Experimental observation of supramolecular carbonyl-π/π-π/ π-carbonyl and carbonyl-π/π-π/π-anion assemblies supported by theoretical studies

Somnath Ray Choudhury, Patrick Gamez, Arturo Robertazzi, Chih Yuan Chen, Hon Man Lee, Subrata Mukhopadhyay

Research output: Contribution to journalArticle

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Abstract

Mononuclear nickel(II) and copper(II) complexes, namely, (C 6H9N2)2[Ni(ntaH)2] (1), (C5H7N2)2[Cu(mal)2(H 2O)2] (2), and (C5H7N 2)4[Ni(mal)2(H2O) 2](NO3)2 (3) [ntaH3 = nitrilotriacetic acid; C6H8N2H = protonated 2-amino-4-picoline; malH2 = malonic acid; C5H 7N2 = protonated 2-aminopyridine] have been synthesized in water and their crystal structures have been determined by single crystal X-ray diffraction. In all the complexes, robust bimolecular cyclic hydrogen bonding R22(8) motifs are observed between the protonated heteroaromatic N-rings and the metal-carboxylate complexes. Moreover, the aromatic molecules are engaged in carbonyl⋯ π and ⋯π interactions with the noncoordinated carbonyl moieties of the metal complexes and with a nitrate ion respectively, giving rise to remarkable carbonyl ⋯π/π⋯π/carbonyl⋯π and carbonyl ⋯π/π⋯π/π⋯-anion interactions having sandwich type topologies. In 1 and 3, the carbonyl ⋯π interactions are one of the weak forces responsible for the stabilization of the final assemblies, whereas in 2, it strongly contributes to the stabilization of the one-dimensional tape generated from monomeric [Cu(mal)2(H 2O)2]2- units. Density functional theory studies reveal a high stability of the unique lone pair ⋯π/ π⋯π/lone pair ⋯π supramolecular self-assembly observed in compound 2 and confirm the favorable formation of the lone pair ⋯π/π⋯π/π⋯anion array present in compound 3. Compounds 1-3 are compared in terms of synthetic aspects and supramolecular interactions with analogous complexes, that is, {[Cu(mal)2](picH) 2· 5H2O}n (4), {[Cu(mal) 2](picH)2· 2H2O}n (5), (picH)2[M(mal)2(H2O)2] ·4H2O (M = Ni/Co/Mn) (6-8), recently obtained with picoline (picH = protonated picoline). The self-assembly pathways involved in the recognition of the heterocyclic amines by the metal-carboxylate complexes and the occurrence of lone pair (l.p.)⋯π and anion ⋯π interactions are examined and related.

Original languageEnglish
Pages (from-to)3773-3784
Number of pages12
JournalCrystal Growth and Design
Volume8
Issue number10
DOIs
Publication statusPublished - 2008 Oct 1

Fingerprint

Picolines
Metal complexes
assemblies
Anions
Negative ions
anions
Self assembly
Stabilization
Nitrilotriacetic Acid
Acids
Coordination Complexes
carboxylates
interactions
self assembly
Nickel
Nitrates
Tapes
stabilization
Amines
Density functional theory

