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1.
The complex [Ag(DDM)2(CH3C6H4NH2)]NO3, where DDM is 4,4-diaminodiphenylmethane [CH2(C6H4NH2)2], was synthesized and its structure was determined. The crystals are monoclinic, space group P21/n, a = 9.543(2) ?, b = 18.056(4) ?, c = 1.901(2) ?, β = 106.94(3)°, V = 1796.8(6) ?3, ρcalcd = 1.443 g/cm3, Z = 4. The Ag atom (at the inversion center) is coordinated at the vertices of an almost undistorted octahedron by six nitrogen atoms of the primary amino groups from four bridging DDM molecules and two terminal p-toluidine molecules (Ag-N, 2.546(3) ?; NAgN, 89.7–90.3°). Wavelike layers composed of conjugate multiunit metal rings, each containing four Ag+ ions and four bridging DDM ligands, are formed in the structure in the [101] direction (a 2D polymer). Uncoordinated NO 3 anions are arranged in the cavities between the layers and link them by N-H⋯O hydrogen bonds. Original Russian Text ? Yu.V. Kokunov, V.V. Kovalev, Yu.E. Gorbunova, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 12, pp. 1992–1998.  相似文献   

2.
The cationic complexes [({Ph3P}2C)Ag(C{PPh3}2)]X (2+, X = Cl, BF4) with a linear arrangement of the ligands were obtained from the reaction of C(PPh3)2 (1) with the appropriate AgX in THF. The 31P NMR spectrum of the cation 2+ exhibits a doublet with J(Ag,P) = 15.3 Hz. The cation was also formed when the adduct O2C ← 1 was allowed to react with AgX in CH2Cl2 in the first step as shown by 31P NMR; however, deprotonation of the solvent finally produced the cation (HC{PPh3}2)+, (H1)+ quantitatively. In the absence of coordinating anions, the tricationic complex [({Ph3P}2CH)Ag(CH{PPh3}2)](BF4)3 (3), containing the cation (H1)+ as ligand, could be isolated by reacting AgBF4 with the salt (H1)(BF4). All compounds were characterized by IR and 31P NMR spectroscopy; the structures of the compounds [2]Cl·1.25THF, 3·5CH2Cl2, 3·4C2H4Cl2, and (H1)(BF4) could be established by X-ray analyses.  相似文献   

3.
Single crystals of diammonium tetranitratouranylate (NH4)2[UO2(NO3)4] (I) and a new diammonium tetranitratouranylate complex with 18-crown-6 [(NH4)(18C6)]2[UO2(NO3)4] (II) have been synthesized by the reaction of diaquadinitratouranyl tetrahydrate with ammonium nitrate in a nitric acid solution and the reaction of the same reagents with 18C6 in an ethanol solution, respectively. The X-ray diffraction analysis of compounds I and II has been performed. Crystals of compounds I and II are monoclinic, Z = 2, space group P21/n, a = 6.4075(5) ?, b = 7.7851(7) ?, c = 12.4461(12) ?, β = 101.239(1)°, V = 608. 94(9) ?3 for compound I and a = 10.542(9) ?, b = 8.590(8) ?, c = 22.5019(19) ?, β = 101.632(1)°, V = 2058.3(3) ?3 for compound II. The [UO2(NO3)4]2− complex anion in compounds I and II contains two monodentate and two bidentate cyclic nitrato groups, and the coordination number of uranyl is 6. The 18C6 molecule in the structure of compound II has the classic crown conformation and combined with the ammonium ion by three hydrogen bonds. Compounds I and II formed by electrostatic attraction forces between counterions are stabilized by (NH4+)NH...O(NO3) interionic hydrogen bonds.  相似文献   

4.
Dark brown single crystals of [Ag(NH3)2]Ag(OsO3N)2 were obtained from the reaction of Ag2CO3, OsO4, and NH3 in aqueous solution. The crystal structure was solved in the monoclinic space group C2/m, with the following unit-cell dimensions: a=1962.5(3), b=633.1(1), c=812.6(1) pm, β=96.71(1)°. The final reliability factor was R=0.0256 for 1034 reflections with I>2σ(I). Linear [Ag(NH3)2]+ ions are present oriented perpendicular to the [010] direction, leading to short Ag+-Ag+ distances of 316 pm. A second type of Ag+ ions in the crystal structure present coordination number “6+1” and are surrounded by oxygen and nitrogen atoms of the nitridoosmate groups. Within the first of the two crystallographically distinguishable anions one can clearly differentiate between oxygen and nitrogen atoms while the second one exhibits a N/O disorder over two positions. The infrared spectrum of [Ag(NH3)2]Ag(OsO3N)2 shows the typical absorptions which can be attributed to the complex anions and the NH3 ligands.  相似文献   

