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Preparation and crystal structure of Ln{sub 3}VO{sub 4}Cl{sub 6} (Ln = La, Ce, Pr, Nd)

Journal Article · · Journal of Solid State Chemistry
;  [1]
  1. Institut fuer Anorganische und Analytische Chemie der Justus-Liebig-Universitaet, Giessen (Germany)

The new compounds Ln{sub 3}VO{sub 4}Cl{sub 6}(Ln=La, Ce, Pr, Nd) were prepared by heating a mixture of LnCl{sub 3}, LnOCl, and V{sub 2}O{sub 5} (3:3:1) in evacuated, sealed silica ampoules (850{degrees}C, 5 d). Single crystals of the lanthanum compound could be obtained by chemical vapor transport (900 {r_arrow} 800{degrees}C; 10 d; transport agent Cl{sub 2}, p(298 K) = 1 atm). The single-crystal study showed that La{sub 3}VO{sub 4}Cl{sub 6} crystallizes in the hexagonal space group P6{sub 3}/m (No. 176), (Z = 2), with {alpha} = 12.5346(9) {Angstrom} and c = 4.1331(4) {Angstrom} (diffractometer data). Least-squares refinement based on 618 unique reflections led to a conventional R value of 1.49% for all data. Vanadium is tetrahedrally coordinated (d{sub v-o} = 1.72-1.75 {Angstrom}). For lanthanum, a C.N. = 10 (3 x O d{sub La-O} = 2.44-2.98 {Angstrom}, 7 x Cl d{sub La-Cl} = 2.95-3.12 {Angstrom}) was found. Apart from the smaller coordination number of V{sup 5+} as compared to Nb{sup 5+}, the structure is closely related to that of Pr{sub 3}NbO{sub 4}Cl{sub 6}.

Sponsoring Organization:
USDOE
OSTI ID:
263729
Journal Information:
Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 122; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English