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1.
Single crystals of a new phosphate AgCr2(PO4)(P2O7) have been prepared by the flux method and its structural and the infrared spectrum have been investigated. This compound crystallizes in the monoclinic system with the space group C2/c and the parameters are, a = 11.493 (3) Å, b = 8.486 (3) Å, c = 8.791 (2) Å, β = 114.56 (2)°, V = 779.8 (3) Å3and Z = 4. Its structure consists of CrO6 octahedra sharing corners with P2O7 units to form undulating chains extending infinitely along the [110] direction. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the Ag+ ions are located. The infrared spectrum of this compound was interpreted on the basis of P2O74? and PO43? vibrations. The appearance of νsP–O–P in the spectrum suggests a bent P–O–P bridge for the P2O74? ions in the compound, which is in agreement with the X-ray data. The electrical measurements allow us to obtain the activation energy of (1.36 eV) and the conductivity measurements suggest that the charge carriers through the structure are the silver captions.  相似文献   

2.
A new zero-dimensional (0D) aluminophosphate monomer [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4 (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en)3Cl3 as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO4)2(H1.5PO4)2(H2PO4)2]6? monomer. Notably, there exists intramolecular symmetrical O?H?O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by 31P NMR and 1H NMR spectra. The crystal data are as follows: AlPO-CJ38, [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4, M = 1476.33, monoclinic, C2/c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å3, Z = 4, R1 = 0.0509 (I > 2σ(I)) and wR2 = 0.1074 (all data). CCDC number 689491.  相似文献   

3.
《Solid State Sciences》2007,9(8):672-677
A cerium(IV) phosphate has been prepared using precipitation methods and its structure has been solved by single crystal X-ray diffraction (R1 = 0.0292 for 3092 reflections with I>2σ(I) and wR2 = 0.0540). Ce(H2O)(PO4)3/2(H3O)1/2(H2O)1/2 crystallises in the monoclinic space group C2/c (a = 15.7058(17) Å, b = 9.6261(9) Å, c = 10.1632(4) Å, ß = 121.623(7)°, and V = 1308.4 (2) Å3). Its structure is based on a negatively charged 3D framework, made of cerium atoms connected by PO4 tetrahedra. There are two types of PO4 units; one shares only corners with the cerium coordination polyhedra while the other one shares edges and corners. This structure also includes hydronium cations, to balance the framework charge, and water molecules. One special feature of this 3D framework is the formation of interconnected tunnels which extend along the c axis and contain the hydronium cations and the water molecules. This open framework and the presence of cationic species in the tunnels are in perfect agreement with the previously reported ion exchange properties.  相似文献   

4.
Compound Cu2(H2O)2{O3PCH2N(C2H4)2NCH2PO3} (1) has a pillared layered structure in which the organic groups of N,N′-piperazinebis(methylenephosphonate) are sandwiched between the inorganic layers. Compared with other copper phosphonates with layered or pillared layered structures, the inorganic layer in 1 is unique in that each {CPO3} tetrahedron is corner-shared with three {CuO4N} square pyramids through three oxygen donors. Ferromagnetic interactions are mediated between the metal centers. Crystal data: Pbca, a=10.0830(16) Å, b=9.4517(15) Å, c=13.218(2) Å, V=1259.7(3) Å3, Z=4.  相似文献   

5.
We have extended our research interest on titanium oxyphosphates (MII(TiO)2(PO4)2, with MII = Mg, Fe, Co, Ni, Cu, Zn) to vanadium oxyphosphates MII(VIVO)2(PO4)2 (MII = Co, Ni). For each compound two phases, named α and β according to synthesis conditions, have been stabilized at room temperature, then characterized. The four crystal structures M(VO)2(PO4)2 (α and β for M = Co, Ni) have been determined in monoclinic P21/c space group using X-ray single crystals diffraction data. Structure of the α phase is derived from the Li(TiO)(PO4) (orthorhombic Pnma) and LiNi0.50(TiO)2(PO4)2 (monoclinic P21/c) types, with cell parameters: a = 6.310(1) Å, b = 7.273(1) Å, c = 7.432(1) Å, β = 90.43(1)° for M = Co, and a = 6.297(2) Å, b = 7.230(2) Å, c = 7.421(2) Å, β = 90.36(2)° for M = Ni. Structure of the β phase is derived from the Ni(TiO)2(PO4)2-type (monoclinic P21/c) with cell parameters: a = 7.2742(2) Å, b = 7.2802(2) Å, c = 7.4550(2) Å, β = 120.171(2)° for M = Co, and a = 7.2691(2) Å, b = 7.2366(2) Å, c = 7.4453(2) Å, β = 120.231(2)° for M = Ni. All these structures consist of a three dimensional (3D) framework built up of infinite chains of tilted corner-sharing [VO6] octahedra, cross-linked by corner-sharing [PO4] tetrahedra. The M2+ ion (M = Co, Ni) is located in a triangular based antiprism which shares faces with two [VO6] octahedra. Structural filiation is discussed based on a common structural unit, a sheet where divalent cations M2+ (M = Co, Ni) are inserted. A thermal study of the α ? β transition is also presented.  相似文献   

