OH stretch IR spectra of (H2O)3 and benzene-(H2O)3

The OH stretch IR spectrum of (H₂O)₃ is significantly altered upon complexation of the cluster with a benzene molecule. Theoretical calculations show that the differences in the OH stretch spectra of (H₂O)₃ and benzene-(H₂O)₃ are primarily due to mode localization induced by the benzene molecule. Received: 27 January 1997 / Accepted: 28 January 1997     

Thermal behaviour and vibrational spectra of (NH4)3Ga(C2O4)3 · 3H2O and (NH4)3Al(C2O4)3 · 3H2O

The IR and Raman spectra and the thermal behaviour of the isomorphous compounds (NH₄)₃Ga(C₂O₄)₃·3H₂O and (NH₄)₃Al(C₂O₄)₃·3H₂O were investigated. Detailed stoichiometries, sustained by TG, DTA and IR spectroscopic analyses, were found in both cases. Different results, associated with the different polarizing powers of the metal cations, were obtained. The first evidence was found of the formation of basic gallium carbonates.     

Two new open framework cobalt phosphates: NaCo3(OH)(PO4)2.1/4H2O and Na(NH4)Co2(PO4)2.H2O

Two new cobalt phosphates, NaCo₃(OH)(PO₄)₂.1/4H₂O (1) and Na(NH₄)Co₂(PO₄)₂.H₂O (2) have been synthesized hydrothermally and characterized by single crystal X-ray diffraction methods, vibrational (IR and Raman) spectroscopy, thermogravimetric analysis and magnetic measurements. The structure of 1 is a new framework type while 2 is an example of a chiral cobalt phosphate. Both phases contain channels in which the Na⁺, NH₄⁺ cations and H₂O molecules are located.     

Infrared and polarized Raman spectra of (CH3)2NH2Al(SO4)2 x 6H2O

FTIR and single crystal Raman spectra of (CH3)2NH2Al(SO4)2 x 6H2O have been recorded at 300 and 90 K and analysed. The shifting of nu1 mode to higher wavenumber and its appearance in Bg species contributing to the alpha(xz) and alpha(yz) polarizability tensor components indicate the distortion of SO4 tetrahedra. The presence of nu1 and nu2 modes in the IR spectrum and the lifting of degeneracies of nu2, nu3, and nu4 modes are attributed to the lowering of the symmetry of the SO4(2-) ion. Coincidence of the IR and Raman bands for different modes suggest that DMA+ ion is orientationally disordered. One of the H atoms of the NH2 group of the DMA+ ion forms moderate hydrogen bonds with the SO4(2-) anion. Al(H2O)6(3+) ion is also distorted in the crystal. The shifting of the stretching modes to lower wavenumbers and the bending mode to higher wavenumber suggest that H2O molecules form strong hydrogen bonds with SO4(2-) anion. The intensity enhancement and the narrowing of nu1SO4, deltaC2N and Al(H2O)6(3+) modes at 90 K confirm the settling down of the protons in the hydrogen bonds formed with H2O molecules and NH2 groups. This may be one of the reasons for the phase transition observed in the crystal.     

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 x 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 x 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3- and H2O vibrations. Additional bands obtained in the region of v3 and v1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of v3 modes, since the BrO3- ion occupies a site of lower symmetry. The appearance v1 mode of BrO3- anion at a lower wavenumber (771 cm(-1)) is attributed to the attachment of hydrogen to the BrO3- anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 x 3H2O structure is confirmed. The lifting of degeneracy of v4 mode indicates that the symmetry of BrO3- anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77-523 K for various temperatures. A small structural rearrangement takes place in BrO3- ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3- ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Synthesis and crystal structure of AlH2P3O10.2H2O; a new structure-type for layered acid phosphates

The crystal structure of the layered acid phosphate, AlH2P3O10.2H2O, has been determined and provides a new structure-type for a series of metal phosphates with interlamellar regions likely to be highly suited to intercalation behaviour.     

Structural investigations of two bismuth-ammonium condensed phosphates: BiHNH4P3O10 and BiNH4(PO3)4

Chemical preparations and crystal structures are described for two new bismuth salts: BiHNH₄P₃O₁₀ and BiNH₄(PO₃)₄. The first one is a new type of tripolyphosphate, while the second one, a long chain polyphosphate, is isostructural with RbNd(PO₃)₄ and some other M^ILn(PO₃)₄ compounds. BiHNH₄P₃O₁₀ is triclinic, P1 , with a = 7.032(8), b = 7.696(4), c = 8.659(3) Å, α = 106.20(4), β = 105.86(4), γ = 82.78(4)°, Z = 2, V = 432.3 ų, Dx = 3.694. BiNH₄(PO₃)₄ is monoclinic, P2₁/n, with a = 10.925(9), b = 9.034(8), c = 10.438(9) Å, β = 106.18(4), Z = 4, V = 989.4 ų, Dx = 3.644. The crystal structure of BiHNH₄P₃O₁₀ has been solved by using 4253 independent reflexíons with a final R value of 0.056. The unit cell contains two P₃O₁₀^5? groups related by an inversion center while bismuth atoms in a eightfold coordination build infinite chains of edge-sharing BiO₈ polyhedra running parallel to the a axis. The crystal structure of BiNH₄(PO₃)₄ has been solved using 4330 independent reflexions with a final R value of 0.047. Infinite (PO₃)_∞ chains spread along the [101] direction, alternating with isolated BiO₈ polyhedra.     

