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Syntheses and structures of discrete copper(II) and cadmium(II) supramolecular complexes based on 1,4‐diacylthiosemicarbazone ligands
Author(s) -
Jiao Chen,
Zhang Si-Si,
Li Zuo-Yin,
Liu Jian-Jun,
Lin Mei-Jin,
Huang Chang-Cang
Publication year - 2016
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229616000310
Subject(s) - copper , supramolecular chemistry , cadmium , chemistry , crystallography , combinatorial chemistry , stereochemistry , crystal structure , organic chemistry
Thiosemicarbazides and their metal complexes have attracted considerable interest because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Discrete copper(II) and cadmium(II) complexes have been prepared by crystallization of N ‐[2‐(2‐hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H 3 L ) with Cu(CH 3 COO) 2 or Cd(NO 3 ) 2 in a dimethylformamide/methanol mixed‐solvent system at room temperature, affording the complexes di‐μ‐acetato‐bis{μ 4 ‐1‐[(2‐oxidophenyl)carbonyl]‐2‐(propanamidomethanethioyl)hydrazine‐1,2‐diido}tetracopper(II) dimethylformamide disolvate, [Cu 4 (C 11 H 10 N 3 O 3 S) 2 (C 2 H 3 O 2 ) 2 ]·2C 3 H 7 NO, (I), and bis{μ 2 ‐[(2‐hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4′‐bipyridine)nitratocadmium(II)] dihydrate, [Cd 2 (C 11 H 12 N 3 O 3 S) 2 (NO 3 ) 2 (C 10 H 8 N 2 ) 2 ]·2H 2 O, (II). Complex (I) consists of four Cu II cations, two μ 4 ‐bridging trianionic ligands and two μ 2 ‐bridging acetate ligands, while complex (II) is composed of two Cd II cations, two μ 2 ‐bridging monoanionic ligands, two nitrate ligands and two 4,4′‐bipyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals interactions to form a three‐dimensional supramolecular architecture. Compared with (I), the phenolic hydroxy group and hydrazide N atom of the thiosemicarbazide ligand of (II) are not involved in coordination and lead to a binuclear Cd II complex. This different coordination mode may be attributed to the larger ionic radius of the Cd II ion compared with the Cu II ion.