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Crystal Chemistry of the Saccharinato Complexes of Trivalent Lanthanides and Yttrium
Author(s) -
Piro Oscar E.,
Castellano Eduardo E.,
Baran Enrique J.
Publication year - 2002
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 - 10.1002/1521-3749(200203)628:3<612::aid-zaac612>3.0.co;2-g
Subject(s) - triclinic crystal system , lanthanide , monoclinic crystal system , chemistry , crystallography , yttrium , crystal structure , coordination number , square antiprism , crystal chemistry , stereochemistry , ion , organic chemistry , oxide
Saccharinate complexes of the fourteen trivalent lanthanide cations and Y III were prepared by reaction between the respective lanthanide carbonates and saccharin in aqueous solution. Their crystal structures were determined by single crystal X‐ray diffractometry. They represent three different structural types. The first family, of composition [Ln(sac)(H 2 O) 8 ](sac) 2 H 2 O (sac = anion of saccharin; Ln = La, Ce, Pr, Nd.Sm, Eu), belongs to the monoclinic space group P2 1 /c with Z = 4 and the Ln III cation is in a tricapped trigonal prismatic environment with nine‐fold oxygen coordination. The second group of composition [Ln(sac) 2 (H 2 O) 6 ]‐(sac)(Hsac)4H 2 O with Ln = Gd, Dy, Ho, Er, Yb, Lu, and Y, pertains to the triclinic P1¯‐ space group, with Z = 2 and constitutes a new example of complexes containing simultaneously saccharin and its anion in the lattice. The Tm III and Tb III compounds, which are also triclinic (space group P1¯‐ and Z = 2) present two closely related structures conformed by three and two [Ln(sac)(H 2 O) 7 ] 2+ crystallographically independent complexes, respectively, with the [Tm(sac)(H 2 O) 7 ] 3 (sac) 6 9H 2 O and [Tb(sac)(H 2 O) 7 ]2(sac) 4 6H 2 O composition. For all the heavier lanthanides (Gd‐Lu) and yttrium the cation presents eight‐fold oxygen coordination, with the ligands at the corners of a slightly distorted square Archimedean antiprism.