吡嗪桥连异三核配合物的合成及晶体结构

Ag(Ⅰ)配合物的几何构型多变,最常见的是配位数为2的线性构型和配位数为4的四面体构型。前者如Ag(NH_3)_2~+及Ag(CN)_2,后者如[Ag(SC(CH_3)NH_2)_4]Cl、[(Ph_3)Ag(Cl)]和[(Ph_3MeP)_3Ag(BH_4]等。配位数为4的平面四方构型却罕见,只在当有一定刚性的四氮杂环十四烷和Ag(Ⅰ)生成配合物时才是平面四方构型。 本文报道一种新型异三核含银配合物的合成及其晶体结构,其中Ag是平面四方构型。     

Synthesis, structure, and photoluminescence property of a new layered zirconium phosphate |Co(dien)(2)|[Zr(4)H(8)P(5)O(26)] x 3H(2)O

A new layered zirconium phosphate |Co(dien)(2)|[Zr(4)H(8)P(5)O(26)] x 3H(2)O (denoted ZrPO-CJ37) has been synthesized hydrothermally by using a racemic mixture of a chiral cobaltammine complex Co(dien)(2)Cl(3) as the template. Its structure is determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, inductively coupled plasma, thermogravimetric, UV-vis, and photoluminescence analyses. The inorganic layer of ZrPO-CJ37 is built up from the linkage of Zr-centered octahedra and P-centered tetrahedra via vertex oxygen atoms forming a 4.6-net sheet. Its structure features the edge-sharing chains of Zr(OM)(6) (M = P, H) octahedra. The cobaltammine complex cations are located in the interlayer region and interact with the host network through H bonds. ZrPO-CJ37 exhibits interesting photoluminescence in the UV-vis spectral region. The edge-sharing chains of Zr(OM)(6) octahedra in the inorganic layer might be responsible for this unusual photoluminescence.     

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.     

Vibrational spectra of MII3Pb(P2O7)2 (MII = Ni,Co)

Raman and IR spectra of polycrystalline Ni₃Pb(P₂O₇)₂ and Co₃Pb(P₂O₇)₂ have been recorded and analyzed. The internal modes are assigned in terms of PO₃ and POP vibrations. The results point to a bent POP bridge configuration in Co₃Pb(P₂O₇)₂ as in Ni₃Pb(P₂O₇)₂. In the cobalt compound, the P₂O⁴⁻₇ ions are distorted. Non-coincidence of the majority of the Raman and IR bands confirms a centrosymmetric structure for Ni₃Pb(P₂O₇)₂, and Co₃Pb(P₂O₇)₂. The POP bridge angle is slightly higher in the cobalt compound than in the nickel compound.     

配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n的合成及晶体结构

以均苯四甲酸(pmts)和CoCl2·6H2O为原料,在碱件水溶液中通过水热法合成了配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n,并对其进行了红外、紫外-可见吸收光谱和单品X-射线衍射结构测定.结果表明,Co2+分别与桥配体pmts的1,4位羧基氧及端配体水分子中的氧以轻度畸变的八血体...     

Chemical Preparation,Crystallographic Data,Thermal Behavior,and IR Studies of MnNa 4 (P 3 O 9 ) 2 ·4H 2 O

Chemical preparation, crystallographic data, thermal behavior, and IR studies are given for two cyclotriphosphates MnNa 4 (P 3 O 9 ) 2 ;4H 2 O and its anhydrous form MnNa 4 (P O 9 ) 2 . MnNa 4 (P 3 O 9 ) 2 ;4H 2 O, isotypic of CuK 4 (P 3 O 9 ) 2 ;4H 2 O, is monoclinic P2 1 /a with the following unit-cell dimensions: a = 8.536(2) Å, b = 14.309(3) Å, c = 8.508(2) Å, g = 96.452(2); and Z = 2. MnNa 4 (P 3 O 9 ) 2 , isotypic of CaNa 4 (P 3 O 9 ) 2 , is monoclinic C2/c with the following unit-cell dimensions: a = 13.198(2) Å, b = 8.241(1) Å, c = 14.228(2) Å, g = 95.045(1); and Z = 4. The thermal behavior has been investigated and interpreted by comparison with IR absorption spectrometry and x-ray diffraction experiments.     

Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides Part II. Al(ClO4)3·9H2O

Aluminium hydroxide was precipitated during a hydrolysis of aluminium perchlorate in ammonia medium. The materials were studied with the following methods: thermal analysis, IR spectroscopy, X-ray diffraction, low-temperature nitrogen adsorption and adsorption–desorption of benzene vapours. Freshly precipitated boehmite had a high value of S_BET=211 m² g^–1 determined from nitrogen adsorption, good sorption capacity for benzene vapours, developed mesoporous structure and hydrophobic character. After prolonged refluxing at elevated temperature its crystallinity increased which was accompanied by an increase of specific surface determined from nitrogen adsorption up to 262m²g^–1 , decrease of sorption capacity for benzene vapours and stronger hydrophobic character. The calcinations of all boehmites at temperature up to 1200°C resulted in formation of à-Al₂O₃ via transition form of γ-, δ- and θ-Al₂O₃. The samples of aluminium oxides obtained after calcination at 550 and 900°C were characterised with high values of specific surface area of 205–220 and 138–153 m² g^–1 , respectively. The SBET values calculated for the oxide samples derived from aged hydroxides and calcined at 1200°C are higher than for the analogous sample prepared without the ageing step. It was concluded that the process of ageing at elevated temperature developed thermal stability of aluminium oxides.