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1.
Classical trajectory simulations are used to study the intramolecular dynamics of isolated CF3H and the CF3H(H2O)3 cluster, by either exciting the CH stretch local mode to then=6 level or by adding an equivalent amount of energy to an OH stretch normal mode. Energy transfer from the CH local mode is statistically the same for CF3H(H2O)3 as for isolated CF3H, and agrees with previous experimental studies. Clusters excited with 6 quanta in the CH local mode are remarkably stable. Though the CF3H-(H2O)3 intermolecular potential is only 1.5 kcal/mol, only 1 of 26 clusters excited with 6 quanta in the CH local mode dissociate within 10 ps. The absorption linewidth for the CH local mode in CF3H(H2O)3 is related to IVR within CF3H and not to the unimolecular lifetime of the cluster. When an OH stretch normal mode of the cluster is excited, energy transfer to CF3H is negligible and nearly one half of the clusters dissociate within 10 ps.  相似文献   

2.
In poly[[diaquaoxido[μ3‐trioxidoselenato(2−)]vanadium(IV)] hemihydrate], {[VO(SeO3)(H2O)2]·0.5H2O}n, the octahedral V(H2O)2O4 and pyramidal SeO3 building units are linked by V—O—Se bonds to generate ladder‐like chains propagating along the [010] direction. A network of O—H...O hydrogen bonds helps to consolidate the structure. The O atom of the uncoordinated water molecule lies on a crystallographic twofold axis. The title compound has a similar structure to those of the reported phases [VO(OH)(H2O)(SeO3)]4·2H2O and VO(H2O)2(HPO4)·2H2O.  相似文献   

3.
The pathways and activation barriers of cooperative biproton migrations in the associates of the formic acid molecule with H2O and X molecules (X=CH3OH, NH2OH, H2O2, FOH, and H2O) are calculated by an ab initio method (3-21G and 6-31G** basis sets). A cooperative triproton transfer occurs in the system with X=H2O. The activation barriers of this transfer calculated in the 3-21G and 6-31G** basis sets are 6.94 and 27.29 (through the structure of C2 symmetry) or 7.99 and 26.08 kcal/mole (through the structure of Cs symmetry), respectively. In the systems with X=H3COH, HOOH, and FOH, the biproton transfer is accompanied by synchronous shifts of two hydroxyl groups and overcomes high activation barriers (>40 kcal/mole), which is accounted for by poor stereochemical similarity for the low-barrier cooperative processes in the given molecular associates. Scientific Research Institute of Physical and Organic Chemistry, Rostov State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 5, pp. 845–858, September–October, 1996. Translated by I. Izvekova  相似文献   

4.
Crystal Structures of Sr(OH)2 · H2O, Ba(OH)2 · H2O (o.-rh. and mon.), and Ba(OH)2 · 3 H2O The crystal structures of Ba(OH)2 · 3 H2O (Pnma, Z = 4), γ-Ba(OH)2 · H2O (P21/m, Z = 2) and the isotypic Sr(OH)2 · H2O and β-Ba(OH)2 · H2O (Pmc21, Z = 2) were determined using X-ray single crystal data. Ba(OH)2 · 3 H2O and Ba(OH)2 · H2O mon. crystallize in hitherto unknown structure types. The structure of Ba(OH)2 · H2O mon. is strongly related to that of rare earth hydroxides M(OH)3 with space group P63/m (super group of P21/m). The metal-oxygen distances are significantly shorter for OH? ions (mean Ba—O bond lengths of all hydroxides under investigation 278.1 pm) than for H2O molecules (289.9 pm). Corresponding to other hydrates of ionic hydroxides, the water molecules form strong hydrogen bonds to adjacent OH? ions whereas the hydroxide are not H-bonded.  相似文献   

5.
Colourless single crystals of [Hg(OH)](NO3)(H2O) were obtained by slow evaporation of an aqueous solution of Hg(NO3)2 and Bi(NO3)3. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R1(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H2O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg2+ has an effective 2+2+2(+1) coordination.  相似文献   

6.
 The external and internal surface area of the calcium aluminum double hydroxide [Ca2Al(OH)6] NO3 ⋅ 2H2O were hydrophobized by the anionic surfactants sodium dodecylsulfate and sodium dodecyl-benzene sulfonate. The adsorption behavior towards liquid mixtures (benzene/n-heptane and n-propanol/ toluene) was studied by determining the surface excess adsorption isotherms, the heats of immersion in these liquids, and the basal spacing, i.e. the expansion of the interlayer space. Both hydrophobic layered double hydroxides (LDHs) adsorbed n-hep-tane, benzene, toluene, and n-pro-panol between the layers with considerable increase of the basal spacing. Interlamellar swelling of the hydrophobizised LDHs in n-heptane was fundamentally different to the behavior of hydrophobized 2 : 1 clay minerals (smectites, vermiculites). The surface excess isotherms for benzene/ heptane mixtures were U-shaped and indicate preferential adsorption of benzene. Dodecylbenzene sulfonate double hydroxide preferentially adsorbed propanol from n-propanol/ toluene mixtures but the dodecyl-sulfate derivative adsorbed both compounds. Received: 23 January 1997 Accepted: 10 February 1997  相似文献   

