Substitution mechanism of alkali metals for strontium in strontium hydroxyapatite

Strontium hydroxyapatites substituted by alkali metals are synthesized by double decomposition method in basic medium. Structures of Sr_9.50Na_0.30(PO₄)₆(OH)_1.30 (SrNaHAp) and Sr_9.81K_0.12(PO₄)₆(OH)_1.74 (SrKHAp) are determined by X-ray powder diffraction. Both compounds are isotypic and crystallize in hexagonal system (space group P63/m) with the following cells: a=9.751(3) Å and c=7.279(3) Å for SrNaHAp and a=9.755(4) Å and c=7.284(3) Å for SrKHAp. Results are compared to those of Sr₁₀(PO₄)₆(OH)₂. According to the site occupancy factors, in SrNaHAp sodium is localized in site (I) and in SrKHAp potassium in site (II). Both structures contain vacancies in hydroxyl and metal sites. The mechanism of alkali metals substitution for strontium proposed explains the vacancies formation.     

Reinvestigation of the binary diagram Na3PO4-FePO4 and crystal structure of a new iron phosphate Na3Fe3(PO4)4

A new iron(III) phosphate Na₃Fe₃(PO₄)₄ has been synthesized and characterized. It decomposes before melting at 860°C into FePO₄ and Na₃Fe₂(PO₄)₃. The structure of the compound was determined by single-crystal X-ray diffraction. The unit cell is monoclinic with the following parameters: a=19.601(8) Å, b=6.387(1) Å, c=10.575(6) Å and β=91.81(4)°; Z=4; space group: C2/c. Na₃Fe₃(PO₄)₄ exhibits a layered structure involving corner-linkage between FeO₆ octahedra, and corner- and edge-sharing between FeO₆ octahedra and PO₄ tetrahedra. The Na⁺ cations occupying the interlayer space are six- and seven-fold coordinated by oxygen atoms. The relationship between the structure of Na₃Fe₃(PO₄)₄ and the previous reported hydrate K₃Fe₃(PO₄)₄·H₂O will be discussed.     

Hydrothermal synthesis, structural and physico-chemical characterizations of two Nasicon phosphates: M0.50Ti2(PO4)3 (M = Mn, Co)

The family of titanium Nasicon-phosphates of generic formula M_0.5^IITi₂(PO₄)₃ has been revisited using hydrothermal techniques. Two phases have been synthesized: Mn_0.5^IITi₂(PO₄)₃ (MnTiP) and Co_0.5^IITi₂(PO₄)₃ (CoTiP). Single crystal diffraction studies show that they exhibit two different structural types. Mn_0.5^IITi₂(PO₄)₃ phosphate crystallizes in the R-3 space group, with the cell parameters a = 8.51300(10) Å and c = 21.0083(3) Å (V = 1318.52(3) Å³ and Z = 6). The Co_0.5^IITi₂(PO₄)₃ phosphate crystallizes in the R-3c space group, with a = 8.4608(9) Å and c = 21.174(2) Å (V = 1312.7(2) Å³ and Z = 6). These two compounds are clearly related to the parent Nasicon-type rhombohedral structure, which can be described using [Ti₂(PO₄)₃] framework composed of two [TiO₆] octahedral interlinked via three [PO₄] tetrahedra. ³¹P magic-angle spinning nuclear magnetic resonance (MAS-NMR) data are presented as supporting data. Curie-Weiss-type behavior is observed in the magnetic susceptibility. The phases are also characterized by IR spectroscopy and UV-visible.     

Synthesis, crystal structure and infrared study of LiEr(PO3)4

A single-crystal X-ray diffraction analysis has been performed on LiEr(PO₃)₄ prepared by the flux method. The compound crystallizes in the monoclinic system with space group C2/c and cell parameters: a = 16.262(2), b = 7.032(1), c = 9.549(2) Å and β = 125.95(1)°. The crystal structure was refined based on 1272 independent reflections with I > 2σ(I). Final values of the reliability factors were improven considerably: R(F²) = 0.0180 and wR(F²) = 0.0490. The LiEr(PO₃)₄ structure is characterized by infinite chains (PO₃)_n, extending parallel to the b direction. The ErO₈ dodecahedra and LiO₄ tetrahedra alternate on two-fold axes in the middle of four (PO₃)_n chains. The vibrational study by infrared absorption spectroscopy is reported.     

