Journal
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
Volume 632, Issue 12-13, Pages 1995-2002Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/zaac.200600159
Keywords
lanthanides; nitride sulfides; crystal structures; magnetism
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Nitride sulfides of the trivalent lanthanides with the composition M3NS3 (M = La - Nd, Sm, Gd - Dy) can be prepared by the oxidation of the respective lanthanide metal with sulfur, sodium azide (NaN3) and the corresponding lanthanide tribromide (MBr3) when an additional flux (NaBr) is used. Temperature ranges from 800 to 900 degrees C for the thermal treatment of the reaction mixtures in evacuated silica tubes secure the formation of bright to dark brown, transparent, lath shaped single-crystals. The orthorhombic crystal structure (Pnma, Z = 4) was determined from single-crystal X-ray diffraction data (La3NS3: a = 1215.13(5), b = 415.90(2), c = 1322.12(5) pm, Ce3NS3: a = 1206.28(4), b = 410.16(1), c = 1307.18(5) pm, Pr3NS3: a = 1205.45(7), b = 405.35(2), c = 1297.58(8) pm, Nd3NS3: a = 1207.82(5), b = 401.31(1), c = 1295.20(4) pm, Sm3NS3: a = 1201.58(6), b = 394.84(2), c = 1285.63(7) pm, Gd3NS3: a = 1197.17(7), b = 388.22(3), c = 1286.92(8) pm, Tb3NS3: a = 1191.62(7), b = 385.07(3), c = 1282.44(8) pm, and Dy3NS3: a = 1187.66(7), b = 382.55(3), c = 1276.77(8)pm). There are three crystallographically different M3+ cations present in coordination of both the N3- and the S2- anions. However, [NM4](9+) tetrahedra connected via two common corners (c) to form linear chains (1)(infinity){[N(M1)(1/1)(t)(M2)(1/1)(t)(M3)(2/2)(c)](6+)} along [010] build up the main structural feature. A non-linear behaviour for the decreasing lattice constants of the pseudo-isotypic series from La3NS3 to Dy3NS3 concerning the a- and c-axes is observed along with the lanthanoid contraction caused by the diminishing coordination sphere of (M1)(3+) (CN = 7) and (M3)(3+) (CN = 7) moving from the light to the heavier lanthanides. Curie-Weiss-type magnetic behaviour for Dy3NS3 with mu(eff) = 10.3(1) mu(B) for DyN1/3S corresponding to a H-6(15/2) groundstate for Dy3+ at higher temperatures and antiferromagnetic ordering of the Dy3+ moments below 5 K is observed.
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