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Syntheses and Crystal Structures of Mercury( II ) and Copper( II ) Complexes of an 18‐Membered NS 4 ‐Macrocycle
Author(s) -
Lee Eunji,
Lee Shim Sung
Publication year - 2015
Publication title -
bulletin of the korean chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.237
H-Index - 59
ISSN - 1229-5949
DOI - 10.1002/bkcs.10007
Subject(s) - chemistry , thiocyanate , denticity , crystallography , octahedron , square pyramidal molecular geometry , coordination geometry , octahedral molecular geometry , crystal structure , stereochemistry , ligand (biochemistry) , tetrahedral molecular geometry , isostructural , metal ions in aqueous solution , copper , ion , metal , molecule , inorganic chemistry , hydrogen bond , biochemistry , receptor , organic chemistry
An 18‐membered NS 4 ‐macrocycle was employed, and its complexation behaviors with hard and soft metal ions were investigated. Reactions of L with mercury( II ) nitrate and thiocyanate afforded endocyclic mononuclear complexes [Hg( L )( NO 3 ) 2 ] ( 1 ) and [Hg( L )( SCN ) 2 ] ( 2 ), respectively, with anion coordinations. In the nitrato complex 1 , the mercury( II ) center is six‐coordinate, being bound to three S donors and one pyridine N atom in L , and the coordination sphere is completed by two monodentate nitrate ions from both sides of the macrocyclic plane adopting a distorted octahedral geometry. The thiocyanato complex 2 , which contains two crystallographically independent but almost isostructural complex units is five‐coordinate, being bound to NS 2 donors in L and two monodentate thiocyanate ions on the same side of the bound macrocycle unlike 1 , adopting a distorted square pyramidal geometry. Reaction of L with CuCl 2 · 2H 2 O yielded a dark‐green bis(macrocycle) trinuclear complex, [Cu 3 ( L ) 2 Cl 6 ] · 0.5 CH 2 Cl 2 ( 3 ), in which two endocyclic monocopper( II ) complex units are linked by an exocyclic one Cu and two bridging Cl atoms. In 3 , interestingly, the local coordination environments of the three copper( II ) atoms are different, with four, five, or six coordination, adopting a distorted square pyramidal, tetrahedral, or octahedral geometry, respectively. From these results, it is found that the ditopic ligand L reacts with both soft and hard metal‐ion species to give diverse types of endocyclic complexes whose structures are also dependent on the anions used.