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Choudhury, Somnath Ray ; Gamez, Patrick ; Robertazzi, Arturo ; Chen, Chih Yuan ; Lee, Hon Man ; Mukhopadhyay, Subrata. / Experimental observation of supramolecular carbonyl-π/π-π/ π-carbonyl and carbonyl-π/π-π/π-anion assemblies supported by theoretical studies. In: Crystal Growth and Design. 2008 ; Vol. 8, No. 10. pp. 3773-3784.
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title = "Experimental observation of supramolecular carbonyl-π/π-π/ π-carbonyl and carbonyl-π/π-π/π-anion assemblies supported by theoretical studies",
abstract = "Mononuclear nickel(II) and copper(II) complexes, namely, (C 6H9N2)2[Ni(ntaH)2] (1), (C5H7N2)2[Cu(mal)2(H 2O)2] (2), and (C5H7N 2)4[Ni(mal)2(H2O) 2](NO3)2 (3) [ntaH3 = nitrilotriacetic acid; C6H8N2H = protonated 2-amino-4-picoline; malH2 = malonic acid; C5H 7N2 = protonated 2-aminopyridine] have been synthesized in water and their crystal structures have been determined by single crystal X-ray diffraction. In all the complexes, robust bimolecular cyclic hydrogen bonding R22(8) motifs are observed between the protonated heteroaromatic N-rings and the metal-carboxylate complexes. Moreover, the aromatic molecules are engaged in carbonyl⋯ π and ⋯π interactions with the noncoordinated carbonyl moieties of the metal complexes and with a nitrate ion respectively, giving rise to remarkable carbonyl ⋯π/π⋯π/carbonyl⋯π and carbonyl ⋯π/π⋯π/π⋯-anion interactions having sandwich type topologies. In 1 and 3, the carbonyl ⋯π interactions are one of the weak forces responsible for the stabilization of the final assemblies, whereas in 2, it strongly contributes to the stabilization of the one-dimensional tape generated from monomeric [Cu(mal)2(H 2O)2]2- units. Density functional theory studies reveal a high stability of the unique lone pair ⋯π/ π⋯π/lone pair ⋯π supramolecular self-assembly observed in compound 2 and confirm the favorable formation of the lone pair ⋯π/π⋯π/π⋯anion array present in compound 3. Compounds 1-3 are compared in terms of synthetic aspects and supramolecular interactions with analogous complexes, that is, {[Cu(mal)2](picH) 2· 5H2O}n (4), {[Cu(mal) 2](picH)2· 2H2O}n (5), (picH)2[M(mal)2(H2O)2] ·4H2O (M = Ni/Co/Mn) (6-8), recently obtained with picoline (picH = protonated picoline). The self-assembly pathways involved in the recognition of the heterocyclic amines by the metal-carboxylate complexes and the occurrence of lone pair (l.p.)⋯π and anion ⋯π interactions are examined and related.",
author = "Choudhury, {Somnath Ray} and Patrick Gamez and Arturo Robertazzi and Chen, {Chih Yuan} and Lee, {Hon Man} and Subrata Mukhopadhyay",
year = "2008",
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journal = "Crystal Growth and Design",
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Experimental observation of supramolecular carbonyl-π/π-π/ π-carbonyl and carbonyl-π/π-π/π-anion assemblies supported by theoretical studies. / Choudhury, Somnath Ray; Gamez, Patrick; Robertazzi, Arturo; Chen, Chih Yuan; Lee, Hon Man; Mukhopadhyay, Subrata.

In: Crystal Growth and Design, Vol. 8, No. 10, 01.10.2008, p. 3773-3784.

Research output: Contribution to journalArticle

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T1 - Experimental observation of supramolecular carbonyl-π/π-π/ π-carbonyl and carbonyl-π/π-π/π-anion assemblies supported by theoretical studies