6.
A new hybrid organic–inorganic material with the structural formula unit [La(H2O)4(m-PO3C6H4COOH)(m-PO2(OH)C6H4COOH)(m-PO(OH)2C6H4COOH)]2 (or [La(H2O)4C21H18O15P3]2) has been synthesized under hydrothermal condition from La(NO3)3·6H2O and 3-phosphonobenzoic acid (m-PO(OH)2–C6H4–COOH) which is a rigid organic precursor possessing two types of functional groups: phosphonic acid and carboxylic acid. The two units of the produced hybrid are linked together by hydrogen bonds leading to a layered framework composing of by a repetition of inorganic and organic slices. The organic layers consist of dimeric units made of two meta-phosphono-benzoic acid linked together by hydrogen bonds involving their COOH groups. Two kinds of dimeric units are observed: PO3C6H4COOH?HOOCC6H4PO(OH)2, present 2 times in the structure, and PO2(OH)C6H4COOH?HOOCC6H4PO2(OH). The material crystallises in a monoclinic cell (C2/c (15) space group) with the following parameters: a = 42.515(4) Å, b = 7.4378(6) Å, c = 20.307(2) Å, β = 118.031(6)°, V = 5668.2(9) Å3, Z = 4, density = 1.908 g/cm3.  相似文献   

7.
A new molybdenum complex (C4H12N2)2[(MoV2O4)(MoVIO4)(C2O4)2]·2H2O, was solvothermally synthesized and characterized by single-crystal X-ray diffraction. The structure of the compound consists of oxalate acid-coordinated mixed-valent [MoV2O4][MoVIO4] helical chains and protonated piperazine cations. The helical chains are built up from the [MoV2O4] units and [MoVIO4] tetrahedral. The central axis about helical chain is a 2-fold screw axis. The compound crystallizes in the space group P21/n of monoclinic system with a = 11.396(2) Å, b = 14.107(3) Å, c = 15.805(3) Å, β = 102.09(3)°, V = 2484.6(9) Å3, Z = 4. Other characterizations by elemental analysis, IR, and thermal analysis for this compound are also given.  相似文献   

8.
A novel zinc diphosphonate, Zn[HO3PCH2(C6H4)CH2PO3H] (1) was synthesized from tetraethyl para-xylylenediphosphonate, Et2O3PCH2C6H4CH2PO3Et2, and Zn (AcO)2·2H2O under solvothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction, which reveals that the structure crystallizes in the monoclinic space group C2/c (No. 15), with a = 22.4844(19) Å, b = 6.4361(5) Å, c = 8.1194(7) Å, β = 102.595(2)°, V = 1146.70(16) Å3, T = 298(2) K, Z = 8. The novel three-dimensional (3D) construction is simply built up from linear inorganic chains of corner-sharing four-rings of tetrahedral [ZnO4] and [PO3C] which connected adjacent chains by the organophosphorus ligand para-xylylenediphosphonate. The framework has 10 Å × 4 Å (containing the van der Waals radii of atoms) channels running along the b-axis.  相似文献   

