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Silicon‐Tin‐Ordering in RE 3 Rh 9 Si 2 Sn 3 ( RE = Y, Sm, Gd – Lu)
Author(s) -
Voßwinkel Daniel,
Niehaus Oliver,
Gerke Birgit,
Benndorf Christopher,
Eckert Hellmut,
Pöttgen Rainer
Publication year - 2015
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400458
Subject(s) - rhodium , tin , crystallography , silicon , materials science , intermetallic , bismuth , analytical chemistry (journal) , paramagnetism , diffractometer , bar (unit) , alloy , crystal structure , chemistry , metallurgy , physics , biochemistry , chromatography , quantum mechanics , meteorology , catalysis
Abstract The quaternary intermetallic compounds RE 3 Rh 9 Si 2 Sn 3 ( RE = Y, Sm, Gd – Lu) were obtained from the elements by arc‐melting and investigated by powder X‐ray diffraction. Needle‐shaped single crystals of Ho 3 Rh 9 Si 2 Sn 3 and Lu 3 Rh 9 Si 2 Sn 3 were grown in bismuth fluxes and their structures were refined from single‐crystal X‐ray diffractometer data: P $\bar{6}$ 2 m , a = 968.3(2), c = 345.6(1) pm, wR 2 = 0.0278, 426 F 2 values, 22 variables for Ho 3 Rh 9 Si 2 Sn 3 , and a = 962.4(2), c = 343.1(2) pm, wR 2 = 0.0260, 501 F 2 values, 23 variables for Lu 3 Rh 9 Si 2 Sn 3 . The phases RE 3 Rh 9 Si 2 Sn 3 adopt a new simple structure type with complete silicon‐tin ordering. The silicon atoms have trigonal prismatic rhodium coordination (239 pm Si–Rh in Ho 3 Rh 9 Si 2 Sn 3 ) and the tin atoms are located in slightly distorted square prisms of rhodium (268–274 pm Sn–Rh in Ho 3 Rh 9 Si 2 Sn 3 ). Magnetic investigations were performed for RE 3 Rh 9 Si 2 Sn 3 ( RE = Y, Gd – Yb). Except of Y 3 Rh 9 Si 2 Sn 3 , all investigated compounds exhibit Curie‐Weiss paramagnetism, but ferromagnetic ordering could only be observed for samples containing Gd – Er as rare earth metal. 119 Sn Mössbauer spectroscopic measurements were carried out on Gd 3 Rh 9 Si 2 Sn 3 . A single resonance at an isomer shift of 1.52(1) mm · s –1 clearly underlines that tin is not part of the polyanionic network and therefore not of a stannide character. Representative 29 Si solid state NMR spectroscopy investigations were carried out on the diamagnetic yttrium compound Y 3 Rh 9 Si 2 Sn 3 . The spectrum indicates the existence of only one distinct Si site consistant with the refined single crystal data.