7.
The ability to use calculated OH frequencies to assign experimentally observed peaks in hydrogen bonded systems hinges on the accuracy of the calculation. Here we test the ability of several commonly employed model chemistries—HF, MP2, and several density functionals paired with the 6‐31+G(d) and 6‐311++G(d,p) basis sets—to calculate the interaction energy (De) and shift in OH stretch fundamental frequency on dimerization (δ(ν)) for the H2O → H2O, CH3OH → H2O, and H2O → CH3OH dimers (where for XY, X is the hydrogen bond donor and Y the acceptor). We quantify the error in De and δ(ν) by comparison to experiment and high level calculation and, using a simple model, evaluate how error in De propagates to δ(ν). We find that B3LYP and MPWB1K perform best of the density functional methods studied, that their accuracy in calculating δ(ν) is ≈ 30–50 cm?1 and that correcting for error in De does little to heighten agreement between the calculated and experimental δ(ν). Accuracy of calculated δ(ν) is also shown to vary as a function of hydrogen bond donor: while the PBE and TPSS functionals perform best in the calculation of δ(ν) for the CH3OH → H2O dimer their performance is relatively poor in describing H2O → H2O and H2O → CH3OH. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010  相似文献   

8.
Summary.  Single crystals of sodium dithiophosphate undecahydrate (Na3PO2S2 · 11H2O) and sodium trithiophosphate undecahydrate (Na3POS3 · 11H2O) were grown from aqueous solution. The crystal structures of Na3PO2S2 · 11H2O (P212121; a = 1248.1(1), b = 945.2(1), c = 1383.1(1) pm; R 1 = 0.0202, wR 2 = 0.0502) and Na3POS3 · 11H2O (Pna21; a = 1262.0(2), b = 947.6(2), c = 1431.5(2) pm; R 1 = 0.0720, wR 2 = 0.1371) are related to each other in a sense that all constituting units are arranged in similar positions and with similar orientations. The geometries of the anions were determined with high accuracy; thus, the structural parameters of the POS3− 3 anion were measured for the first time. Received September 25, 2001. Accepted January 21, 2002  相似文献   

9.
The blue copper complex [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl2 · 2 H2O and Na2CO3 in the presence of succinic acid in CH3OH/H2O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) Å3, Z = 1. The crystal structure consists of dinuclear [Cu2(H2O)2(phen)2(OH)2]2+ complex cations, dinuclear [Cu2(phen)2(OH)2(CO3)2]2– complex anions and hydrogen bonded H2O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H2O molecule or one CO32– anion to complete distorted [CuN2O3] square‐pyramids with the H2O molecule or the CO32– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN2O3] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.  相似文献   

10.
Crystal Structure of (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2 . (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2 crystallizes from hydrobromic acid solution of Re3Br9 · 2 H2O and NMe4Br at 0 – 5°C. The crystal structure (monoclinic; P21/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; Rw = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re3Br11(H2O)]2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re3Br9(H2O)3](H2O)2}.  相似文献   

11.
The assumption that OH (OD) stretch vibrations in CsMnCl3-2H2O and -2D2O govern the rate of the 4T16A1 multiphonon transitions in Mn2+ is shown to account quantitatively for the observed 16-fold increase in the 4T1 lifetime upon replacing H2O by D2O. The argument is generalized to include other coordination compounds.  相似文献   

12.
Rb2Co3(H2O)2[B4P6O24(OH)2]: A Borophosphate with ‐Tetrahedral Anionic Partial Structure and Trimers of Octahedra (Co O12(H2O)2) Rb2Co3(H2O)2[B4P6O24(OH)2] is formed under mild hydrothermal conditions (T = 165 °C) from mixtures of RbOH(aq), CoCl2, H3BO3, and H3PO4 (molar ratio 1 : 1 : 1 : 2). The crystal structure (orthorhombic system) was solved by X‐ray single crystal methods (space group Pbca, No. 61; R‐values (all data): R1 = 0.0699, wR2 = 0.0878): a = 950.1(1) pm, b = 1227.2(2) pm, c = 2007.4(2) pm; Z = 4. The anionic partial structure consists of tetrahedral [B4P6O24(OH)28–] layers, which contain three‐ and nine‐membered rings. CoII is octahedrally coordinated by oxygen and oxygen and H2O ligands, respectively (coordination octahedra CoO6 and CoO4(H2O)2). Three adjacent coordination octahedra are condensed via common edges to form trimeric units (CoO12(H2O)2). The oxidation state +2 of cobalt was confirmed by magnetic measurements. The octahedral trimers are quasi‐isolated. No long‐range magnetic ordering occurs down to 2 K. Rb+ is disordered over three crystallographically independent sites within channels of the structure running parallel [010]; the coordination sphere of Rb+ is formed by nine oxygen species of the tetrahedral layers, one OH group and one H2O molecule.  相似文献   