9.
A new indium hydroxyphosphate containing silver, AgIn[PO3(OH)]2, has been synthesized using hydrothermal method. It crystallizes in the P21/c space group with the cell parameters a = 6.6400(2) Å, b = 14.6269(6) Å, c = 6.6616(4) Å, β = 95.681(5)°, V = 643.82(6) Å3, Z = 4. Its three-dimensional framework, built up of corner-sharing PO3(OH) tetrahedra and InO6 octahedra, presents intersecting tunnels running along <111> and [100] directions, in which the Ag+ cations are located. The presence of hydroxyl groups has been confirmed from IR spectroscopy studies and hydrogen atoms were located from the single crystal X-ray diffraction study. The structural relationships with the other compounds of general formula AIMIII[PO3(OH)]2 are analyzed.  相似文献   

10.
《Solid State Sciences》2007,9(10):955-960
The spin exchange interactions of PbCu2(PO4)2 were examined by performing the spin dimer analysis based on the extended Hückel tight-binding method, and were compared with those of SrCu2(PO4)2. The two strongest Cu–O⋯O–Cu super–superexchange interactions, J1 (with Cu⋯Cu = 5.868 Å) and J2 (with Cu⋯Cu = 5.184 Å), are strong and lead to a linear-four-spin-cluster model for both PbCu2(PO4)2 and SrCu2(PO4)2. Adjacent linear-four-spin-clusters interact substantially in SrCu2(PO4)2, but weakly in PbCu2(PO4)2. The difference in the magnetization behaviors of the two compounds was examined by calculating the magnetic excitation energies of the linear-four-spin-cluster model.  相似文献   

11.
A new layered compound, K4Mn3(HPO4)4(H2PO4)2 (1), has been synthesized under hydrothermal conditions. It crystallizes in the monoclinic space group P21/n with a = 8.874(2) Å, b = 6.554(1) Å, c = 18.075(4) Å, and β = 93.39(3)°. The structure consists of zigzag [Mn3O14]n chains of edge-sharing MnO6 octahedrons and MnO7 pentagonal bi-pyramids, which form layers of formula [Mn3(HPO4)4(H2PO4)2]4? in the ab plane via H2PO4 and HPO4 units with vertex-sharing. Potassium ions lie between these layers. Magnetic measurements indicate Curie–Weiss behavior above 6 K for 1. A Heisenberg model, with alternating exchange interactions J1J1J2… within the chain and exchange interactions J3J3… between the chains, is proposed to describe the magnetic behavior.  相似文献   

12.
An inorganic compound formulated as K5NH4[TeMo6O24].Te(OH)6.6H2O (1) has been isolated by conventional solution method and structurally characterized by single-crystal X-ray diffraction methods, scanning electron microscopy (SEM), IR, UV–vis spectra, and cyclic voltammetry measurements. This compound crystallizes in the monoclinic system, space group C2/c with unit a = 18.6841(1) Å, b = 10.0513(1) Å, c = 21.1065(1) Å, β = 116.495(1)°, V = 3547.49(4) Å3, Z = 4, R = 0.033 and wR (F2) = 0.087 for 3432 unique observed reflexions [I > 2σ(I)]. The crystal structure of (1) is built up from an Anderson clusters connected through hydrogen-bonding interactions into a three-dimensional supramolecular network.  相似文献   

13.
A new piperazinium dihydrogen orthophosphate, C4H12N2(H2PO4)2 was discovered and characterized by combining information from X-ray diffraction, 31P CP/MAS NMR and thermal analysis (TG/DTA). The compound C4H12N2(HPO4)·H2O, was also studied in order to compare these two similar materials. The hydrothermal stability is investigated for the system: 1.0 C4H10N2: n H3PO4: 55–60 H2O, 0.5 < n < 3. The reaction mixtures with pH in the range 1.6–8.4 were placed at a fixed temperature in the range 20–180 °C for ca. 5 days. C4H12N2(H2PO4)2 was obtained when n > ca. 2. A crystal of piperazinium dihydrogen phosphate, C4H12N2(H2PO4)2 was structurally investigated using X-ray diffraction: triclinic, space group P1¯, a = 7.023(2), b = 7.750(3), c = 12.203(4) Å, α = 84.668(7), β = 81.532(7) and γ = 63.174(6)°, V = 586.0(4) Å3 and Z = 2. The reactivity of C4H12N2(H2PO4)2 was investigated by systematic solvothermal syntheses.  相似文献   