AU - Choudhury, Somnath Ray

AU - Gamez, Patrick

AU - Robertazzi, Arturo

AU - Chen, Chih Yuan

AU - Lee, Hon Man

AU - Mukhopadhyay, Subrata

PY - 2008/10/1

Y1 - 2008/10/1

N2 - Mononuclear nickel(II) and copper(II) complexes, namely, (C 6H9N2)2[Ni(ntaH)2] (1), (C5H7N2)2[Cu(mal)2(H 2O)2] (2), and (C5H7N 2)4[Ni(mal)2(H2O) 2](NO3)2 (3) [ntaH3 = nitrilotriacetic acid; C6H8N2H = protonated 2-amino-4-picoline; malH2 = malonic acid; C5H 7N2 = protonated 2-aminopyridine] have been synthesized in water and their crystal structures have been determined by single crystal X-ray diffraction. In all the complexes, robust bimolecular cyclic hydrogen bonding R22(8) motifs are observed between the protonated heteroaromatic N-rings and the metal-carboxylate complexes. Moreover, the aromatic molecules are engaged in carbonyl⋯ π and ⋯π interactions with the noncoordinated carbonyl moieties of the metal complexes and with a nitrate ion respectively, giving rise to remarkable carbonyl ⋯π/π⋯π/carbonyl⋯π and carbonyl ⋯π/π⋯π/π⋯-anion interactions having sandwich type topologies. In 1 and 3, the carbonyl ⋯π interactions are one of the weak forces responsible for the stabilization of the final assemblies, whereas in 2, it strongly contributes to the stabilization of the one-dimensional tape generated from monomeric [Cu(mal)2(H 2O)2]2- units. Density functional theory studies reveal a high stability of the unique lone pair ⋯π/ π⋯π/lone pair ⋯π supramolecular self-assembly observed in compound 2 and confirm the favorable formation of the lone pair ⋯π/π⋯π/π⋯anion array present in compound 3. Compounds 1-3 are compared in terms of synthetic aspects and supramolecular interactions with analogous complexes, that is, {[Cu(mal)2](picH) 2· 5H2O}n (4), {[Cu(mal) 2](picH)2· 2H2O}n (5), (picH)2[M(mal)2(H2O)2] ·4H2O (M = Ni/Co/Mn) (6-8), recently obtained with picoline (picH = protonated picoline). The self-assembly pathways involved in the recognition of the heterocyclic amines by the metal-carboxylate complexes and the occurrence of lone pair (l.p.)⋯π and anion ⋯π interactions are examined and related.

AB - Mononuclear nickel(II) and copper(II) complexes, namely, (C 6H9N2)2[Ni(ntaH)2] (1), (C5H7N2)2[Cu(mal)2(H 2O)2] (2), and (C5H7N 2)4[Ni(mal)2(H2O) 2](NO3)2 (3) [ntaH3 = nitrilotriacetic acid; C6H8N2H = protonated 2-amino-4-picoline; malH2 = malonic acid; C5H 7N2 = protonated 2-aminopyridine] have been synthesized in water and their crystal structures have been determined by single crystal X-ray diffraction. In all the complexes, robust bimolecular cyclic hydrogen bonding R22(8) motifs are observed between the protonated heteroaromatic N-rings and the metal-carboxylate complexes. Moreover, the aromatic molecules are engaged in carbonyl⋯ π and ⋯π interactions with the noncoordinated carbonyl moieties of the metal complexes and with a nitrate ion respectively, giving rise to remarkable carbonyl ⋯π/π⋯π/carbonyl⋯π and carbonyl ⋯π/π⋯π/π⋯-anion interactions having sandwich type topologies. In 1 and 3, the carbonyl ⋯π interactions are one of the weak forces responsible for the stabilization of the final assemblies, whereas in 2, it strongly contributes to the stabilization of the one-dimensional tape generated from monomeric [Cu(mal)2(H 2O)2]2- units. Density functional theory studies reveal a high stability of the unique lone pair ⋯π/ π⋯π/lone pair ⋯π supramolecular self-assembly observed in compound 2 and confirm the favorable formation of the lone pair ⋯π/π⋯π/π⋯anion array present in compound 3. Compounds 1-3 are compared in terms of synthetic aspects and supramolecular interactions with analogous complexes, that is, {[Cu(mal)2](picH) 2· 5H2O}n (4), {[Cu(mal) 2](picH)2· 2H2O}n (5), (picH)2[M(mal)2(H2O)2] ·4H2O (M = Ni/Co/Mn) (6-8), recently obtained with picoline (picH = protonated picoline). The self-assembly pathways involved in the recognition of the heterocyclic amines by the metal-carboxylate complexes and the occurrence of lone pair (l.p.)⋯π and anion ⋯π interactions are examined and related.

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