5.
The structure of the product formed on boiling [RuNO(NH3)3(NO2)(OH)]Cl·0.5H2O in 3 M HNO3 is determined by XRD. The crystals belong to monoclinic symmetry. Crystallographic data for H11ClN6O8Ru are: a = 13.7924(4) ?, b = 6.9114(2) ?, c = 12.3577(4) ?, β = 111.863(1)°, V = 1093.27(6) ?3, Z = 4, d calc = 2.185 g/cm3, space group Cc. The structure is built of complex [RuNO(NH3)3(H2O)Cl]2+ cations and NO3 anions. The compound is studied by IR spectroscopy and X-ray phase analysis. Original Russian Text Copyright ? 2009 by V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 598–601, May–June, 2009.  相似文献   

6.
Mamata Singh  R.J. Butcher  N.K. Singh   《Polyhedron》2008,27(14):3151-3159
Two novel mononuclear mixed-ligand complexes [Ni(en)2(3-pyt)2] (1) and [Cu(en)2](3-pyt)2 (2), derived from potassium [N′-(pyridine-3-carbonyl)-hydrazinecarbodithioate [K+(H2L)] and containing en as a co-ligand, have been synthesized. The [K+(H2L)] undergoes cyclization in the presence of ethylenediamine (en) and is converted to 5-(3-pyridyl)-1,3,4-oxadiazole-2-thione (3-pyt). [Ni(en)2(3-pyt)2] and [Cu(en)2](3-pyt)2 have been characterized with the aid of elemental analyses, IR, UV–Vis, magnetic susceptibility and single crystal X-ray studies. The complexes 1 and 2 crystallize in the orthorhombic and monoclinic systems with space groups Pca2(1) and C2/c, respectively. The single crystal X-ray diffraction studies of both complexes indicate that (3-pyt) adopts a thione form in 1 but is present as a thiolato form in 2.  相似文献   

7.
Coordination polymers [Ag(Me4Pyz)] PF6(I) and [Ag2(Me4Pyz)3](BF4)2·H2O (II) have been synthesized, and their structures have been determined. The crystals of I are monoclinic, space group C2/c, a = 9.440(2) ?, b = 10.587(2) ?, c = 13.165(3) ?, β= 107.19(3)°, V = 1257.0(5) ?3, d = 2.056 g/cm3, Z = 4. The crystals of II are monoclinic, space group P21/n, a = 13.062(3) ?, b = 12.259(2) ?, c = 18.996(4) ?, β = 97.73(3)°, V = 3014.1(11)?3, ρ = 1.798 g/cm3, Z = 4. The structure of I is built of linear polymeric cations [Ag(C8H12N2)] + and octahedral anions [PF6]. Upon the interaction of tetramethylpyrazine molecule with Ag+ ions, intersecting polymeric chains [Ag(C8H12)] + (1D polymer) are formed extending in mutually perpendicular diagonal directions. The structure of II consists of layers (2D polymers) formed by fused sixmembered rings. These rings consist of Ag+ ions linked by bridging ligands Me4Pyz. Original Russian Text ? Yu.V. Kokunov, Yu.E. Gorbunova, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 5, pp. 743–750.  相似文献   

8.
New uranyl vanadates A3(UO2)7(VO4)5O (M=Li (1), Na (2), Ag (3)) have been synthesized by solid-state reaction and their structures determined from single-crystal X-ray diffraction data for 1 and 3. The tetragonal structure results of an alternation of two types of sheets denoted S for 2[UO2(VO4)2]4− and D for 2[(UO2)2(VO4)3]5− built from UO6 square bipyramids and connected through VO4 tetrahedra to 1[U(3)O5-U(4)O5]8− infinite chains of edge-shared U(3)O7 and U(4)O7 pentagonal bipyramids alternatively parallel to a- and b-axis to construct a three-dimensional uranyl vanadate arrangement. It is noticeable that similar [UO5]4− chains are connected only by S-type sheets in A2(UO2)3(VO4)2O and by D-type sheets in A(UO2)4(VO4)3, thus A3(UO2)7(VO4)5O appears as an intergrowth structure between the two previously reported series. The mobility of the monovalent ion in the mutually perpendicular channels created in the three-dimensional arrangement is correlated to the occupation rate of the sites and by the geometry of the different sites occupied by either Na, Ag or Li. Crystallographic data: 293 K, Bruker X8-APEX2 X-ray diffractometer equipped with a 4 K CCD detector, MoKα, λ=0.71073 Å, tetragonal symmetry, space group Pm2, Z=1, full-matrix least-squares refinement on the basis of F2; 1,a=7.2794(9) Å, c=14.514(4) Å, R1=0.021 and wR2=0.048 for 62 parameters with 782 independent reflections with I?2σ(I); 3, a=7.2373(3) Å, c=14.7973(15) Å, R1=0.041 and wR2=0.085 for 60 parameters with 1066 independent reflections with I?2σ(I).  相似文献   

