond. The calculated bond orders suggest that there are only (NH2)3Mo–PO and (NH2)3Mo–NO double bonds which comes from the larger polarization of the σ and π contributions but a closer inspection of the bonding shows that these bonds should also be considered as electron-sharing triple bonds. The bonding situation in the positively charged complexes [(CO)5Mo–(PO)]+ and [(CO)5Mo–(NO)]+ is best described in terms of (CO)5Mo → XO+ donation and (CO)5Mo ← XO+ backdonation (X = P, N) using the Dewar–Chatt–Duncanson model. The latter bonds are stronger and have a larger π character than the Mo-CO bonds.  相似文献   

10.
Crystal structures of [Co(MH)2(Thio)2][BF4] · H2O (I) and [Co(DH)2(NH3)2][BF4] (II), where MH is H3C–C(NOH)–C(NO)–H and DH is H3C–C(NOH)–C(NO)–CH3, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N4S2 for I and N6 for II. In the crystals of I and II, the complex cations and the outer-sphere [BF4] anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.  相似文献   

11.
The binuclear complexes [Cu2L2(H2O)4] · 5H2O (1) and [Ni2L2(H2O)4] · 2H2O (2) (where L = C11H11NO5S, H 2 L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P21/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) Å3; Z = 4; D Calcd = 1.729 g cm?3; F(000) = 1712; μ = 1.554 mm?1; R 1 = 0.0519, wR 2 = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) Å3; Z = 2; D Calcd = 1.604 g cm?3; F(000) = 800; μ = 1.388 mm?1; R 1 = 0.1859, wR 2 = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H2O)4 water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.  相似文献   

12.
Compounds [Rh(NH3)5(NO2)](NO3)2·H2O (I) with a = 7.6230(3) Å, b = 7.6230(3) Å, c = 10.3584(4) Å, space group I-42m, Z = 2, d calc = 2.026 g/cm3, V = 601.93(4) Å3, Rh-NH3 eq = 2.074 Å, Rh-NH3 ax (NO2) = 2.048 Å; [Rh(NH3)5(NO2)][Pd(NO2)4] (II) with a = 8.095(3) Å, b = 22.422(8) Å, c = 7.887(3) Å, β = 98.559(17)°, space group Cc, Z = 4, d calc = 2.461 g/cm3, V = 1415.6(9) Å3, Rh-NH3 eq = 2.069 Å, Rh-NH3 ax = 2.090 Å, Rh-NO2 = 2.002 Å; K2[Rh(NH3)(NO2)5]·H2O (III) with a = 7.5177(5) Å, b = 20.9856(15) Å, c = 7.7017(5) Å, space group Cmc21, Z = 4, d calc = 2.439 g/cm3, V = 1215.05(14) Å3, Rh-NH3 ax (NO2) = 2.094 Å, Rh-NO2 eq = 2.030 Å are synthesized and studied using single crystal X-ray diffraction.  相似文献   

13.
The crystal structure of [Co(NH3)5NO2](NO3)2·0.25H2O has been determined. Co1N8O8.25H15.5, a=7.582(3), c=10.331(3) Å, V=593.9(5) Å3, dcalc=1.782 g/cm3 for Z=2, space group I 4mm (C 4v 9 , No. 107). The structure is of the island type. Complex (distorted octahedral) cations are bonded to the NO 3 ? anions by electrostatic forces. Crystallization water is located in the vicinity of the labile NO2 group.  相似文献   

14.
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   

15.
《Polyhedron》1986,5(10):1639-1643
2-D 11B-11B correlation (COSY) spectra have been obtained on the series of monosubstituted and disubstituted octahydrotriborate anions, [B3H7(X)] (X = Cl, NCS, NCSe, NCBH3, NCBH2Cl, NCBPh3, NCBH2CN, NCB3H7 or CNB3H6Cl) and [B3H6(Cl)(X)] (X = Cl, NCS, NCBH2Cl or NCB3H7). All monosubstituted derivatives and [B3H6(Cl)2] showed a coupling correlation between the substituted and unsubstituted borons. The unsymmetrically disubstituted derivatives showed only one coupling correlation, between the borons carrying the substituents. The absence of other correlations is attributed to relaxation phenomena. The correlations are independent of the solid-state structural type.  相似文献   

16.
Binary complex salts, [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH3, hydrocarbons, and ethylenediamine.  相似文献   

17.