Phase transitions, structure and ion conductivity of zirconium hydrogen phosphates, H1±XZr2−XMX(PO4)3·H2O (M = Nb, Y)

Structure transformations and proton conductivity of hydrogen zirconium phosphates with the NASICON structure, H_1±XZr_2−XM_X(PO₄)₃·H₂O (X = 0, 0.02 and 0.1, M = Nb, Y), were studied by X-ray powder diffraction, calorimetry, IR- and impedance spectroscopy. Substitution of zirconium by niobium leads to decrease of the lattice parameters, while yttrium doping leads to their increase. H_0.9Zr_1.9Nb_0.1(PO₄)₃ structure was determined at 493 and 733 K. This phase crystallizes in rhombohedral space group with lattice parameters a = 8.8564(5) Å, c = 22.700(1) Å at 493 K and a = 8.8470(2) Å, c = 22.7141(9) Å at 733 K. The a parameter and lattice volume were found to decrease with temperature increasing. Structure transformations upon heating are caused mainly by the decrease of the M1 site and C cavities. Ion conductivity of obtained materials was found to increase in humid atmosphere. Activation energies of conductivity were calculated. Rhombohedral-triclinic phase transition found by X-ray powder diffraction was proved by calorimetry data. According to XRD and IR spectroscopy data hydrogen bond in HZr₂(PO₄)₃ was found to be weaker than in hydrated material.     

Crystal structure and EPR study of Mn-doped β-tricalcium phosphate

Mn-doped β-tricalcium phosphate was prepared by solid state reaction at 1100 °C. The crystal structure of Ca_2.85Mn_0.15(PO₄)₂, was determined by single crystal X-ray diffraction and found to be rhombohedral, R3c. Unit cell parameters are: a = 10.3419(3); c = 37.025(3) Å (hexagonal setting), Z = 21. Structure refinement data show that from the five Ca positions the Ca(4) site is only half filled and that the Mn²⁺ ions occupy the hexacoordinated Ca(5) site solely. EPR spectroscopy reveals that manganese in solid solutions Ca_3−xMn_x(PO₄)₂ (x = 0.1; 0.28; 0.6) is divalent and supports the structure refinement results that Mn occupies the Ca(5) site with a geometry very near to a regular octahedron.     

Synthesis and characterization of a new monophosphate (5-Cl-2,4-(OCH3)2C6H2NH3)H2PO4

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation 5-chloro(2,4-dimethoxy)anilinium monophosphate H₂PO₄ are given. This new compound crystallizes in the monoclinic system, with the space group P2₁/c and the following parameters: a = 5.524(2) Å, b = 9.303(2) Å, c = 23.388(2) Å, β = 90.66(4), V = 1201.8(2) Å³, Z = 4 and D_x = 1.573 g cm⁻³. Crystal structure has been determined and refined to R = 0.031 and R_w = 0.080 using 1702 independent reflections. Structure can be described as an infinite (H₂PO₄)_nⁿ⁻ corrugated chains in the a-direction. The organic groups (5-Cl-2,4-(OCH₃)₂C₆H₂NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. This compound is also investigated by IR, thermal, and solid-state, ¹³C, ³¹P MAS NMR spectroscopies.     

Synthesis and characterization of a layered chlorozincophosphate Zn(HPO4)Cl·[C4H10NO]

A chlorozincophosphate of the composition Zn(HPO₄)Cl·[C₄H₁₀NO] has been synthesised under mild condition water medium in the presence of morpholine as organic template. Its unit cell is monoclinic P2₁/a with parameters a = 8.655(6) Å, b = 9.302(5) Å, c = 12.180(5) Å, β = 101.10(4)°, Z = 4 and V = 962.1(9) Å³. The structure was determinated by single crystal X-ray diffraction. The structure involves a network of ZnO₃Cl and PO₃(OH) tetrahedra forming macroanionic inorganic layers with four- and eight-membered rings. Charge balance is achieved by the protonated amine which is trapped in the interlayers space and interacts with the organic framework through hydrogen bonding. Solid state ³¹P and ¹³C MAS-NMR spectroscopies are in agreement with the X-ray structure.     

