A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry

Constantinos G. Efthymiou; Constantina Papatriantafyllopoulou; Nadia I. Alexopoulou; Catherine P. Raptopoulou; Roman Boča; Jerzy Mrozinski; Evangelos G. Bakalbassis; Spyros P. Perlepes

doi:10.1016/j.poly.2009.06.049

A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry

Constantinos G. Efthymiou
, Constantina Papatriantafyllopoulou
, Nadia I. Alexopoulou
, Catherine P. Raptopoulou
, Roman Boča
, Jerzy Mrozinski
, Evangelos G. Bakalbassis
, Spyros P. Perlepes

University of Patras
University of Florida
Institute of Materials Science, Athens
Slovak University of Technology in Bratislava
University of Wroclaw
Aristotle University of Thessaloniki

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

24 Citations (Scopus)

Abstract

The reactions of 2-(hydromethyl)pyridine, hmpH, with Ni(O₂CMe)₂·4H₂O in H₂O, in the absence of counterions, have been investigated. The synthetic study has led to the two new complexes [Ni(O₂CMe)₂(hmpH)₂] (1) and [Ni₄(O₂CMe)₄(hmp)₄(H ₂O)₂] (2). Complex 1 can also be transformed into 2 by reacting with an excess of NaOH in H₂O. The structures of 1 and 2·2.25H₂O·0.5(1,4-dioxane) have been solved by single-crystal, X-ray crystallography. The octahedral Ni^II center in centrosymmetric 1 is coordinated by two 1.10 (Harris notation) MeCO₂^- groups and two N,O-chelating (1.11) hpmH ligands. The tetranuclear cluster molecule of 2·2.25H₂O·0.5(1,4-dioxane) possesses a distorted cubane {Ni₄(μ₃-OR′)₄}⁴⁺ core [R′ = (2-pyridyl)CH₂-] with the Ni^II ions and the oxygen atoms from the 3.31 hmp^- ligands occupying alternate vertices of the cube. Two 2.11 MeCO₂^- groups cap two opposite faces of the cube, while two 1.10 MeCO₂^- ions and two aqua ligands complete the octahedral coordination sphere of the metal centers. Characteristic IR bands for the two complexes are discussed in terms of the nature of bonding and the structures of the two complexes. The variable-temperature magnetic properties of 2 have been modeled with two J values, and reveal antiferromagnetic exchange interactions between the four Ni² ions to give a diamagnetic ground state.

Original language	English
Pages (from-to)	3373-3381
Number of pages	9
Journal	Polyhedron
Volume	28
Issue number	15
DOIs	https://doi.org/10.1016/j.poly.2009.06.049
Publication status	Published - 13 Oct 2009
Externally published	Yes

Keywords

2-(Hydroxymethyl)pyridine metal complexes
Acetate ligands
Crystal structures
Magnetic properties
Nickel(II) cubane clusters

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10.1016/j.poly.2009.06.049

Cite this

@article{6f271777747a4a01ad0b93871750078a,

title = "A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry",

abstract = "The reactions of 2-(hydromethyl)pyridine, hmpH, with Ni(O2CMe)2·4H2O in H2O, in the absence of counterions, have been investigated. The synthetic study has led to the two new complexes [Ni(O2CMe)2(hmpH)2] (1) and [Ni4(O2CMe)4(hmp)4(H 2O)2] (2). Complex 1 can also be transformed into 2 by reacting with an excess of NaOH in H2O. The structures of 1 and 2·2.25H2O·0.5(1,4-dioxane) have been solved by single-crystal, X-ray crystallography. The octahedral NiII center in centrosymmetric 1 is coordinated by two 1.10 (Harris notation) MeCO2- groups and two N,O-chelating (1.11) hpmH ligands. The tetranuclear cluster molecule of 2·2.25H2O·0.5(1,4-dioxane) possesses a distorted cubane \{Ni4(μ3-OR′)4\}4+ core [R′ = (2-pyridyl)CH2-] with the NiII ions and the oxygen atoms from the 3.31 hmp- ligands occupying alternate vertices of the cube. Two 2.11 MeCO2- groups cap two opposite faces of the cube, while two 1.10 MeCO2- ions and two aqua ligands complete the octahedral coordination sphere of the metal centers. Characteristic IR bands for the two complexes are discussed in terms of the nature of bonding and the structures of the two complexes. The variable-temperature magnetic properties of 2 have been modeled with two J values, and reveal antiferromagnetic exchange interactions between the four Ni2 ions to give a diamagnetic ground state.",

keywords = "2-(Hydroxymethyl)pyridine metal complexes, Acetate ligands, Crystal structures, Magnetic properties, Nickel(II) cubane clusters",

author = "Efthymiou, \{Constantinos G.\} and Constantina Papatriantafyllopoulou and Alexopoulou, \{Nadia I.\} and Raptopoulou, \{Catherine P.\} and Roman Bo{\v c}a and Jerzy Mrozinski and Bakalbassis, \{Evangelos G.\} and Perlepes, \{Spyros P.\}",

year = "2009",

month = oct,

day = "13",

doi = "10.1016/j.poly.2009.06.049",

language = "English",

volume = "28",

pages = "3373--3381",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

number = "15",

}

A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry. / Efthymiou, Constantinos G.; Papatriantafyllopoulou, Constantina; Alexopoulou, Nadia I. et al.
In: Polyhedron, Vol. 28, No. 15, 13.10.2009, p. 3373-3381.

