ISSN:
0044-2313
Keywords:
Lanthanide sesquisulfides
;
crystal structures
;
preparation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Single Crystals of A—Nd2S3, U—Ho2S3, D—Er2S3, and E—Lu2S3 through the Oxidation of Reduced Lanthanide Chlorides with SulfurThe oxidation of reduced chlorides (MCl2) or chloridehydrides (MClHx) of the lanthanides with sulfur (850°C, 7 d, tantalum ampoule) usually results in the formation of their sesquisulfides (M2S3) as the main product. In the presence of appropriate fluxes (e. g., NaCl), they often are obtained as single crystals, and the flux appears to decide which modification is favourized. Single crystals of Nd2S3, (from NdCl2 + NaCl + S, 2 : 2 : 1, A-type: orthorhombic, Pnma (no. 62), Z = 4; a = 743.97(5), b = 402.78(3), c = 1551.96(9) pm, Vm = 70.015(8) cm3/mol, R, = 0.026, Rw = 0.023), Ho2S3, (from Na0.25HoClH0.75 + S, 8 : 9, U type: orthorhombic, Pnma (no. 62), Z = 4, a = 1057.24(7), b = 384.48(4), c = 1041.15(7) pm, Vm = 63.716(9) cm3/mol, R, = 0.023, Rw = 0.020), Er2S3, (from ErClH0.67 + NaCl + S, 2 : 2 : 1, D type: monoclinic, P21/m (no. 11), Z = 6, a = 1744.18(9), b = 398.22(3), c = 1010.13(6) pm, β = 98.688(4)°, Vm = 69.610(7) cm3/mol, R = 0.031, Rw = 0.029) and Lu2S3, (from LuClH0.67 + NaCl + S, 2 : 2 : 1, E type: trigonal, R3c (no. 167), Z = 6, a = 672.86(2), c = 1816.84(9) pm, c/a = 2.70, Vm = 71.497(6) cm3/mol, R = 0.023, Rw = 0.020) as well as more systematic general investigations (syntheses of the lanthanide sesquisulfides from the elements in the presence of NaCl as a flux in sealed tantalum containers at 850°C) are the main topic of the work presented here.
Notes:
Bei der Oxidation „reduzierter“ Chloride (MCl2) bzw. Chlorid-Hydride (MClHx) der Lanthanide mit Schwefel (850°C, 7 d, Tantal-Ampulle) entstehen oft die Sesquisulfide (M2S3) als Hauptprodukt. In Gegenwart geeigneter Flußmittel (z. B. NaCl) fallen sie meist einkristallin an, wobei das Flußmittel einen entscheidenden Einfluß auf die bevorzugt gebildete Modifikation hat. Einkristalle von Nd2S3, (aus NdCl2 + NaCl + S, 2 : 2 : 1, A-Typ: orthorhombisch, Pnma (Nr. 62), Z = 4; a = 743,97(5); b = 402,78(3); c = 1551,96(9) pm; Vm = 70,015(8) cm3/mol; R = 0,026; Rw = 0,023), Ho2S3, (aus Na0,25HoClH0,75 + S, 8 : 9, U-Typ: orthorhombisch, Pnma (Nr. 62), Z = 4; a = 1057,24(7); b = 384,48(4); c = 1041,15(7) pm; Vm = 63,716(9) cm3/mol; R = 0,023; Rw = 0,020), Er2S3, (aus ErClH0,67 + NaCl + S, 2 : 2 : 1, D-Typ: monoklin, P21/m (Nr. 11), Z = 6; a = 1744,18(9); b = 398,22(3); c = 1010,13(6)pm; β = 98,688(4)°; Vm = 69,610(7) cm3/mol; R = 0,031; Rw = 0,029) und Lu2S3, (aus LuClH0,67 + NaCl + S, 2 : 2 : 1, E-Typ: trigonal, R3c (Nr. 167), Z = 6; a = 672,86(2); c = 1816,84(9) pm; c/a = 2,70; Vm = 71,497(6) cm3/mol; R = 0,023; Rw = 0,020) sowie systematisierte Folgeuntersuchungen (Darstellung der Lanthanid-Sesquisulfide aus den Elementen in Gegenwart von NaCl als Flußmittel in verschweißten Tantal-Ampullen bei 850°C) sind Gegenstand der vorliegenden Arbeit.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19926150905
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