9.
Electrical conductivities were measured for the ternary systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, La(NO3)3+Nd(NO3)3+H2O, and their binary subsystems Y(NO3)3+H2O, La(NO3)3+H2O, Ce(NO3)3+H2O, and Nd(NO3)3+H2O at (293.15, 298.15 and 308.15) K. The measured conductivities were used to test the generalized Young’s rule and the semi-ideal solution theory. The comparison results show that the generalized Young’s rule and the semi-ideal solution theory can yield good predictions for the conductivities of the ternary electrolyte solutions, implying that the conductivities of aqueous solutions of (1:3 + 1:3) electrolyte mixtures can be well predicted from those of their constituent binary solutions by the simple equations.  相似文献   

10.
Syntheses were developed, and compounds of composition (NH4)2x K2y Rb2z Th(NO3)6(x + y + z = 1) were prepared. These compounds were structurally studied using X-ray diffraction and IR spectroscopy. Incomplete miscibility in the solid phase of the title system was found, and the impossibility of existence of a hexanitratothorate complex in the (NH4)2Th(NO3)6-K2Th(NO3)6 system at 298.15 K and the component molar ratio 1: 3 was demonstrated. Calorimetric standard enthalpies of formation and mixing at 298.15 K were determined. Original Russian Text ? N.G. Chernorukov, A.V. Knyazev, A.A. Sazonov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 7, pp. 1066–1071.  相似文献   

11.
Two novel heterometallic trinuclear incomplete cubane-like clusters [(CH3CH2)4N][{M2CuS4}(edt)2(PPh3)] (M = Mo, W) have been synthesized by reaction of [(CH3CH2)4N]2[M2S4(edt)2] (M = Mo, W) with Cu(PPh3)2(dtp) [where edt is 1,2-ethane-dithiolato ligand, dtp is S2P(OCH2CH3)2]. The two crystals are isomorphous in space group P1 (No. 1). The unit cell contains two independent molecules, but the two discrete anions have the same orientation for the PPh3 ligands along one axis so the space group is undoubtedly non-centrosymmetric. The discrete anion contains two edt ligands and one PPh3 ligand attached to one incomplete cubane-like cluster core {M2CuS4}3+ (M = Mo, W). The bond lengths of Mo---Mo[W---W] and the two Mo---Cu[W-Cu] are 2.852(2)[2.844(1)], 2.802(2)[2.765(3)], 2.760(2)[2.762(3)] Å, respectively. The M 2S4(edt)2 (M = Mo, W) moiety remains almost unchanged, except that for the compound 1 the Mo=S double bond length elongates from av. 2.10 to av. 2.165 Å. The title clusters provide a new type of unsymmetric μ2-bridging sulphido ligand. The incomplete cubane-like cluster core {Mo2CuS4}3+ of compound 1 is distorted because the two Cu---μ2---S bond lengths are significantly different (2.313 Å and 2.409 Å), but the core {W2CuS4}3+ of compound 2 has approximately Cs symmetry. The IR spectra of the two title clusters and two starting materials are assigned.  相似文献   

12.
A polymeric silver(I) complex, bis(N-methylthiourea)silver(I) nitrate, {[Ag(Metu)2]NO3} n is prepared and its crystal structure is determined. The compound crystallizes in the monoclinic C2/c space group. In the structure, distorted AgS4 tetrahedra are linked through the sulfur atoms of the Metu ligand to form isolated infinite chains of the type [Ag(SR)2] n n+. The cationic chains are separated from each other by nitrate ions that do not coordinate to the metal ion. The chains are bridged via N-H...O hydrogen bonds involving the nitrate ions. The complex exhibits an Ag—Ag separation of ∼3.21 ? indicating the existence of significant argentophilic interactions. An upfield shift in the >C=S resonance of Metu in 13C NMR and downfield shift in the N-H resonance in 1H NMR are consistent with sulfur coordination to silver(I).  相似文献   

13.
The first organically templated 3d-4f mixed metal sulfates, [H2en]2{La2M(SO4)6(H2O)2} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediamine cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions).  相似文献   

14.
The ion-solvent interaction of Sr(NO3)2 and Cd(NO3)2 in 10, 20 and 30 wt.% organic solvent (dioxane, glycol, methyl alcohol)-water mixtures at different temperatures has been studied using electrolytic conductivity data. The dissociation constant of the ion-pair Sr(NO3)+ and Cd(NO3)+ has been calculated along with ΔG0t, ΔG0t(cl) and ΔG0t(ch). The ion pairs interact with the solvents and the interaction is of the order dioxane+water>methyl alcohol+water>glycol+water.  相似文献   