Synthesis and crystal sructure of a new dihydrogenomonophosphate (4-C2H5C6H4NH3)H2PO4

Chemical preparation, crystal structure, calorimetric, and spectroscopic investigations are given for a new organic-cation dihydrogenomonophosphate, (4-C₂H₅C₆H₄NH₃)H₂PO₄ in the solid state. This compound crystallizes in the orthorhombic space group Pbca with the following unit cell parameters: a=8.286(3) Å, b=9.660(2) Å, c=24.876(4) Å, Z=8, V=1991.2(7) Å³, and D_X=1.442 g cm⁻³. Crystal structure was solved with a final R=0.054 for 3305 independent reflections. The atomic arrangement coaled described as H₂PO₄⁻ layers between which are located the 4-ethylanilinium cations.     

Reaction of π-Ti2O(PO4)2·2H2O with molten alkali nitrates: Synthesis of the fibrous materials π-M0.5H0.5TiOPO4 (M = Na, K)

Powder X-ray diffraction data for π-Ti₂O(PO₄)₂·2H₂O (π-TiP) is indexed in a monoclinic cell [a=5.067(4), b=10.898(3), c=14.533(8) Å, β=96.0(1)°]. Structural correlations with other titanium phosphates are discussed. The reaction of π-TiP with molten MNO₃ (M=Na, K) originates new metal phases with a KTP-type formula, π-M_0.5H_0.5TiOPO₄. These compounds maintain the fibrous morphology of their precursor. The reactions are monitored by thermogravimetric analysis. Thermal decomposition of the novel compounds is described.     

Synthesis and crystal structure of a novel lithium bismuth phosphate, Li2Bi14.67(PO4)6O14

A lithium bismuth phosphate, Li₂Bi_14.67(PO₄)₆O₁₄, has been synthesized for the first time by the solid-state method. The crystal structure was determined by single crystal X-ray diffraction at 150 K. Li₂Bi_14.67(PO₄)₆O₁₄ crystallizes in the monoclinic system C2/c (No. 15), with a = 30.8189(4) Å, b = 5.2691(3) Å, c = 24.5302(3) Å, β = 122.84(2)°, V = 3346.81(1) Å³ and Z = 2. The structure along the b axis consists of layers of [Bi₂O₂] units as the basic building block. These are separated by isolated PO₄ and LiO₄ tetrahedra. The oxygen co-ordination around two of the phosphorus atoms is disordered. Solid-state ⁷Li NMR studies confirm the presence of lithium in the structure. The material shows ionic conductivity of the order of 10⁻⁵ S cm⁻¹ at 600 °C.     

Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb7Fe7(PO4)8O2·2H2O

A new iron oxophosphate of composition Rb₇Fe₇(PO₄)₈O₂·2H₂O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2₁/c space group and the unit cell parameters a = 8.224(8) Å, b = 22.162(6) Å, c = 9.962(6) Å and β = 109.41(8)°. Its structure is built up from Fe₇O₃₂ clusters of edge- and corner-sharing FeO₅ and FeO₆ polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb⁺ cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |θ/T_N| ≈ 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Mössbauer spectroscopy results confirmed the presence of only Fe³⁺ ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.     