13.
[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2? [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl3 and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; Vm = 573.9(4) cm3mol?1; R = 0.060; Rw = 0.038) is the connection of two anions [Re3(μ-Cl)3Br7(H2O)2]? via a water molecule to dimers, {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb+ cations and crystal water.  相似文献   

14.
The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV3(H2O)2[B2P4O16(OH)4] CsV3(H2O)2[B2P4O16(OH)4] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH(aq), VCl3, H3BO3, and H3PO4 (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP2O8(OH)2]5–, which are built up by a central BO2(OH)2 tetrahedron and two PO4 tetrahedra sharing common corners. VIII is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H2O molecules, respectively (coordination octahedra VO4(OH)2 and VO4(H2O)2). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via VIII‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO4(OH)2 and VO4(H2O)2 octahedra as well as BO2(OH)2 and PO4 tetrahedra results. The structure contains channels running along [001], which are occupied by Cs+ in a distorted octahedral coordination (CsO4(H2O)2).  相似文献   

15.
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode.  相似文献   

16.
Hydrothermal investigations in the system MgO/B2O3/P2O5(/H2O) yielded two new magnesium borophosphates, Mg2(H2O)[BP3O9(OH)4] and Mg(H2O)2[B2P2O8(OH)2]·H2O. The crystal structures were solved by means of single crystal X‐ray diffraction. While the acentric crystal structure of Mg2(H2O)[BP3O9(OH)4] (orthorhombic, P212121 (No. 19), a = 709.44(5) pm, b = 859.70(4) pm, c = 1635.1(1) pm, V = 997.3(3) × 106 pm3, Z = 4) contains 1D infinite chains of magnesium coordination octahedra interconnected by a borophosphate tetramer, Mg(H2O)2[B2P2O8(OH)2]·H2O (monoclinic, P21/c (No. 14), a = 776.04(5) pm, b = 1464.26(9) pm, c = 824.10(4) pm, β = 90.25(1)°, V = 936.44(9) × 106 pm3,Z = 4) represents the first layered borophosphate with 63 net topology. The structures are discussed and classified in terms of structural systematics.  相似文献   

17.
Crystal Structure of Sr(BrO3)2 · H2O, Ba(BrO3)2 · H2O, Ba(IO3)2 · H2O, Pb(ClO3)2 · H2O, and Pb(BrO3)2 · H2O The crystall structures of the isostructural halates Sr(BrO3)2 · H2O, Ba(BrO3)2 · H2O, Ba(IO3)2 · H2O, Pb(ClO3)2 · H2O, and Pb(BrO3)2 · H2O were determined using X-ray single crystal data (monoclinic space group C2/c? C, Z = 4), The mean bond lengths and bond angles of the halate ions in the Ba(ClO3)2 · 1 H2O-type compounds, which correspond to those of other halates, are Cl? O, 149.0, Br? O, 165.9, I? O, 180.2 pm, ClO3?, 106.4, BrO3?, 104.0, and IO3?, 99.6°. The structure data obtained are discussed in terms of possible orientational disorder of the water molecules, strengths of the hydrogen bonds, influence of the lead ions on the structure, and site group distortion of the halate ions.  相似文献   

18.
Reactions of a freshly prepared Zn(OH)2‐2x(CO3)x · yH2O precipitate, phenanthroline with azelaic and sebacic acid in CH3OH/H2O afforded [Zn(phen)(C9H15O4)2] ( 1 ) and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C9H15O4)2] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C9H15O4)2] complexes. Compound 2 is built up from crystal H2O molecules and the centrosymmetric binuclear [Zn2(phen)2(H2O)2(C10H16O4)2] complex, in which two [Zn(phen)(H2O)]2+ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H2O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)Å3, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)Å3, Z = 1.  相似文献   

19.
A new magnesium borate Mg2[B2O4(OH)2]·H2O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg2[B2O4(OH)2]·H2O in 0.9764 mol L–1 HCl was determined. With the incorporation of the enthalpies of solution of H3BO3 in HCl (aq), of MgO in (HCl+H3BO3) (aq), and the standard molar enthalpies of formation of MgO(s), H3BO3(s), and H2O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol–1 of Mg2[B2O4(OH)2]·H2O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

20.
The two complexes, [Ln(Ala)2(Im)(H2O)](ClO4)3 (Ln=Pr, Gd), were synthesized and characterized. Using a solution-reaction isoperibol calorimeter, standard enthalpies of reaction of two reactions: LnCl3⋅6H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Ln(Ala)2(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l) (Ln=Pr, Gd), at T=298.15 K, were determined to be (39.26±0.10) and (5.33±0.12) kJ mol–1 , respectively. Standard enthalpies of formation of the two complexes at T=298.15 K, ΔfHΘm {[Ln(Ala)2(Im)(H2O)](ClO4)3(s)} (Ln=Pr, Gd), were calculated as –(2424.2±3.3) and –(2443.4±3.3) kJ mol–1 , respectively.  相似文献   

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