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An Oxalate‐Bridged Copper(II) Dimer and a Mononuclear Cobalt(III) Azide Complex Containing N ‐Nitrile‐Functionalized 1, 4, 7‐Triazacyclononane Terminals: Synthesis, Crystal Structure, and Magnetic Characterization
Author(s) -
Zhang Zhong,
Shao DaLin,
Geng ZhiRong,
Wang ZhiLin
Publication year - 2012
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.201100507
Subject(s) - azide , nitrile , oxalate , crystallography , denticity , dimer , chemistry , monoclinic crystal system , isopropyl , crystal structure , cobalt , copper , intramolecular force , stereochemistry , inorganic chemistry , medicinal chemistry , organic chemistry
The stable dinuclear [Cu(μ‐C 2 O 4 )Cu] 2+ entity is facially coordinated at each end by a N ‐nitrile functionalized triazamacrocycle, 1, 4, 7‐tris(cyanomethyl)‐1, 4, 7‐triazacyclononane ( L ), to generate a centrosymmetric compound [Cu 2 L 2 (μ‐C 2 O 4 )](ClO 4 ) 2 · 4DMF ( 1 ) containing a bis‐bidentate oxalate bridge. The variable‐temperature magnetic measurement for the crystallographically characterized compound exhibits quite strong antiferromagnetic coupling interaction between two oxalate‐linked Cu II atoms separated by 5.149 Å with a singlet‐triplet energy gap of –345.5 cm –1 . On the other hand, a mononuclear Co III compound [Co L (N 3 ) 3 ] · 2.5H 2 O ( 2 ) with monodentate azide terminal groups was synthesized. Structural elucidation by X‐ray diffraction shows that the compound has crystallographically imposed C 3 symmetry. Enantiomerically pure crystals were obtained upon crystallization indicated by a Flack parameter of 0.04(5).