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Abstract: The crystallization of complex phosphates from the melts of Cs2O–P2O5–CaO–M III 2O3 (M III—Al, Fe, Cr) systems have been investigated at fixed value Cs/P molar ratios equal to 0.7, 1.0 and 1.3 and Са/Р=0.2 and Ca/М III=1. The fields of crystallization of CsCaP3O9, β-Ca2P2O7, Cs2CaP2O7, Cs3CaFe(P2O7)2, Ca9 M III(PO4)7 (M III—Fe, Cr), Cs0.63Ca9.63Fe0.37(PO4)7 and CsCa10(PO4)7 were determined. Obtained phosphates were investigated using powder X-ray diffraction and FTIR spectroscopy. Novel whitlockite-related phases CsCa10(PO4)7 and Cs0.63Ca9.63Fe0.37(PO4)7 have been characterized by single crystal X-ray diffraction: space group R3c, a=10.5536(5) and 10.5221(4)Å, с=37.2283(19) and 37.2405(17)Å, respectively. [Copyright &y& Elsevier]

Crystals of dipotassium iron(III) tin(IV) tris(orthophosphate) were grown from a self-flux in the system K2O-P2O5-Fe2O3-SnO2. The title compound is isotypic with the mineral langbeinite, K2Mg2(SO4)3. Its three-dimensional [M2(PO4)3]∞ framework is composed of [MO6] (M = Sn, Fe) octahedra and [PO4] tetrahedra interlinked via vertices. In comparison with the previous refinement from X-ray powder data [Aatiq, Haggouch, Bakri, Lakhdar & Saadoune. (2006). Powder Diffr. 21, 214-219], the present reinvestigation from single-crystal data allows a more precise determination of the distribution of the Fe and Sn atoms over two crystallographic positions and a revision of the P-O and M-O [M = K, (Fe, Sn)] bond lengths. For the two K+ cations, two different polyhedra with coordination numbers of 9 and 12 are observed. The (Fe, Sn) and K atoms are located on three-fold axes. [ABSTRACT FROM AUTHOR]

Dipotassium bismuth phosphate tungstate has been synthesized using the flux technique. It crystallizes in the space group Ibca and is isotypic with Na2Y(PO4)(MoO4). It exhibits a layered structure, which is built up from [Bi(PO4)(WO4)]∞2- layers. Each layer is composed of [BiO8]∞ zigzag chains, which are connected via PO4 and WO4 tetrahedra. The parallel anionic [Bi(PO4)(WO4)]∞2- layers are stacked along [100] and are held together by K+ counter-cations which occupy sites in the interlayer space. Bi, W and P atoms are all located on twofold axes. [ABSTRACT FROM AUTHOR]

The title compound is prepared from KPO3 and NiO (Pt crucible, 1173 K) as a self-flux to which K2ZrF6 is added. [ABSTRACT FROM AUTHOR]

Nonacalcium chromium(III) heptakis(orthophosphate) has been obtained from a melt in the system Cs2O–CaO–Cr2O3 using a polyphosphate flux. The three-dimensional framework is related to the whitlockite structure [β-Ca3(PO4)3] and is built up from CaO8 and CaO9 polyhedra sharing vertices, edges and faces, further connected by PO4 tetrahedra and CrO6 octahedra. The Cr, one P and one O atom are located on threefold rotation axes. Ca9Cr(PO4)7 is isotypic with Ca9Fe(PO4)7. The crystal studied was an inversion twin. [ABSTRACT FROM AUTHOR]

Nine novel phosphates, based upon a combination of caesium, zirconium and lanthanide ions, were obtained from fluoride-containing fluxes using high-temperature crystallization. The structures of Cs1.80Eu0.80Zr1.20(PO4)3 (CsEuZrP), Cs1.79Gd0.79Zr1.21(PO4)3 (CsGdZrP), Cs1.87Tb0.87Zr1.13(PO4)3 (CsTbZrP), Cs1.67Dy0.67Zr1.33(PO4)3 (CsDyZrP), Cs1.75Ho0.75Zr1.25(PO4)3 (CsHoZrP), Cs1.78Er0.78Zr1.22(PO4)3 (CsErZrP), Cs1.70Tm0.70Zr1.30(PO4)3 (CsTmZrP), Cs1.52Yb0.52Zr1.48(PO4)3 (CsYbZrP) and Cs1.63Lu0.63Zr1.37(PO4)3 (CsLuZrP) were solved using single-crystal X-ray diffraction. All compounds are isostructural to the mineral langbeinite (cubic system, space group P213). Their framework structures originate from the cross-linking of metal octahedra [ MO6] ( M = Zr, Ln) by phosphate tetrahedra. Cs+ cations are located in the closed cavities of the framework and preferentially occupy one of the two available sites. The principles of crystallization of the equilibrium langbeinite-related phosphates in the fluxes of the system Cs2O–P2O5–LnF3–ZrF4 (Ln = La–Nd, Sm–Lu) are discussed based on their crystal structures. [ABSTRACT FROM AUTHOR]

The interaction in the molten system Rb2O-P2O5-TiO2-NiO was investigated at different molar ratios Rb/P = 0.5-1.3, fixed Ti/P = 0.15, Ti/Ni = 1.0 at temperature range 1073-953 K. The conditions of formation of complex phosphates RbTi2(PO4)3, Rb2Ni0.5Ti1.5(PO4)3 and RbNiPO4 have been determined. The new phosphate Rb2Ni0.5Ti1.5(PO4)3 (space group P213, a = 9.9386(2) Å) has been obtained and investigated by the single crystal X-ray diffraction and FTIR-spectroscopy. It has langbeinite-like structure, that is built up from mixed (Ni/Ti)O6-octahedra and РО4-tetrahedra. Rubidium atoms are located in closed cavities of 3D-framework. [ABSTRACT FROM AUTHOR]