14.
Crystal structure of a new natural strontium, iron and aluminium hydroxyphosphate (lulzacite): Sr2Fe(Fe0.63Mg0.37)2Al4(PO4)4(OH)10. The crystal structure of a new natural strontium, iron and aluminium hydroxyphosphate (lulzacite) has been solved through an X-ray study of a single crystal:– symmetry: triclinic (P1̄);– unit cell parameters: a=5.457(1) Å, b=9.131(2) Å, c=9.769(2) Å, α=108.47(3)°, β=91.72(3)° and γ=97.44(3);– structural formula: (Sr0.96Ba0.04)2Fe(Fe0.63Mg0.37)2Al4[(P0.98V0.02)O4]4(OH)10 (Z=1).The structure presents along the b axis the alternation, on one hand of infinite chains of edge sharing octahedra (one Fe2+O6 and an AlO6 pair), and, on the other hand, of trimers with a central AlO6 octahedron framed by two mixed (Fe2+,Mg)O6 octahedra. Trimers and chains are linked by the corners of one AlO6 octahedron and two PO4 tetrahedra. Strontium ions are located in the channels of the structure. This structure is isotypic with that of jamesite, a lead arsenate. Similar octahedral building blocks are present in other mineral species: trimers in ludlamite (iron phosphate), chains in various hydroxysalts. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASlulzacite / hydroxyphosphate / phosphate / strontium / iron / aluminium  相似文献   

15.
《Solid State Sciences》2001,3(6):677-687
Partial substitution of P by As, leading to the solid solution CsH2(PO4)1−x(AsO4)x, with x=0.28 (abbreviated as CDAP) has been shown. The structural characteristics of the crystals were analyzed by means of X-ray diffraction, which revealed that the new title compound is nearly isomorphous with the monoclinic phase of CsH2PO4 (CDP). The structure was solved from 796 independent reflections with R1=0.0292 and Rw2=0.0702, refined with 59 parameters. The following results have been obtained: space group P21, a=4.9250(4) Å, b=6.4370(3) Å, c=7.9280(6) Å, β=107.316(3)°, V=239.94(3) Å3, Z=2 and ρcal=3.349 g cm−3. The hydrogen bonds are clearly distinguished in the electron density maps which display distributions corresponding to order of protons. The shorter bond (2.452(4) Å), links the phosphate–arsenate groups into chains running along the b-axis and the longer bond (2.531(3) Å), crosslinks the chains to form (001) layers. The Raman and infrared spectra of CDAP recorded at room temperature in the frequency ranges 15–1200 cm−1 and 400–4000 cm−1, respectively, confirm the presence of PO3−4 and AsO3−4 groups in the crystal. Differential scanning calorimetry traces show three phase transitions at 333, 449 and 490 K in this material, which are characterized by X-ray powder diffraction at high temperature.  相似文献   

16.
《Solid State Sciences》2007,9(11):1012-1019
Two novel inorganic–organic hybrid compounds composed of Keggin tungstocobaltate framework and cobalt(II)–N coordination complexes, K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O (1) (phen = 1,10-phenanthroline) and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)][HCoW12O40]·0.5H2O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials, which were characterized by elemental analyses, IR, TG analyses and X-ray single crystal diffraction. Crystal data for compound 1: C48H41Co3KN8O44W12, triclinic, space group P-1, a = 10.918(5) Å, b = 13.401(5) Å, c = 13.693(5) Å, α = 69.291(5)°, β = 71.568(5)°, γ = 78.421(5)°, V = 1768.9(12) Å3, Z = 1; for compound 2: C130H104Co7N26O83W24, orthorhombic, space group, C2/c, a = 46.839(9) Å, b = 14.347(3) Å, c = 26.147(5) Å, α = β = γ = 90°, V = 17,570(6) Å3, Z = 4. Compound 1 exhibits a pseudo-1D chainlike structure, in which potassium ions act as linkages of Keggin unit doubly grafted by [Co(phen)2(H2O)] complex. Compound 2 represents a [Co(2,2′-bipy)2(H2O)]2+ mono-grafted Keggin tungstocobaltate derivative with 1.5[Co(2,2′-bipy)3]2+ countercations. The cyclic voltammetric behavior of 1-CPE is similar to the parent 3-CPE, but the cyclic voltammetric behavior of CoII shows a little difference. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.  相似文献   

