Two new transition-metal gallophosphates, (H2C4H 10N2)3[(Ti2.5(H2O) 4Ga5.5(PO4)10]·2H 2O (TGP-1) and [H3.5(C4H13N 3)2]-[(Ni0.5(OH)4Ga 5.5(PO4)3(HPO4)4] ·2H2O (NGP-1), have been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, electron paramagnetic resonance, electron probe microanalysis, and magnetic susceptibility data. TGP-1 exhibits a unique two-dimensional structure consisting of tetrahedral and octahedral metals centers and is the foremost paramagnetic TiGaPO material ever prepared. NGP-1 as well represents the first NiGaPO compound and adopts a layer structure that is constructed from hexameric M-O clusters of trigonal bipyramids and octahedra. In both compounds, the transition metals incorporate with gallium into octahedral sites only, while the four- and five-coordinated metals centers are only Ga 3+ ions. The unique sites for Ti3+ and Ni2+ ions have been initially elucidated from single-crystal structure refinements and further confirmed by bond-valence-sum calculations, EPR, and magnetic susceptibility studies. Crystal data: TGP-1, monoclinic, P21/c; a = 25.692(2) Å, b = 9.6552(8) Å c = 9.8418(8) Å, β = 96.737(2)°, V = 2424.5(3) Å3, and Z = 2; NGP-1, monoclinic, C2/c, a = 20.8363(12) Å, b = 11.9546(7) Å, c = 16.4577(9) Å, β = 117.285(1)°, V = 3643.3(1) Å3, Z = 4.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry