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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]

Abstract: Two new mixed valence manganese-containing orthophosphates with a langbeinite structure have been obtained from the complex fluoride–phosphate melts using the high-temperature flux technique. M IVF4 and K2 M IVF6 (M IV—Zr, Hf) were used as fluoride and polyvalent metal precursors. Obtained langbeinites were investigated using a single-crystal X-ray diffraction, FTIR-, UV–VIS- and electron paramagnetic resonance (EPR)-spectroscopy. Both compounds crystallize in a cubic system (sp. gr. P213) with cell parameters a=10.2106(12) and 10.1896(9)Å for K1.96Mn0.57Zr1.43(PO4)3 and K1.93Mn0.53Hf1.47(PO4)3, respectively. The rigid langbeinite-like framework is built up from the isolated [MO6] octahedra and [PO4] tetrahedra interlinked via oxygen vertices. Potassium cations occupy positions in the large closed cavities of the framework. Statistical distribution of manganese and tetravalent metal over two crystallographic positions in octahedral oxygen environment can be observed. The presence of the mixed valence manganese in the reported phosphates was confirmed using UV–VIS and EPR-spectroscopy. [Copyright &y& Elsevier]

Abstract: The single crystals of caesium magnesium titanium (IV) tri-oxo-tetrakis-diphosphate bis-monophosphate, Cs3.70Mg0.60Ti2.78(TiO)3(P2O7)4(PO4)2, crystallize in sp. gr. P-1 (No. 2) with cell parameters a=6.3245(4), b=9.5470(4), c=15.1892(9)Å, α=72.760(4), β=85.689(5), γ=73.717(4), z=1. The titled compound possesses a three-dimensional tunnel structure built by the corner-sharing of distorted [TiO6] octahedra, [Ti2O11] bioctahedra, [PO4] monophosphate and [P2O7] pyrophosphate groups. The Cs+ cations are located in the tunnels. The partial substitution of Ti positions with Mg atoms is observed. The negative charge of the framework is balanced by Cs cations and Mg atoms leading to pronounced concurrency and orientation disorder in the [P2O7] groups, which coordinate both. [Copyright &y& Elsevier]

Abstract: New complex phosphates of the general formula K2 M 0.5Ti1.5(PO4)3 (M=Mn, Co) have been obtained from the melting mixture of KPO3, K4P2O7, TiO2 and CoCO3·mCo(OH)2 or Mn(H2PO4)2 by means of a flux technique. The synthesized phosphates have been characterized by the single-crystal X-ray diffraction and the FTIR-spectroscopy. The compounds crystallize in the cubic system with the space group P213 and cell parameters a=9.9030(14)Å for K2Mn0.5Ti1.5(PO4)3 and a=9.8445(12)Å for K2Co0.5Ti1.5(PO4)3. Both phosphates are isostructural with the langbeinite mineral and contain four formula unit K2 M 0.5Ti1.5(PO4)3 per unit cell. The structure can be described using [M 2(PO4)3] framework composed of two [MO6] octahedra interlinked via three [PO4] tetrahedra. The Curie–Weiss-type behavior is observed in the magnetic susceptibility. [Copyright &y& Elsevier]