摘要
Two new transition-metal gallophosphates, (H 2 C 4 H 10 N 2 ) 3 [(Ti 2.5 (H 2 O) 4 Ga 5.5 (PO 4 ) 10 ]·2H 2 O (TGP-1) and [H 3.5 (C 4 H 13 N 3 ) 2 ]-[(Ni 0.5 (OH) 4 Ga 5.5 (PO 4 ) 3 (HPO 4 ) 4 ] ·2H 2 O (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 Ti 3+ and Ni 2+ 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, P2 1 /c; a = 25.692(2) Å, b = 9.6552(8) Å c = 9.8418(8) Å, β = 96.737(2)°, V = 2424.5(3) Å 3 , 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) Å 3 , Z = 4.