Magneto-structural studies of two new cobalt(ii)-N,N-diisobutylisonicotinamide compounds: [CoLCl2]n and [Co(L)2(H2O)4][CoLBr3]2·2H2OElectronic supplementary information (ESI) available: CCDC reference numbers 808174-808175. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt10991j
Two similar synthetic pathways using the ligand N , N -diisobutylisonicotinamide (L) with anhydrous CoX 2 salts (being X = Cl − , Br − ) led to different species: a one-dimensional system, [CoLCl 2 ] n , 1 , and an ionic product [Co(L) 2 (H 2 O) 4 ][CoLBr 3 ] 2 ·2H 2 O, 2 , respectively. Compound 1...
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Format | Journal Article |
Language | English |
Published |
18.11.2011
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Abstract | Two similar synthetic pathways using the ligand
N
,
N
-diisobutylisonicotinamide (L) with anhydrous CoX
2
salts (being X = Cl
−
, Br
−
) led to different species: a one-dimensional system, [CoLCl
2
]
n
,
1
, and an ionic product [Co(L)
2
(H
2
O)
4
][CoLBr
3
]
2
·2H
2
O,
2
, respectively. Compound
1
is a polymer in which ligand L coordinates to tetrahedral Co
II
ions in a bidentate bridging fashion using the pyridine nitrogen and carbonyl oxygen atoms. Compound
2
consists of one octahedral cationic [Co(L)
2
(H
2
O)
4
]
2+
entity and two tetrahedral anionic [CoLBr
3
]
−
units. In this system, the ligand molecules coordinate only through the pyridine nitrogen atoms. The magnetic properties of
1
and
2
were investigated in the temperature range of 2.0 to 300.0 K and correlations between both (due to the existence of similar features) examined. The study of the magnetic properties of
1
was carried out by considering each Co
II
ion as a perfectly isolated system, hence,
J
= 0, but taking into account a significant zero-field splitting contribution due to distortions on the tetrahedral environment of the cobalt atoms. The fit of the magnetic susceptibility data together with reduced magnetization
vs H
/
T
measurements provided similar parameters (|
D
| = 10.8 cm
−1
,
g
= 1.92,
g
|
= 2.92 for the former and |
D
| = 11.04 cm
−1
and
g
= 2.05 for the latter, respectively). On the other hand, the magnetic response of compound
2
has been analyzed using a model which considers the presence of two tetrahedral and one octahedral Co(
ii
) ions (Co
Td
and Co
Oh
). The study was carried out in two separated blocks, above and below 80 K, where only the most significant effects at each interval of temperature were considered. As a result, the analysis of the magnetic data shows weak antiferromagnetic interactions between the Co
Oh
and the two Co
Td
ions (
J
= −0.41 cm
−1
) in
2
. The best fit parameters were
g
Co
Td
= 2.89,
g
Co
Oh
= 3.50, |
D
Co
Td
| = 10.62 cm
−1
, |
E
Co
Td
| = 2.95 cm
−1
, Δ = 240.9 cm
−1
and
J
L-S
= −107.1 cm
−1
, from where
λ
was calculated with a final value of −144.8 cm
−1
(
J
L-S
=
Aκλ
). The approximations performed to obtain these values provide reasonable results in agreement with compound
1
and also to other systems in the literature.
Structural and magnetic properties of two new Co(
ii
) compounds containing
N
,
N
-diisobutylisonicotinamide as the coordinating ligand. |
---|---|
AbstractList | Two similar synthetic pathways using the ligand
N
,
N
-diisobutylisonicotinamide (L) with anhydrous CoX
2
salts (being X = Cl
−
, Br
−
) led to different species: a one-dimensional system, [CoLCl
2
]
n
,
1
, and an ionic product [Co(L)
2
(H
2
O)
4
][CoLBr
3
]
2
·2H
2
O,
2
, respectively. Compound
1
is a polymer in which ligand L coordinates to tetrahedral Co
II
ions in a bidentate bridging fashion using the pyridine nitrogen and carbonyl oxygen atoms. Compound
2
consists of one octahedral cationic [Co(L)
2
(H
2
O)
4
]
2+
entity and two tetrahedral anionic [CoLBr
3
]
−
units. In this system, the ligand molecules coordinate only through the pyridine nitrogen atoms. The magnetic properties of
1
and
2
were investigated in the temperature range of 2.0 to 300.0 K and correlations between both (due to the existence of similar features) examined. The study of the magnetic properties of
1
was carried out by considering each Co
II
ion as a perfectly isolated system, hence,
J
= 0, but taking into account a significant zero-field splitting contribution due to distortions on the tetrahedral environment of the cobalt atoms. The fit of the magnetic susceptibility data together with reduced magnetization
vs H
/
T
measurements provided similar parameters (|
D
| = 10.8 cm
−1
,
g
= 1.92,
g
|
= 2.92 for the former and |
D
| = 11.04 cm
−1
and
g
= 2.05 for the latter, respectively). On the other hand, the magnetic response of compound
2
has been analyzed using a model which considers the presence of two tetrahedral and one octahedral Co(
ii
) ions (Co
Td
and Co
Oh
). The study was carried out in two separated blocks, above and below 80 K, where only the most significant effects at each interval of temperature were considered. As a result, the analysis of the magnetic data shows weak antiferromagnetic interactions between the Co
Oh
and the two Co
Td
ions (
J
= −0.41 cm
−1
) in
2
. The best fit parameters were
g
Co
Td
= 2.89,
g
Co
Oh
= 3.50, |
D
Co
Td
| = 10.62 cm
−1
, |
E
Co
Td
| = 2.95 cm
−1
, Δ = 240.9 cm
−1
and
J
L-S
= −107.1 cm
−1
, from where
λ
was calculated with a final value of −144.8 cm
−1
(
J
L-S
=
Aκλ
). The approximations performed to obtain these values provide reasonable results in agreement with compound
1
and also to other systems in the literature.