15.
We have synthesised (Et4N)[ReBr2(NCCH3)2(CO)2] 1 in two steps from [ReBr3(CO)3]2−. Complex 1 is water and air stable and the two Br ligands are easily exchanged for coordinating solvent molecules such as water. The reactivity of 1 with several ligands such as imidazole (imz) and 2-picolinic acid (2-pic) are easily possible with substitution exclusively occurring in trans-position to the carbonyl groups. The resulting complexes [Re(imz)2(NCCH3)2(CO)2]+ and [Re(2-pic)(NCCH3)2(CO)2] have been isolated and structurally characterised. The two acetonitrile ligands are strongly bound and are not substituted under any conditions. Complex 1 represents therefore the new moiety “trans,cis-[Re(NCCH3)2(CO)2]+” which can be considered as a further building block in organometallic chemistry.  相似文献   

16.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.  相似文献   

17.
A phase diagram for the hexane-[Y(NO3)3(TBP)3]-acetonitrile (1-2-3) liquid ternary at T = 298.15 K was studied. This ternary consists of two pairs of incompletely miscible liquids (hexane-acetonitrile and [Y(NO3)3(TBP)3]-hexane). It contains two homogeneous liquid fields and one two-phase liquid field. One phase is depleted of acetonitrile and contains variable proportions of [Y(NO3)3(TBP)3] and hexane; the other contains variable proportions of acetonitrile and [Y(NO3)3(TBP)3] and small proportions of hexane. Intermolecular interaction parameters and excess Gibbs energies g E were calculated for binaries and the liquid ternary along binodal curves proceeding from miscibility data for the [Y(NO3)3(TBP)3]-hexane and hexane-acetonitrile binaries and the liquid ternary and using equations of the NTRL model. For the liquid ternary, g E > 0.g E decreases in the following order of pairs of liquids: (1, 3), (1, 2), (2, 3). A computer algorithm is given for calculating binodal curves and tie-lines for the liquid ternary with the use of equations of the NTRL model proceeding from the intermolecular interaction parameters. Original Russian Text ? A.K. Pyartman, V.A. Keskinov, N.A. Charykov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 350–356.  相似文献   

18.
The reaction between cadmium nitrate dihydrate and benzil bis(4-methyl-3-thiosemicarbazone), LMe2H4, depends on the working conditions. In methanol the reaction gives the novel complex [Cd(LMe2H4)(NO3)2][Cd(LMe2H4)(NO3)(H2O)]NO3 · H2O (1). Its crystal structure shows the presence of two cadmium atoms with different coordination numbers, seven and eight, and the ligands acting as N2S2 neutral molecules. One cadmium has the coordination sphere completed by a bidentate nitrato group and a water molecule, whereas the other one is bonded to two bidentate nitrato groups. Both molecules are joined to one nitrate ion and to an additional water molecule by hydrogen bonds. In the presence of lithium hydroxide, the reaction leads to a binuclear complex with the ligand doubly deprotonated [Cd(LMe2H2)]2 (2). The complexes were characterized by elemental analysis, mass spectrometry, 13C and 113Cd CP/MAS NMR and, in the case of complex 1, by X-ray diffraction.  相似文献   

19.
Phase diagram of a ternary liquid system [Th(NO3)4(TBP)2]-[UO2(NO3)2(TBP)2]-Exide 100 solvent was studied at 298.15–333.15 K. Original Russian Text ? A.K. Pyartman, V.A. Keskinov, V.V. Lishchuk, Ya.A. Reshetko, V.E. Skobochkin, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 8, pp. 1243–1245.  相似文献   

20.
The heteroligand complex Nd(Phen){(iso-C4H9)2PS2}2(NO3) (I) was synthesized and its IR spectrum was analyzed. The anions (iso-C4H9)2PS2/− and N3/− act as bidentate cyclic ligands. The single crystals of [Nd(Phen){iso-C4H9)2PS2}3] (II) were obtained on evaporation of a solution of complex I in a mixture CH2Cl2-hexane and were studied by X-ray diffraction. Crystals II are triclinic: a = 10.5509(5); b = 14.7432(8), c = 16.8503(10) ?; α = 102.882(2)°, β = 97.211(2)°, γ= 108.087(2)°, V = 2374(2) ?3, Z = 2, ρ(calcd.) = 1.332 g/cm3, space group . The coordination polyhedron of the Nd atom in a separate mononuclear molecule II is a distorted dodecahedron N2S6. The molecules are bound by weak van der Waals and π-π interactions. The photoluminescence spectra of complexes I, II were measured and interpreted. Original Russian Text ? S.V. Larionov, V.L. Varand, R.F. Klevtsova, T.G. Leonova, L.A. Glinskaya, E.M. Uskov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 12, pp. 944–950.  相似文献   

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