Structural diversity in the self-assembly of Ag(I) complexes containing 2-amino-5-halopyrimidine
The isomorphous complexes Ag( L- Cl) 2(CF 3SO 3) ( L- Cl = 2-amino-5-chloropyrimidine), 1, and Ag( L- Br) 2(CF 3SO 3) ( L- Br = 2-amino-5-bromopyrimidine), 2, are mononuclear, while [Ag( L- Br)(CF 3SO 3)] 6·6C 4H 10O, 3, and [Ag( L- I)(CF 3SO 3)] 6 ( L- I = 2-amino-5-iodopyrimidine), 4, show a cycli...
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Published in | Polyhedron Vol. 30; no. 13; pp. 2260 - 2267 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier Ltd
23.08.2011
|
Subjects | |
Online Access | Get full text |
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Summary: | The isomorphous complexes Ag(
L-
Cl)
2(CF
3SO
3) (
L-
Cl
=
2-amino-5-chloropyrimidine),
1, and Ag(
L-
Br)
2(CF
3SO
3) (
L-
Br
=
2-amino-5-bromopyrimidine),
2, are mononuclear, while [Ag(
L-
Br)(CF
3SO
3)]
6·6C
4H
10O,
3, and [Ag(
L-
I)(CF
3SO
3)]
6 (
L-
I
=
2-amino-5-iodopyrimidine),
4, show a cyclic self-assembly of six Ag(Ι) atoms and six
L-
X ligands, resulting in 24-membered metallocycles. The complex [Ag(
L-
I)(CF
3SO
3)]
∞,
5, forms 1D zigzag chains and the iodine atoms of the pyrimidyl rings coordinate to the silver atoms through C–I⋯Ag and Ag⋯O interactions, resulting in a 3D structure. The tetranuclear complexes [Ag(
L-
X)(NO
3)]
4 [X
=
Cl,
6; Br,
7] form 16-membered metallocycles, while [Ag(
L-
X)(ClO
4)]
∞ [X
=
Cl,
8; Br,
9] form helical chains. The different structure of
5 from
1 and
2 appears to be due to the stronger nucleophilic character of the iodine atom. In these complexes, the relatively smaller NO
3
− anions lead to the formation of tetranuclear metallocycles and the larger CF
3SO
3
− anions support hexanuclear metallocycles, whereas the ClO
4
− anions induce helical chains.
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► We report nine Ag(I) complexes containing the 2-amino-5-haloropyrimidine ligands. ► We examine the roles of halogen atom and anion in the structural types. ► Formation of strong Ag⋯I interaction is found for the iodo ligand. ► The size of the anion is important in determining the structural type.
A series of Ag(I) complexes containing the 2-amino-5-halopyrimidine ligands have been synthesized and their structures characterized by X-ray crystallography. The isomorphous complexes Ag(
L-
Cl)
2(CF
3SO
3) (
L-
Cl
=
2-amino-5-chloropyrimidine),
1, and Ag(
L-
Br)
2(CF
3SO
3) (
L-
Br
=
2-amino-5-bromopyrimidine),
2, are mononuclear, while [Ag(
L-
Br)(CF
3SO
3)]
6·6C
4H
10O,
3, and [Ag(
L-
I)(CF
3SO
3)]
6 (
L-
I
=
2-amino-5-iodopyrimidine),
4, show cyclic self-assembly of six Ag(Ι) atoms and six
L-
X ligands, resulting in 24-membered metallocycles. The complex [Ag(
L-
I)(CF
3SO
3)]
∞,
5, forms 1D zigzag chains which are linked through C–I⋯Ag and Ag⋯O interactions to form a 3D structure. The tetranuclear complexes [Ag(
L-
X)(NO
3)]
4 [X
=
Cl,
6; Br,
7] form 16-membered metallocycles, while [Ag(
L-
X)(ClO
4)]
∞ [X
=
Cl,
8; Br,
9] exhibit helical chains. The different structure of
5 from
1 and
2 appears to be due to the stronger nucleophilic character of the iodine atom. In these complexes, the relatively smaller NO
3
− anions lead to the formation of tetranuclear metallocycles and the larger CF
3SO
3
− anions support the hexanuclear metallocycles, whereas the ClO
4
− anions induce the helical chains. |
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ISSN: | 0277-5387 |
DOI: | 10.1016/j.poly.2011.06.016 |