17.
《Solid State Sciences》2007,9(7):644-652
Na2Cu(PO2NH)4·7H2O and KxNa2−xCu(PO2NH)4·7H2O (x  0.5) were synthesized by gel crystallization in sodium silicate gels. The crystal structures were solved by single-crystal X-ray methods and found to be isotypic (Pnma, Z = 4; Na2Cu(PO2NH)4·7H2O: a = 627.5(2) pm, b = 1456.0(3) pm, c = 1900.5(4) pm, R1 = 0.0352; K0.47Na1.53Cu(PO2NH)4·7H2O: a = 632.2(2) pm, b = 1460.0(3) pm, c = 1936.4(4) pm, R1 = 0.0345). The P4N4 rings of the tetrametaphosphimate anion exhibit a distorted chair-2 conformation with admixtures of saddle and crown conformation. The M+ ions are six- and sevenfold coordinated by oxygen atoms, the Cu2+ ions are fivefold coordinated, respectively. The MO7 and the CuO5 units form pairs of face-sharing polyhedra, which are connected by common corners forming chains and are further interconnected by tetrametaphosphimate anions, forming a three-dimensional network structure with channels along [100] and [010]. The MO6 units form chains of face-sharing polyhedra, which are situated in the channels along [100]. Extended hydrogen bonding reinforces the three-dimensional framework structure of the compounds. 23Na-MAS NMR experiments were conducted to verify the K/Na distribution on the M sites derived from the X-ray crystal structure refinement.  相似文献   

18.
《Solid State Sciences》2007,9(2):149-154
The mild-condition syntheses, single-crystal structures and properties of H3N(CH2)5NH3·Zn3(HPO3)4 and β-H3N(CH2)6NH3·Zn3(HPO3)4 are reported. Both are constructed from (3,4)-nets of ZnO4 tetrahedra and HPO3 pyramids, sharing vertices to result in three-dimensional anionic open-frameworks. In both materials, the organic species interacts with the framework by way of N–H⋯O bonds. Crystal data: H3N(CH2)5NH3·Zn3(HPO3)4, Mr = 620.22, orthorhombic, Pccn (No. 56), a = 9.5364 (9) Å, b = 21.8015 (19) Å, c = 9.1118 (7) Å, V = 1894.4 (3) Å3, Z = 4, R(F) = 0.044, wR(F2) = 0.111. β-H3N(CH2)6NH3·Zn3(HPO3)4, Mr = 634.25, monoclinic, P21/n (No. 14), a = 8.7627 (1) Å, b = 13.8117 (2) Å, c = 16.6187 (3) Å, β = 92.680 (1)°, V = 2009.12 (5) Å3, Z = 4, R(F) = 0.072, wR(F2) = 0.187.  相似文献   

19.
《Solid State Sciences》2007,9(5):385-393
Beige crystals of a new magnesium hydrogen orthophosphate salt, Mg3.5H2(PO4)3, as well as nanoparticles of an amorphous, non-Mg-containing phosphate material, Fe1−yKyPO4 (0 < y < 1), have been produced by hydrothermal reactions in supercritical water (SCW) of equivalent quantities of aqueous MgCl2·6H2O (2 M), and K4P2O7 (1 M) in concentrated HCl in a stainless-steel batch reactor at 400–450 °C and 25–32 MPa. The new salt has been characterized by single-crystal X-ray diffraction and IR and Raman spectroscopies. It crystallizes in the triclinic space group , Z = 2 with the following unit-cell parameters: a = 6.438(1), b = 7.856(1), c = 9.438(1) Å; α = 104.57(1), β = 108.61(1), γ = 101.28(1)°, V = 739.99 Å3. The effects of the SCW conditions on the nature of the products and their yields and morphologies have been studied by IR and Raman spectroscopies, X-ray powder diffraction, X-ray energy dispersive analysis, scanning electron microscopy, transmission electron microscopy and inductively coupled plasma analysis.  相似文献   

20.
Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO4, and cerium(IV) oxidophosphate, Ce2O(PO4)2, which were shown to complement the classes of isostructural compounds M(OH)PO4 and R2O(PO4)2, where M=Th, U and R=Th, U, Np, Zr. Ce2O(PO4)2 oxidophosphate is formed by elimination of H2O from the crystal structure of Ce(OH)PO4 during its thermal decomposition. The structures of Ce(OH)PO4 and Ce2O(PO4)2 are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) Å3, Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) Å3, Z=4, respectively).  相似文献   

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