Synthesis and Crystal Structures of Zirconium Phosphate Fluorides with New 2D and 3D Structure Types

✍ Scribed by Martin Wloka; Sergei I. Troyanov; Erhard Kemnitz

• Publisher: Elsevier Science
• Year: 2000
• Tongue: English
• Weight: 351 KB
• Volume: 149
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1999.8475

✦ Synopsis

Three new zirconium phosphate 6uorides, [amH 2 ] 0.5 [Zr 2 (PO 4 )(HPO 4 ) 2 F 2 ] ' 0.5H 2 O (1), [amH 2 ] 1.5 [Zr 3 (PO 4 ) 3 F 6 ] ' 1.5H 2 O (2) (am ‫؍‬ trans-1,4-diaminocyclohexane for 1 and 2), and [amH 2 ] 0.5 [Zr 3 (PO 4 ) 3 (HPO 4 )F 2 ] ' 1.5H 2 O (am ‫؍‬ 2,2dimethyl-1,3-diaminopropane) (3), were synthesized under hydrothermal conditions and structurally characterized. Zr is octahedrally coordinated in all three structures. In 1, the octahedra consist of ZrO 6 and ZrO 4 F 2 units. Compound 2 is made exclusively of ZrO 4 F 2 . In 3, there are three di4erent types of Zroctahedra, namely, ZrO 6 , ZrO 5 F, and ZrO 4 F 2 . The Zr octahedra and PO 4 tetrahedra are connected via non-OH oxygen atoms. In 1 and 2, all F atoms are terminal, whereas in 3, one of the two F atoms bridges between the ZrO 5 F and ZrO 4 F 2 octahedra. In structures 1 and 2 with higher F/Zr ratios, twodimensional inorganic networks exist. The inorganic sheets are connected by the protonated templates via N+H2F and in 1 additionally by O+H2F hydrogen bonds. In 3, the lower F/Zr ratio results in the formation of a three-dimensional inorganic framework with characteristic 99double:: channels in which the highly disordered templates are located. The existence of several structure types in the ZrPOF-n family is discussed on the basis of di4erent template geometry and F/Zr ratios.