Preparation of New Ba4M3S10 Phases (M = Zr, Hf) and Single Crystal Structure Determination of Ba4Zr3S10

✍ Scribed by Bai-Hao Chen; Winnie Wong-Ng; Bryan W. Eichhorn

• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 223 KB
• Volume: 103
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1993.1080

✦ Synopsis

Two new Ruddlesden-Popper (\mathrm{Ba}{n+1} M{n} \mathrm{~S}{3 n+1}) compounds where (M=\mathrm{Zr}, \mathrm{Hf}) and (n=3) have been prepared in good yield from (\mathrm{BaS}, M), and (\mathrm{S}) in a (\mathrm{BaCl}{2}) flux at (1050^{\circ} \mathrm{C}). The structures comprise triple layer perovskite slabs separated by double (\mathrm{BaS}) layers. The single crystal structure of (\mathrm{Ba}{4} \mathrm{Zr}{3} \mathrm{~S}{10}) revealed (\mathrm{Zr}-\mathrm{S}) distances of 2.493(3) (\AA) (average) with one long (\mathrm{Zr}-\mathrm{S}) contact of 2.562(5) (\AA) for the distal bond of the (\mathrm{ZrS}{6}) octahedron at the perovskite/double BaS interface. The Ba-S contacts average (3.52(1) \AA) inside the perovskite blocks and range between (3.084(5)) and (3.552(1) \AA) in the double (B a S) layers. Crystal data for (\mathrm{Ba}{4} \mathrm{Zr}{3} \mathrm{~S}{10}\left(25^{\circ} \mathrm{C}\right)) are (a=7.0314(5) \AA, b=7.0552(7) \AA, c=35.544(7) \AA, Z=4, D{\text {calc }}) (=4.038 \mathrm{~g} / \mathrm{cm}^{3}), orthorhombic, space group (F m m m, R(F)=0.038, R_{\mathrm{w}}(F)=0.058). Single crystals of (\mathrm{Ba}{4} \mathrm{Hf}{3} \mathrm{~S}_{10}) were indexed on an orthorhombic cell with (a=6.989(3) \AA, b=7.022(2) \AA), and (c=35.428(8)) (\AA) but the structure was not refined due to poor quality data. ○1993 Academic Press. Inc.