Study of the solid-liquid equilibria in the LiPO3-Y(PO3)3 binary system

The LiPO₃-Y(PO₃)₃ system has been studied for the first time. Microdifferential thermal analysis (μ-DTA), infrared spectroscopy (IR) and X-ray diffraction were used to investigate the liquidus and solidus relations. The only new compound observed within this system is LiY(PO₃)₄, melting incongruently at 1104 K. An eutectic appears at 4±1 mol% Y(PO₃)₃ at 933 K. LiY(PO₃)₄ crystallizes in the monoclinic system C_2/c with a unit cell: a=16.201(4) Å, b=7.013(2) Å, c=9.573(2) Å, β=125.589(9)°, Z=4 and V=884.5 Å³, which is isostructural to LiNd(PO₃)₄. The infrared absorption spectrum indicates that this salt is a chain polyphosphate.     

Synthesis, crystal structure and magnetic properties of a new lithium cobalt metaphosphate, LiCo(PO3)3

A new lithium cobalt metaphosphate, LiCo(PO₃)₃, is reported for the first time, which was discovered during the exploratory synthesis in Li-Co-P-O system by solid state reaction. The structure has been refined by powder X-ray Rietveld refinement method (P2₁2₁2₁, a = 8.5398(2) Å, b = 8.6326(2) Å and c = 8.3520(2) Å, Z = 4, R_p = 13.6%, R_wp = 19.4%, R_exp = 17.7%, S = 1.11, χ² = 1.23). It is isostructural with LiM(PO₃)₃ (M = Fe, Cu). It contains (PO₃)¹⁻ chains with the Co atoms localized in the octahedral sites, bridging four neighboring chains. The magnetic susceptibility measurement showed a typical paramagnetic behavior of high spin of Co²⁺, following the Curie-Weiss law in the temperature range of 5-300 K. Unlike the olivine type lithium cobalt phosphate, LiCoPO₄, cyclic voltammetry of LiCo(PO₃)₃ assembled in the coin-type cell showed no electrochemical activity in the voltage region of 1-5 V versus Li/Li⁺.     

Transformation of Dion-Jacobson phase to Aurivillius phase: synthesis of (PbBiO2)MNb2O7 (M = La, Bi)

We describe transformations of the Dion-Jacobson (D-J) phases, KLaNb₂O₇ and RbBiNb₂O₇, to the Aurivillius (A) phases, (PbBiO₂)LaNb₂O₇ (1) and (PbBiO₂)BiNb₂O₇ (2), in a metathesis reaction with PbBiO₂Cl. Oxide 1 adopts centrosymmetric tetragonal structure (a = 3.905(1) Å, c = 25.66(1) Å), whereas oxide 2 crystallizes in a noncentrosymmetric orthorhombic (A2₁am) (a = 5.489(1) Å, b = 5.496(2) Å, c = 25.53(1) Å) structure. Oxide 2 shows a distinct SHG response towards 1064 nm laser radiation. The role of La³⁺ versus Bi³⁺ in the perovskite slabs for the occurrence of noncentrosymmetric structure/ferroic property in these materials is pointed out.     

Synthesis of layered sodium lanthanum selenide through ion exchange reactions

Layered hexagonal KLaSe2 (α-NaFeO₂-type) was synthesized using the reactive flux method and analyzed by powder XRD to determine its lattice constants (space group R-3m, a = 4.40508(5) Å, c = 22.7838(5) Å). NaLaSe₂, which normally crystallizes as a disordered rock salt structure with mixed Na+/La + 3 sites, was synthesized through a solid state ion exchange reaction at 585 °C from a 1:3 molar ratio mixture of KLaSe₂:NaI. The product of this reaction was hexagonally layered NaLaSe₂ (space group R-3m, a = 4.3497(3) Å, c = 20.808(2) Å) isostructural to KLaSe₂. This product was analyzed by comparison with members of the set of solid solutions Na_(1−x)K_(x)LaSe₂ to confirm that the extent ion exchange in this reaction was complete. Cubic (disordered) NaLaSe₂ was also reacted with KI to yield the poorly crystalline hexagonally layered product with the approximate formula Na_0.79K_0.21LaSe₂.     

