Preparation and crystal structure of a new form of Sb{sub 2}(PO{sub 4}){sub 3} and M{sub 1/2}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3} (M = Y, In, and Sc)
Journal Article
·
· Journal of Solid State Chemistry
- Univ. of Tokyo (Japan)
A new form of mixed-valence antimony phosphate Sb{sub 1/2}{sup III}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3} ({beta}-Sb{sub 2}(PO{sub 4}){sub 3}) has been prepared by the reaction of antimony pentachloride with a solution of antimony trichloride in phosphoric acid. The structure has been determined by single crystal X-ray study. Crystal data are as follows: space group R{bar 3}, Z = 24, a = 16.880(2) {angstrom}, c = 21.196(3) {angstrom}, and V = 5230(1) {angstrom}. The structure is basically isotypic with Bi{sub 1/2}{sup III}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3}. The Sb1{sup III} atom is disordered in (0, 0, {+-}z) positions as observed in Bi{sub 1/2}{sup III}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3}. Furthermore, some of the phosphorous and oxygen atoms are distributed in major and minor positions in the ratio of 5:1. Structural consideration has indicated that of the six oxygen atoms bonded with an Sb1{sup III} atom, five are at the major positions and one is at the minor position. This irregular coordination decreases the bond-order sum of the Sb1 atom to 3.07 and also gives a space for the lone-pair electrons. Similar preparations with yttrium trichloride, indium trichloride, and scandium nitrate have yielded Y{sub 1/2}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3}, In{sub 1/2}Sb{sub 3/2}{sub V}(PO{sub 4}){sub 3}, and Sc{sub 1/2}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3}, respectively. X-ray powder diffraction studies have shown that the yttrium compound has the Bi{sub 1/2}{sup III}Sb{sub 3/2}{sup V}(PO{sub 4}){sub 3} structure while other two have the {alpha}-Sb{sub 2}(PO{sub 4}){sub 3} structure.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 146453
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 118; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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