Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co)

Amrita Das, Biswajit Dey, Atish Dipankar Jana, Joanna Hemming, Madeleine Helliwell, Hon Man Lee, Tsun Hung Hsiao, Eringathodi Suresh, Enrique Colacio, Somnath Ray Choudhury, Subrata Mukhopadhyay

Research output: Contribution to journalArticle

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Abstract

Three metal complexes containing malonate as primary ligand and 4-aminopyridine as secondary ligand (counter ion) namely, {(ampyH)2[Cu(mal)2]}n (1), (ampyH)2[Ni(mal)2(H2O)2] (2) and (ampyH)2[Co(mal)2(H2O)2] (3) [ampyH = protonated 4-aminopyridine, malH2 = malonic acid] have been synthesized from purely aqueous media and their crystal structures have been determined by single crystal X-ray diffraction. The copper complex is polymeric, whereas the nickel and cobalt complexes are monomeric in nature. The most striking feature of the present study is the observed ligand induced topological variations of the [Cu(mal)2]2- unit, which is the building block not only for 1, but for several other copper-malonate complexes previously synthesized by us. It is also observed that this influence of the ligand is not reflected in the primary coordination of the analogs Ni(II) and Co(II) complexes, as the same monomeric unit [M(II)(mal)2(H2O)2]2-, [M = Ni/Co] exists not only in 2 and 3, but also in other Ni and Co complexes prepared by us, although there are subtle differences in the overall supramolecular arrangements in the solid state of these complexes (Ni and Co). Starting with 2-amino-4-picoline molecule as an auxiliary ligand [S. Ray Choudhury, A.D. Jana, E. Colacio, H.M. Lee, G. Mostafa, S. Mukhopadhyay, Cryst. Growth Des. 7 (2007) 212], we have found that protonated heterocyclic bases (2-amino-4-picoline and 2-aminopyridine) have a preferred hydrogen bonded recognition motif R2 2 (8) with metal carboxylate frameworks, which has an important role in guiding the crystal packing in the solid state. In the present study, we have extended our investigation by choosing 4-aminopyridine as an auxiliary ligand and discuss its effect in the overall self-assembly. A comprehensive comparison of the present complexes with our previously reported related complexes revealed the delicate nature of the self-assembly process.

Original languageEnglish
Pages (from-to)1317-1325
Number of pages9
JournalPolyhedron
Volume29
Issue number4
DOIs
Publication statusPublished - 2010 Mar 10

Fingerprint

Aminopyridines
divergence
Ligands
4-Aminopyridine
ligands
Self assembly
self assembly
Copper
solid state
copper
Radiation counters
Coordination Complexes
Metal complexes
Cobalt
Nickel
metals
carboxylates
malonic acid
Hydrogen
rays

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Das, Amrita ; Dey, Biswajit ; Jana, Atish Dipankar ; Hemming, Joanna ; Helliwell, Madeleine ; Lee, Hon Man ; Hsiao, Tsun Hung ; Suresh, Eringathodi ; Colacio, Enrique ; Choudhury, Somnath Ray ; Mukhopadhyay, Subrata. / Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co). In: Polyhedron. 2010 ; Vol. 29, No. 4. pp. 1317-1325.
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title = "Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co)",
abstract = "Three metal complexes containing malonate as primary ligand and 4-aminopyridine as secondary ligand (counter ion) namely, {(ampyH)2[Cu(mal)2]}n (1), (ampyH)2[Ni(mal)2(H2O)2] (2) and (ampyH)2[Co(mal)2(H2O)2] (3) [ampyH = protonated 4-aminopyridine, malH2 = malonic acid] have been synthesized from purely aqueous media and their crystal structures have been determined by single crystal X-ray diffraction. The copper complex is polymeric, whereas the nickel and cobalt complexes are monomeric in nature. The most striking feature of the present study is the observed ligand induced topological variations of the [Cu(mal)2]2- unit, which is the building block not only for 1, but for several other copper-malonate complexes previously synthesized by us. It is also observed that this influence of the ligand is not reflected in the primary coordination of the analogs Ni(II) and Co(II) complexes, as the same monomeric unit [M(II)(mal)2(H2O)2]2-, [M = Ni/Co] exists not only in 2 and 3, but also in other Ni and Co complexes prepared by us, although there are subtle differences in the overall supramolecular arrangements in the solid state of these complexes (Ni and Co). Starting with 2-amino-4-picoline molecule as an auxiliary ligand [S. Ray Choudhury, A.D. Jana, E. Colacio, H.M. Lee, G. Mostafa, S. Mukhopadhyay, Cryst. Growth Des. 7 (2007) 212], we have found that protonated heterocyclic bases (2-amino-4-picoline and 2-aminopyridine) have a preferred hydrogen bonded recognition motif R2 2 (8) with metal carboxylate frameworks, which has an important role in guiding the crystal packing in the solid state. In the present study, we have extended our investigation by choosing 4-aminopyridine as an auxiliary ligand and discuss its effect in the overall self-assembly. A comprehensive comparison of the present complexes with our previously reported related complexes revealed the delicate nature of the self-assembly process.",
author = "Amrita Das and Biswajit Dey and Jana, {Atish Dipankar} and Joanna Hemming and Madeleine Helliwell and Lee, {Hon Man} and Hsiao, {Tsun Hung} and Eringathodi Suresh and Enrique Colacio and Choudhury, {Somnath Ray} and Subrata Mukhopadhyay",
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Das, A, Dey, B, Jana, AD, Hemming, J, Helliwell, M, Lee, HM, Hsiao, TH, Suresh, E, Colacio, E, Choudhury, SR & Mukhopadhyay, S 2010, 'Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co)', Polyhedron, vol. 29, no. 4, pp. 1317-1325. https://doi.org/10.1016/j.poly.2009.12.011

Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co). / Das, Amrita; Dey, Biswajit; Jana, Atish Dipankar; Hemming, Joanna; Helliwell, Madeleine; Lee, Hon Man; Hsiao, Tsun Hung; Suresh, Eringathodi; Colacio, Enrique; Choudhury, Somnath Ray; Mukhopadhyay, Subrata.

In: Polyhedron, Vol. 29, No. 4, 10.03.2010, p. 1317-1325.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Effect of protonated aminopyridines on the structural divergences of M(II)-malonate complexes (M = Cu, Ni, Co)

AU - Das, Amrita

AU - Dey, Biswajit

AU - Jana, Atish Dipankar

AU - Hemming, Joanna

AU - Helliwell, Madeleine

AU - Lee, Hon Man

AU - Hsiao, Tsun Hung

AU - Suresh, Eringathodi

AU - Colacio, Enrique

AU - Choudhury, Somnath Ray

AU - Mukhopadhyay, Subrata

PY - 2010/3/10

Y1 - 2010/3/10

N2 - Three metal complexes containing malonate as primary ligand and 4-aminopyridine as secondary ligand (counter ion) namely, {(ampyH)2[Cu(mal)2]}n (1), (ampyH)2[Ni(mal)2(H2O)2] (2) and (ampyH)2[Co(mal)2(H2O)2] (3) [ampyH = protonated 4-aminopyridine, malH2 = malonic acid] have been synthesized from purely aqueous media and their crystal structures have been determined by single crystal X-ray diffraction. The copper complex is polymeric, whereas the nickel and cobalt complexes are monomeric in nature. The most striking feature of the present study is the observed ligand induced topological variations of the [Cu(mal)2]2- unit, which is the building block not only for 1, but for several other copper-malonate complexes previously synthesized by us. It is also observed that this influence of the ligand is not reflected in the primary coordination of the analogs Ni(II) and Co(II) complexes, as the same monomeric unit [M(II)(mal)2(H2O)2]2-, [M = Ni/Co] exists not only in 2 and 3, but also in other Ni and Co complexes prepared by us, although there are subtle differences in the overall supramolecular arrangements in the solid state of these complexes (Ni and Co). Starting with 2-amino-4-picoline molecule as an auxiliary ligand [S. Ray Choudhury, A.D. Jana, E. Colacio, H.M. Lee, G. Mostafa, S. Mukhopadhyay, Cryst. Growth Des. 7 (2007) 212], we have found that protonated heterocyclic bases (2-amino-4-picoline and 2-aminopyridine) have a preferred hydrogen bonded recognition motif R2 2 (8) with metal carboxylate frameworks, which has an important role in guiding the crystal packing in the solid state. In the present study, we have extended our investigation by choosing 4-aminopyridine as an auxiliary ligand and discuss its effect in the overall self-assembly. A comprehensive comparison of the present complexes with our previously reported related complexes revealed the delicate nature of the self-assembly process.

AB - Three metal complexes containing malonate as primary ligand and 4-aminopyridine as secondary ligand (counter ion) namely, {(ampyH)2[Cu(mal)2]}n (1), (ampyH)2[Ni(mal)2(H2O)2] (2) and (ampyH)2[Co(mal)2(H2O)2] (3) [ampyH = protonated 4-aminopyridine, malH2 = malonic acid] have been synthesized from purely aqueous media and their crystal structures have been determined by single crystal X-ray diffraction. The copper complex is polymeric, whereas the nickel and cobalt complexes are monomeric in nature. The most striking feature of the present study is the observed ligand induced topological variations of the [Cu(mal)2]2- unit, which is the building block not only for 1, but for several other copper-malonate complexes previously synthesized by us. It is also observed that this influence of the ligand is not reflected in the primary coordination of the analogs Ni(II) and Co(II) complexes, as the same monomeric unit [M(II)(mal)2(H2O)2]2-, [M = Ni/Co] exists not only in 2 and 3, but also in other Ni and Co complexes prepared by us, although there are subtle differences in the overall supramolecular arrangements in the solid state of these complexes (Ni and Co). Starting with 2-amino-4-picoline molecule as an auxiliary ligand [S. Ray Choudhury, A.D. Jana, E. Colacio, H.M. Lee, G. Mostafa, S. Mukhopadhyay, Cryst. Growth Des. 7 (2007) 212], we have found that protonated heterocyclic bases (2-amino-4-picoline and 2-aminopyridine) have a preferred hydrogen bonded recognition motif R2 2 (8) with metal carboxylate frameworks, which has an important role in guiding the crystal packing in the solid state. In the present study, we have extended our investigation by choosing 4-aminopyridine as an auxiliary ligand and discuss its effect in the overall self-assembly. A comprehensive comparison of the present complexes with our previously reported related complexes revealed the delicate nature of the self-assembly process.

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