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

TY - JOUR

T1 - A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry

AU - Efthymiou, Constantinos G.

AU - Papatriantafyllopoulou, Constantina

AU - Alexopoulou, Nadia I.

AU - Raptopoulou, Catherine P.

AU - Boča, Roman

AU - Mrozinski, Jerzy

AU - Bakalbassis, Evangelos G.

AU - Perlepes, Spyros P.

PY - 2009/10/13

Y1 - 2009/10/13

N2 - The reactions of 2-(hydromethyl)pyridine, hmpH, with Ni(O2CMe)2·4H2O in H2O, in the absence of counterions, have been investigated. The synthetic study has led to the two new complexes [Ni(O2CMe)2(hmpH)2] (1) and [Ni4(O2CMe)4(hmp)4(H 2O)2] (2). Complex 1 can also be transformed into 2 by reacting with an excess of NaOH in H2O. The structures of 1 and 2·2.25H2O·0.5(1,4-dioxane) have been solved by single-crystal, X-ray crystallography. The octahedral NiII center in centrosymmetric 1 is coordinated by two 1.10 (Harris notation) MeCO2- groups and two N,O-chelating (1.11) hpmH ligands. The tetranuclear cluster molecule of 2·2.25H2O·0.5(1,4-dioxane) possesses a distorted cubane {Ni4(μ3-OR′)4}4+ core [R′ = (2-pyridyl)CH2-] with the NiII ions and the oxygen atoms from the 3.31 hmp- ligands occupying alternate vertices of the cube. Two 2.11 MeCO2- groups cap two opposite faces of the cube, while two 1.10 MeCO2- ions and two aqua ligands complete the octahedral coordination sphere of the metal centers. Characteristic IR bands for the two complexes are discussed in terms of the nature of bonding and the structures of the two complexes. The variable-temperature magnetic properties of 2 have been modeled with two J values, and reveal antiferromagnetic exchange interactions between the four Ni2 ions to give a diamagnetic ground state.

AB - The reactions of 2-(hydromethyl)pyridine, hmpH, with Ni(O2CMe)2·4H2O in H2O, in the absence of counterions, have been investigated. The synthetic study has led to the two new complexes [Ni(O2CMe)2(hmpH)2] (1) and [Ni4(O2CMe)4(hmp)4(H 2O)2] (2). Complex 1 can also be transformed into 2 by reacting with an excess of NaOH in H2O. The structures of 1 and 2·2.25H2O·0.5(1,4-dioxane) have been solved by single-crystal, X-ray crystallography. The octahedral NiII center in centrosymmetric 1 is coordinated by two 1.10 (Harris notation) MeCO2- groups and two N,O-chelating (1.11) hpmH ligands. The tetranuclear cluster molecule of 2·2.25H2O·0.5(1,4-dioxane) possesses a distorted cubane {Ni4(μ3-OR′)4}4+ core [R′ = (2-pyridyl)CH2-] with the NiII ions and the oxygen atoms from the 3.31 hmp- ligands occupying alternate vertices of the cube. Two 2.11 MeCO2- groups cap two opposite faces of the cube, while two 1.10 MeCO2- ions and two aqua ligands complete the octahedral coordination sphere of the metal centers. Characteristic IR bands for the two complexes are discussed in terms of the nature of bonding and the structures of the two complexes. The variable-temperature magnetic properties of 2 have been modeled with two J values, and reveal antiferromagnetic exchange interactions between the four Ni2 ions to give a diamagnetic ground state.

KW - 2-(Hydroxymethyl)pyridine metal complexes

KW - Acetate ligands

KW - Crystal structures

KW - Magnetic properties

KW - Nickel(II) cubane clusters

UR - https://www.scopus.com/pages/publications/70349772248

U2 - 10.1016/j.poly.2009.06.049

DO - 10.1016/j.poly.2009.06.049

M3 - Article

SN - 0277-5387

VL - 28

SP - 3373

EP - 3381

JO - Polyhedron

JF - Polyhedron

IS - 15

ER -

A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II) carboxylate chemistry

Abstract

Keywords

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