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Study of the complex formation between the [Cu(bpca)] + secondary building unit and the aromatic N donors 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) and 1,3-bis(4-pyridyl)propane (bpp)
Two new complexes of the formula [{Cu(bpca)} 2 (μ-tppz)](NO 3 ) 2 ·5H 2 O ( 1 ) and [Cu(bpca)(H 2 O)(ClO 4 )(μ-bpp)Cu(bpca)(H 2 O) 2 ]ClO 4 ·H 2 O ( 2 ) [tppz = 2,3,5,6-tetra(2-pyridyl)pyrazine and bpp = 1,3-bis(4-pyridyl)propane] have been prepared by the reaction of the [Cu(bpca)] + [Hbpca = bis(2...
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| Published in: | CrystEngComm 2017, Vol.19 (36), p.5460-5472 |
|---|---|
| Main Authors: | , , , , , , , , , |
| Format: | Article |
| Language: | English |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Two new complexes of the formula [{Cu(bpca)}
2
(μ-tppz)](NO
3
)
2
·5H
2
O (
1
) and [Cu(bpca)(H
2
O)(ClO
4
)(μ-bpp)Cu(bpca)(H
2
O)
2
]ClO
4
·H
2
O (
2
) [tppz = 2,3,5,6-tetra(2-pyridyl)pyrazine and bpp = 1,3-bis(4-pyridyl)propane] have been prepared by the reaction of the [Cu(bpca)]
+
[Hbpca = bis(2-pyridylcarbonyl)imide] building block and the tppz and bpp N donors. An unusual coordination mode of the tppz ligand was observed in
1
, which functions as a bis(bidentate) ligand to two copper(
ii
) atoms each coordinated to a nitrogen atom of the pyrazine moiety and a pyridyl nitrogen atom. This compound presents a layered structure of alternating anionic (
ca.
1.6 Å) and cationic (
ca.
10 Å) slices, providing the opportunity to obtain isomorphic structures by exchanging the counterion, the solvent or both of them. As in
1
, each bpca group in
2
is the end-cap ligand being coordinated to the copper(
ii
) ion through its three nitrogen atoms in equatorial positions. The supramolecular layers in
2
are filled by the disordered water molecules and one of the perchlorate groups where the volume occupied by the disordered water can be considered as a void of 91.9 Å
3
. Additionally, the very weak antiferromagnetic couplings observed in
1
[
J
= −0.16] and
2
[
J
= −0.41 cm
−1
] can be understood by simple orbital symmetry considerations about the type and orientation of the magnetic orbital at each copper(
ii
) ion in both compounds which provide a clear picture of the poor ability of the involved bridges in mediating electronic effects between the paramagnetic centers. |
|---|---|
| ISSN: | 1466-8033 1466-8033 |
| DOI: | 10.1039/C7CE01230F |