Two New Barium-Vanadium(IV) Phases: Ba(VO)2(SeO3)2(HSeO3)2, the First Barium Vanadium Selenite, and Ba8(VO)6(PO4)2(HPO4)11 · 3H2O, a Compound Built Up from Two Types of One-Dimensional Chains
✍ Scribed by William T.A. Harrison; J.T. Vaughey; Allan J. Jacobson; David P. Goshorn; Jack W. Johnson
- Publisher
- Elsevier Science
- Year
- 1995
- Tongue
- English
- Weight
- 477 KB
- Volume
- 116
- Category
- Article
- ISSN
- 0022-4596
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✦ Synopsis
The hydrothermal syntheses, X-ray single-crystal structures, and some properties of (\mathrm{Ba}\left(\mathrm{VO}{2}\right){2}\left(\mathrm{SeO}{3}\right){2}\left(\mathrm{HSeO}{3}\right){2}) and (\mathrm{Ba}{8}(\mathrm{VO}){6}) (\left(\mathrm{PO}{4}\right){2}\left(\mathrm{HPO}{4}\right){11} \cdot 3 \mathrm{H}{2} \mathrm{O}) are described. (\mathrm{Ba}\left(\mathrm{VO}{2}\right){2}\left(\mathrm{SeO}{3}\right){2}\left(\mathrm{HSeO}{3}\right){2}) contains a three-dimensional network of (\mathrm{VO}{6}) and (H) (\mathrm{SeO}{3}) polyhedra, linked via V-O-Se bonds. The Ba cation is 10 -coordinate, the (\mathrm{VO}{6}) group contains a short vanadyl (\mathrm{V}=0) bond typical of (\mathrm{V}^{\mathrm{V}}), and the ((\mathrm{H}) \mathrm{SeO}{3}) groups are pyramidal. Magnetic susceptibility data are consistent with (\mathrm{V}^{\mathrm{NV}}) and show paramagnetic behavior from 4 to (300 \mathrm{~K}). Crystal data for (\mathrm{Ba}\left(\mathrm{VO}{2}\right){2}\left(\mathrm{SeO}{3}\right){2}\left(\mathrm{HSeO}{3}\right){2}: M{\mathrm{r}}=781.06), monoclinic, space group (P 2_{1} / c) (No. 14), (a=9.680(3) \AA, b=) (7.024(2) \AA, c=9.882(4) \AA, \beta=116.42(3)^{\circ}, V=601.75 \AA^{3}, Z=) 2, (R=3.89 %, R_{\mathrm{w}}=3.64 %[1637) observed reflections with (I>) (3 \sigma(I)] . \mathrm{Ba}{8}\left(\mathrm{VO}{6}\right){6}\left(\mathrm{PO}{4}\right){2}\left(\mathrm{HPO}{4}\right){11} \cdot 3 \mathrm{H}{2} \mathrm{O}) contains a complex network of (\mathrm{VO}{6}) and (\mathrm{PO}{4} / \mathrm{HPO}{4}) groups, which form two different types of one-dimensional chains: one chain contains fairly regular (\mathrm{V}^{\mathrm{IV}} \mathrm{O}{6}) and ((\mathrm{H}) \mathrm{PO}{4}) groups; the other is built up from distorted (\mathrm{V}^{\mathrm{IV}} \mathrm{O}{6}) octahedra and (hydrogen) phosphate groups. 10- and 13coordinate (\mathrm{Ba}^{2+}) cations complete the structure, which shows antiferromagnetic ordering of the (\mathrm{V}^{\text {IV }}) centers at (\sim 20 \mathrm{~K}). Crystal data for (\mathrm{Ba}{8}\left(\mathrm{VO}{6}\right){6}\left(\mathrm{PO}{4}\right){2}\left(\mathrm{HPO}{4}\right){11} \cdot 3 \mathrm{H}{2} \mathrm{O}: M_{\mathrm{r}}=2800.05), monoclinic, space group (C 2 / m) (No. 12), (a=31.685(11) \AA, b=5.208(2) \AA), (c=7.784(3) \AA, \beta=90.59(3)^{\circ}, V=1284.5(7) \AA^{3}, Z=1), (R=4.03 %), and (R_{\mathrm{w}}=5.28 %) [1892 observed reflections with (I>) (3 \boldsymbol{\sigma}(I)] . \quad 1995) Academic Press. Inc.