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Synthesis and characterization of two novel bimetallic macrocyclic complexes generated from 1,2,4‐triazole‐containing semi‐rigid ligands and M (NO 3 ) 2 units ( M = Ni and Zn)
Author(s) -
Wu Xiang-Wen,
Yin Shi,
Wu Wan-Fu,
Ma Jian-Ping
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/s205322961600348x
Subject(s) - bimetallic strip , chemistry , sulfanyl , supramolecular chemistry , amine gas treating , 1,2,4 triazole , ligand (biochemistry) , methanol , nickel , zinc , medicinal chemistry , stereochemistry , metal , polymer chemistry , crystallography , crystal structure , organic chemistry , biochemistry , receptor
Bimetallic macrocyclic complexes have attracted the attention of chemists and various organic ligands have been used as molecular building blocks, but supramolecular complexes based on semi‐rigid organic ligands containing 1,2,4‐triazole have remained rare until recently. It is easier to obtain novel topologies by making use of asymmetric semi‐rigid ligands in the self‐assembly process than by making use of rigid ligands. A new semi‐rigid ligand, 3‐[(pyridin‐4‐ylmethyl)sulfanyl]‐5‐(quinolin‐2‐yl)‐4 H ‐1,2,4‐triazol‐4‐amine ( L ), has been synthesized and used to generate two novel bimetallic macrocycle complexes, namely bis{μ‐3‐[(pyridin‐4‐ylmethyl)sulfanyl]‐5‐(quinolin‐2‐yl)‐4 H ‐1,2,4‐triazol‐4‐amine}bis[(methanol‐κ O )(nitrato‐κ 2 O , O ′)nickel(II)] dinitrate, [Ni 2 (NO 3 ) 2 (C 17 H 14 N 6 S) 2 (CH 3 OH) 2 ](NO 3 ) 2 , (I), and bis{μ‐3‐[(pyridin‐4‐ylmethyl)sulfanyl]‐5‐(quinolin‐2‐yl)‐4 H ‐1,2,4‐triazol‐4‐amine}bis[(methanol‐κ O )(nitrato‐κ 2 O , O ′)zinc(II)] dinitrate, [Zn 2 (NO 3 ) 2 (C 17 H 14 N 6 S) 2 (CH 3 OH) 2 ](NO 3 ) 2 , (II), by solution reactions with the inorganic salts M (NO 3 ) 2 ( M = Ni and Zn, respectively) in mixed solvents. In (I), two Ni II cations with the same coordination environment are linked by L ligands through Ni—N bonds to form a bimetallic ring. Compound (I) is extended into a two‐dimensional network in the crystallographic ac plane via N—H…O, O—H…N and O—H…O hydrogen bonds, and neighbouring two‐dimensional planes are parallel and form a three‐dimensional structure via π–π stacking. Compound (II) contains two bimetallic rings with the same coordination environment of the Zn II cations. The Zn II cations are bridged by L ligands through Zn—N bonds to form the bimetallic rings. One type of bimetallic ring constructs a one‐dimensional nanotube via O—H…O and N—H…O hydrogen bonds along the crystallographic a direction, and the other constructs zero‐dimensional molecular cages via O—H…O and N—H…O hydrogen bonds. They are interlinked into a two‐dimensional network in the ac plane through extensive N—H…O hydrogen bonds, and a three‐dimensional supramolecular architecture is formed via π–π interactions between the centroids of the benzene rings of the quinoline ring systems.