Synthesis and Characterization of a Large-Pore, Open-Framework Gallium Phosphate, [NH3(CH2)4NH3]2[Ga4(HPO4)2(PO4)3(OH)3]·yH2O (y∼5.4), and Its Vanadium–Gallium Phosphate Analogue, [NH3(CH2)4NH3]2[Ga4−xVx(HPO4)2(PO4)3(OH)3]·yH2O (x∼0.4, y∼6)

✍ Scribed by Ann M. Chippindale; Katherine J. Peacock; Andrew R. Cowley

• Publisher: Elsevier Science
• Year: 1999
• Tongue: English
• Weight: 406 KB
• Volume: 145
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1998.8071

✦ Synopsis

A new three-dimensional gallium phosphate, [NH 3 (CH 2 ) 4 NH 3 ] 2 [Ga 4 (HPO 4 ) 2 (PO 4 ) 3 (OH) 3 ] ' yH 2 O (y&5.4), has been synthesized under hydrothermal conditions at 433 K in the presence of 1,4-diaminobutane and its structure determined using room-temperature single-crystal X-ray di4raction data (M r ‫؍‬ 1084.03, tetragonal, space group I4 1 /a, a ‫؍‬ 15.261(1), c ‫؍‬ 28.898(2) A s ; V ‫؍‬ 6730.4 A s 3 , Z ‫؍‬ 8, R ‫؍‬ 4.09% and R w ‫؍‬ 4.45% for 3093 observed data (I'3( (I))). The structure consists of chains of GaO 6 octahedra and PO 4 tetrahedra cross-linked by additional PO 4 tetrahedra to generate a three-dimensional framework containing large tunnels in which 1,4-diaminobutane dications and water molecules reside. The tunnels are bounded by 20-ring windows of alternating gallium-and phosphorus-based polyhedra. The framework is closely related to that of a 1,3diaminopropane encapsulating iron (III) phosphate, [NH 3 (CH 2 ) 3 NH 3 ] 2 [Fe 4 (HPO 4 ) 2 (PO 4 ) 3 (OH) 3 ] ' yH 2 O (y&9), Further syntheses in the presence of V 2 O 5 show that up to 12% of the Ga(III) can be replaced by V(III) with retention of the large-pore framework structure.