Crystal structure of rhombohedral MCd(NO2)3 [M = K, Rb, Cs, Tl] from X-ray powder diffraction data

Crystal structure of double nitrites MCd(NO₂)₃ [M=K, Rb, Cs, Tl] at room temperature was ab initio determined from X-ray powder diffraction data. The compounds are isostructural and can be described as rhombohedrally distorted perovskites: space group R3 (no. 146); Z=1; M=K: a=7.5887(1), c=9.1285(2) Å; M=Rb: a=7.6290(1), c=9.2355(2) Å; M=Cs: a=7.7305(1), c=9.4170(3) Å; M=Tl: a=7.6219(1), c=9.2300(2) Å. The coordination polyhedra of cadmium and M cations are the distorted tricapped trigonal prism [(3O+3N)+3O] and cuboctahedron, respectively.     

[NH3(CH2)2NH3][Co(SO4)2(H2O)4]: Chemical preparation, crystal structure, thermal decomposition and magnetic properties

Cobalt ethylenediammonium bis(sulfate) tetrahydrate, [NH₃(CH₂)₂NH₃][Co(SO₄)₂(H₂O)₄], has been synthesised by slow evaporation at room temperature. It crystallises in the triclinic system, space group , with the unit cell parameters: a = 6.8033(2), b = 7.0705(2), c = 7.2192(3) Å, α = 74.909(2)°, β = 72.291(2)°, γ = 79.167(2)°, Z = 1 and V = 317.16(2) Å³. The Co(II) atom is octahedrally coordinated by four water molecules and two sulfate tetrahedra leading to trimeric units [Co(SO₄)₂(H₂O)₄]. These units are linked to each other and to the ethylenediammonium cations through OW-H…O and N-H…O hydrogen bonds, respectively. The zero-dimensional structure is described as an alternation between cationic and anionic layers along the crystallographic b-axis. The dehydration of the precursor proceeds through three stages leading to crystalline intermediary hydrate phases and an anhydrous compound. The magnetic measurements show that the title compound is predominantly paramagnetic with weak antiferromagnetic interactions.     

Crystal structure and spectroscopic investigations of an organic monophosphate

Single crystals of (p-ClC₆H₄NH₃)H₂PO₄ are synthesized in water by interaction of H₃PO₄ and (p-ClC₆H₄NH₂). This compound crystallizes in the orthorhombic system with the Pbca space group. Its unit-cell parameters are a = 9.724(3), b = 7.861(1), c = 25.078(6) Å, V = 1917.1(6) Å³ and Z = 8. The crystal structure has been solved and refined to R = 0.039, using 4298 independent reflections. The atomic arrangement can be described by inorganic layers parallel to ab plane, between which the organic cations are located. This compound exhibits a reversible phase transition at 403 K. The electrical conductivity measurements show that the (p-ClC₆H₄NH₃)H₂PO₄ has a conductivity value which goes from σ = 0.88 × 10⁻⁶ Ω⁻¹ cm⁻¹ at room temperature (293 K) to 3.31 × 10⁻⁴ Ω⁻¹ cm⁻¹ at 433 K. Its characterisation by TA, NMR and IR is reported too.     

Synthesis, structure refinement at 296 K and physico-chemical characterizations of KMnHP3O10

Potassium manganese(III) monohydrogentriphosphate KMnHP₃O₁₀ was synthesized by flux method and characterized by single-crystal X-ray diffraction, crystallizes in the monoclinic system with centric space group C2/c. The parameters of the unit cell are a = 12.104(1), b = 8.287(1). c = 9.150(1) Å, β = 110.97(1)° and Z = 4. The structure was solved at 296 K using 893 independent reflections and refined until R(F) = 0.022; wR(F²) = 0.045. The atomic arrangement of the title compound consists of MnO₆ octahedra linked by hydrogentriphosphate anions to form a three-dimensional framework containing tunnels parallel to the c-axis where the K⁺ cations are inserted. The structure of KMnHP₃O₁₀ contains a single Mn site which is surrounded by typical Jahn-Teller [2 + 2 + 2] distorted octahedron. The title material has been also characterized by different physico-chemical techniques: powder X-ray diffraction, IR, NMR and CI spectroscopies and DTA-TGA-DSC thermal analysis.