Title: Isolated and Edge‐Sharing Interstitially Stabilized Metal Tetrahedra {M<sub>4</sub>Z} in La<sub>4</sub>ZBr<sub>7</sub>, M<sub>9</sub>Z<sub>4</sub>I<sub>16</sub>, and BaM<sub>4</sub>Z<sub>2</sub>I<sub>8</sub> (M = La,Ce). The Nature of Z
Abstract:Abstract Metallothermic reductions of LaBr 3 , LaI 3 and CeI 3 with barium metal resulted in single crystals of La 4 ZBr 7 , M 9 Z 4 I 16 and BaM 4 Z 2 I 8 (M = La,Ce) as by‐products, subject to appar...Abstract Metallothermic reductions of LaBr 3 , LaI 3 and CeI 3 with barium metal resulted in single crystals of La 4 ZBr 7 , M 9 Z 4 I 16 and BaM 4 Z 2 I 8 (M = La,Ce) as by‐products, subject to apparently ubiquitous “oxygen” and/or “nitrogen” (= Z) impurities. The crystal structure of La 4 ZBr 7 ( 1 , orthorhombic, Pnma, Z = 4, a = 1212.4(1), b = 1404.8(2), c = 804.7(1) pm, R 1 = 0.0358 for I>2σI with N:O = 0.91:0.09) is determined by isolated {La 4 Z} tetrahedra surrounded by and connected through bromide ligands. In the crystal structure of Ce 9 Z 4 I 16 ( 2 , orthorhombic, Fddd, Z = 8, a = 890.0(1), b = 2264.1(2), c = 4279.5(4) pm, R 1 = 0.0262 for I>2σI with N:O = 0.75:0.25), {Ce 4 Z} tetrahedra are connected to {Ce 4/2 Z} chains via common edges and further to layers by iodide ligands. The layers are stacked and connected via the ninth cerium atom according to Ce[{Ce 4/2 Z}I 4 ] 4 . Similar {La 4/2 Z} chains and BaI 8/4 chains run perpendicularly to each other and are connected via common iodide ions in the crystal structure of BaLa 4 Z 2 I 8 = Ba 2 [{La 4/2 Z}I 4 ] 4 ( 3 , monoclinic, C2/c, Z = 4, a = 897.5(1), b = 2162.4(3), c = 1229.3(2), β = 110.32(1)°, R 1 = 0.0261 for I>2σI with N:O = 0.54:0.46). The nature of the interstitial Z, oxygen and/or nitrogen, is evaluated.Read More
Publication Year: 2006
Publication Date: 2006-08-23
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 11
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