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Crystal Structure and Magnetic Properties of Bi(Bi 9 )[NbCl 6 ] 3 , a New Member of the Structure Family Bi(Bi 9 )[MX 6 ] 3 , and the Crystal Structure of Bi 8 [Ta 2 O 2 Br 7 ] 2
Author(s) -
Beck Johannes,
Hilbert Tobias
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300646
Subject(s) - chemistry , crystallography , octahedron , paramagnetism , tetragonal crystal system , crystal structure , bismuth , transition metal , magnetic moment , cationic polymerization , metal , ion , oxidation state , catalysis , condensed matter physics , physics , organic chemistry , biochemistry
Bi and Bi III halides comproportionate to form subvalent cationic Bi clusters of various size and shape that can be stabilized in the solid state in the presence of suitable complex ions. Transition metal chlorides and bromides of group 4 elements lead to compounds of the Bi(Bi 9 )[MX 6 ] 3 family, of which all members with M = Zr, Hf; X = Cl, Br are known. At 550 K Bi, BiCl 3 and NbCl 5 , surprisingly, yield the isotypic Bi + (Bi 9 5+ )([NbCl 6 ] 2− ) 3 containing Nb IV formed by reduction of Nb V . The crystal structure [hexagonal; P 6 3 / m ; a = 1377.1(2), c = 1065.5(2) pm; Z = 2] contains Bi 9 5+ clusters, octahedral [NbCl 6 ] 2− and disordered Bi + ions. The low, temperature‐dependent paramagnetic moment (76 K: 0.99 B.M.; 295 K: 1.22 B.M.) confirms the reduction of Nb to the + IV state. Bi 8 [Ta 2 O 2 Br 7 ] 2 , formed by a trace of H 2 O in a reaction of Bi, BiBr 3 and TaBr 5 at 570 K, adopts a new structure type [tetragonal; P 4/ mnc ; a = 1448.0(1), c = 1830.6(2) pm; Z = 4] and consists of square‐antiprismatic Bi 8 2+ clusters and onedimensional polymeric bromooxotantalate( V ) anions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)