A series of new complexes of the Schiff base obtained from trans- cinnamaldehyde and 1,2-diaminoethane (en) with the general formula of M(ca 2 en)X 2 (M = Co(II), Ni(II), Zn(II); X = Cl, Br, I, NCS, N 3 ; (ca 2 en) = N,N '-bis( trans- cinnamaldehyde)-1,2-diiminoethane) have been synthesized and characterized. The crystal structures of three pseudo -tetrahedral complexes, Co(ca 2 en)Cl 2 ( 1 ), Co(ca 2 en)Br 2 ( 2 ), and Ni(ca 2 en)Br 2 ( 5 ), were determined by X-ray diffraction. Crystal data for 1 , Co(ca 2 en)Cl 2 : monoclinic; space group P 2 1 / c ; a = 7.1925(14) Å, b = 20.327(4) Å, c = 14.029(3) Å; g =95.06(3)°; V = 2043.1(7) Å 3 ; Z = 4; and final R 1 = 0.0381 ( wR 2 = 0.0718) for 4653 independent reflections with I > 2 σ ( I ) and 226 parameters; 2 , Co(ca 2 en)Br 2 ; monoclinic, space group P 2 1 / c ; a = 7.3780(6) Å, b = 20.4372(17) Å, c = 14.1649(12) Å; g = 94.902(2)°; V = 2128.1(3) Å 3 ; Z = 4; and final R 1 = 0.0491 ( wR 2 = 0.1052) for 5858 independent reflections with I > 2 σ ( I ) and 227 parameters; 5 , Ni(ca 2 en)Br 2 : monoclinic, space group P 2 1 / c ; a = 7.2388(6) Å, b = 20.4651(16) Å, c = 14.2782(12) Å; g = 94.160(2)°; V = 2109.6(3) Å 3 ; Z = 4; R 1 = 0.0481 ( wR 2 = 0.0907) for 5914 independent reflections with I > 2 σ ( I ) and 227 parameters. The structures consist of discrete molecules in which the coordination polyhedra about the central metal ion are highly distorted tetrahedra with Cl(1)-Co-Cl(2), 115.51(3)°; N(1)-Co-N(2), 83.71(7)°; Br(1)-Co-Br(2), 114.58(4)°; N(1)-Co-N(2), 84.92(19)°; and Br(1)-Ni-Br(2), 125.23(3)°; N(1)-Ni-N(2), 85.11(15)° in 1 , 2 , and 5 , respectively. The stiryl groups are cis -endo with respect to the metal atom and the chelate ring is puckered. Utilization is made of electronic and vibrational spectra in structural diagnosis of other complexes.  相似文献   

18.
An octahedral Zn complex with o-phenanthroline (o-phen) and cyanoguanidine (cnge) has been synthesized and characterized. The crystal structural data show the formation of a ZnN5O core where the metal coordinates to two mutually perpendicular o-phenanthrolines as bidentate ligands [Zn–N bond lengths in the 2.124(2)–2.193(2)?Å range], the cyanide nitrogen of a cnge [d(Zn–N)?=?2.092(2)?Å, ∠(Zn–N–C)?=?161.1(2)°], and a water molecule [d(Zn–Ow)?=?2.112(2)?Å]. Spectral data (FT-IR, Raman, and fluorescence) and speciation studies are in agreement with the structure found in the solid state and the one proposed to exist in the solution. To evaluate the changes in the microbiological activity of Zn, antibacterial studies were carried out by observing the changes in minimum inhibitory concentration of the complex, the ligands, and the metal against five different bacterial strains. The antibacterial activity of Zn improved upon complexation in three of the tested strains.  相似文献   

19.
Three compounds, [Cu(Pic)2(H2O)] (1a), [M(Pic)2(H2O)2]·2H2O] (M=Co (2a), Zn (3a), Pic = 2-picolinic acid) were obtained by solvent-free synthesis through grinding of metal acetate salt with 2-picolinic acid. Favorable comparison of solvent-free with solution based method of 1b, 2b and 3b was observed. Good resemblance of identity of compounds obtained through the two methods was confirmed by elemental analysis, spectroscopic techniques (UV-Vis and FTIR), TGA and PXRD. The single crystal diffraction data for [Co(Pic)2(H2O)2]·2H2O obtained from the Cambridge structure database (CSD), its PXRD simulated patterns closely matched that of complex 2a by solvent-free synthesis. Vapochromic behavior of this complex was studied using colour change, FT-IR, TGA, PXRD and solid state UV-visible spectroscopies. This complex generated specific colour which is also evident in the shifting of the vibrational frequencies (νO-H and ν C=O bands). The resulting inclusion compounds have different colours depending on the solvent used. In addition, exposure of the resultant inclusion compounds to ambient environment or heating for a few minutes regenerate the original material without degradation even after exposure/heating cycles as evident from TGA/DTG thermograms.  相似文献   

20.
Two new coordination polymers, [M(sac)2(μ–pyz)(H2O)2] n [M=ZnII(1), CdII(2), pyz =?pyrazine, and sac =?saccharinate], have been prepared and characterized by elemental analysis, FTIR spectroscopy, thermal analysis and single crystal X-ray diffraction. Both complexes are isomorphous and crystallize in the triclinic P 1 space group. The metal(II) ions are octahedrally coordinated by two sac, two aqua and two pyz ligands. The sac ligands are N-coordinated, while the pyz ligands are bridges between the metal centers, leading to one-dimensional linear chains. Intra-chain M–M separations in 1 and 2 are 7.218 and 7.498 Å, respectively. The individual chains are linked by strong OW–H ··· O(sac) hydrogen bonds into two–dimensional layers, which are further assembled into three–dimensional supramolecular networks by aromatic π(sac) ··· π(sac) stackings interactions.  相似文献   

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