Structural and magnetic properties of two new Co(
ii
) compounds containing
N
,
N
-diisobutylisonicotinamide as the coordinating ligand. |
Author | Singh Pannu, Ajay Pal Kapoor, Pratibha Hundal, Geeta Aliaga-Alcalde, Núria Singh Hundal, Maninder Corbella, Montserrat Kapoor, Ramesh |
AuthorAffiliation | Department of Chemistry Department de Química Inorgànica Universitat de Barcelona (UB) ICREA Junior Researcher at the UB (ICREA: Institució Catalana de Recerca i Estudis Avançats) Indian Institute of Science Education and Research Guru Nanak Dev University Panjab University |
AuthorAffiliation_xml | – name: Universitat de Barcelona (UB) – name: Department of Chemistry – name: Guru Nanak Dev University – name: ICREA Junior Researcher at the UB (ICREA: Institució Catalana de Recerca i Estudis Avançats) – name: Indian Institute of Science Education and Research – name: Department de Química Inorgànica – name: Panjab University |
Author_xml | – sequence: 1 givenname: Ajay Pal surname: Singh Pannu fullname: Singh Pannu, Ajay Pal – sequence: 2 givenname: Pratibha surname: Kapoor fullname: Kapoor, Pratibha – sequence: 3 givenname: Geeta surname: Hundal fullname: Hundal, Geeta – sequence: 4 givenname: Ramesh surname: Kapoor fullname: Kapoor, Ramesh – sequence: 5 givenname: Montserrat surname: Corbella fullname: Corbella, Montserrat – sequence: 6 givenname: Núria surname: Aliaga-Alcalde fullname: Aliaga-Alcalde, Núria – sequence: 7 givenname: Maninder surname: Singh Hundal fullname: Singh Hundal, Maninder |
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ContentType | Journal Article |
DOI | 10.1039/c1dt10991j |
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Discipline | Chemistry |
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Notes | For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: CCDC reference numbers 10.1039/c1dt10991j 808174-808175 |
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PublicationYear | 2011 |
References_xml | – issn: 2003 publication-title: VPMAG doi: Cano – issn: 1984 publication-title: Chemistry of the Elements doi: Greenwood Earnshaw – issn: 1987 end-page: 4 publication-title: Section-4 Inorganic Chemistry. Langes Handbook of Chemistry doi: Dean – issn: 1993 publication-title: Molecular Magnetism doi: Kahn – issn: 2000 publication-title: Molecular Magnetism, New Magnetic Materials doi: Itoh Kinoshita – issn: 2001 publication-title: Magnetism in Condensed Matter doi: Blundell – issn: 1997 publication-title: SHELX-97: Program for Solution and Refinement of Crystal Structures doi: Sheldrick – doi: Rivière – issn: 2000 publication-title: Metal-Organic and Organic Molecular Magnets – issn: 1984 publication-title: Inorganic Electronic Spectroscopy doi: Lever – issn: 1964 publication-title: The Theory of Transition-Metal ions doi: Griffith |
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Snippet | Two similar synthetic pathways using the ligand
N
,
N
-diisobutylisonicotinamide (L) with anhydrous CoX
2
salts (being X = Cl
−
, Br
−
) led to different... |
SourceID | rsc |
SourceType | Enrichment Source Publisher |
StartPage | 1256 |
Title | Magneto-structural studies of two new cobalt(ii)-N,N-diisobutylisonicotinamide compounds: [CoLCl2]n and [Co(L)2(H2O)4][CoLBr3]2·2H2OElectronic supplementary information (ESI) available: CCDC reference numbers 808174-808175. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt10991j |
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