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Synthesis, Structures, And Magnetic Behavior of New Anionic Copper(II) Sulfate Aggregates and Chains.

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Title: Synthesis, Structures, And Magnetic Behavior of New Anionic Copper(II) Sulfate Aggregates and Chains.
Authors: Burrows, Andrew D.1 a.d.burrows@bath.ac.uk, Mahon, Mary F.1, Sebestyen, Viorica M.1, Lan, Yanhua2, Powell, Annie K.2,3
Source: Inorganic Chemistry. 10/15/2012, Vol. 51 Issue 20, p10983-10989. 7p.
Subjects: Clustering of particles, Molecular structure, Copper sulfate, Chemical reactions, Hydrogen bonding, Ligands (Chemistry), Amides, Coordination compounds
Abstract: The reaction between CuSO₄·SH₂O and [NMe₂H₂]Cl in N,N'-dimethylforma-mide (DMF) at 95 °C yielded green crystals of (NMe₂H₂)₄[Cu₆O₂(SO₄)₆(DMF)₄] 1. The discrete [Cu₆(μ₄-O)₂(μ₃-SO₄)₄(μ₂-SO₄)₂(DMF)₄]4⁻ anions present in 1 contain two edge- sharing Cu₄(μ₂-O) tetrahedra, with the copper(II) centers bridged by sulfato ligands. These anions are linked into a two-dimensional network through hydrogen bonds involving the dimethylammonium cations. When the reaction was carried out in the absence of [NMe₂H₂]Cl, yellow-green crystals of (NMe₂H₂)₄[Cu₆O₂(SO₄)₆(DMF)₂] 2 were obtained. The anions in 2 contain similar Cu₆O₂(SO₄)₆ aggregates to those in 1, though these differ in terms of the copper(II) coordination geometries. In addition, the anions in 2 are linked into chains through bridging sulfato ligands. The Cu₆O₂(SO₄)₆ aggregates observed in 1 and 2 are related to those present in the rare copper sulfate mineral fedotovite, K₂Cu₂O(SO₄)₃, and in common with this mineral both 1 and 2 decompose in the presence of moisture. The reaction between CuSO₄·5H₂O and [NMe₂H₂]Cl in DMF at room temperature gave (NMe₂H₂)[Cu₂(OH)-(SO₄)₂(H₂O)₂] 3, the structure of which contains triangular Cu₃(OH)(SO₄) units that share vertices to form tapes. Magnetic measurements revealed that 1 and 3 are both spin-canting metamagnetic systems. Field-induced responses were observed below 5 K, with the critical field indicating metamagnetic behavior from antiferromagnetic to ferromagnetic equal to 110 Oe for both compounds. [ABSTRACT FROM AUTHOR]
Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Synthesis, Structures, And Magnetic Behavior of New Anionic Copper(II) Sulfate Aggregates and Chains.
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  Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 10/15/2012, Vol. 51 Issue 20, p10983-10989. 7p.
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  Data: <searchLink fieldCode="DE" term="%22Clustering+of+particles%22">Clustering of particles</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+sulfate%22">Copper sulfate</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+bonding%22">Hydrogen bonding</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Amides%22">Amides</searchLink><br /><searchLink fieldCode="DE" term="%22Coordination+compounds%22">Coordination compounds</searchLink>
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  Data: The reaction between CuSO₄·SH₂O and [NMe₂H₂]Cl in N,N'-dimethylforma-mide (DMF) at 95 °C yielded green crystals of (NMe₂H₂)₄[Cu₆O₂(SO₄)₆(DMF)₄] 1. The discrete [Cu₆(μ₄-O)₂(μ₃-SO₄)₄(μ₂-SO₄)₂(DMF)₄]4⁻ anions present in 1 contain two edge- sharing Cu₄(μ₂-O) tetrahedra, with the copper(II) centers bridged by sulfato ligands. These anions are linked into a two-dimensional network through hydrogen bonds involving the dimethylammonium cations. When the reaction was carried out in the absence of [NMe₂H₂]Cl, yellow-green crystals of (NMe₂H₂)₄[Cu₆O₂(SO₄)₆(DMF)₂] 2 were obtained. The anions in 2 contain similar Cu₆O₂(SO₄)₆ aggregates to those in 1, though these differ in terms of the copper(II) coordination geometries. In addition, the anions in 2 are linked into chains through bridging sulfato ligands. The Cu₆O₂(SO₄)₆ aggregates observed in 1 and 2 are related to those present in the rare copper sulfate mineral fedotovite, K₂Cu₂O(SO₄)₃, and in common with this mineral both 1 and 2 decompose in the presence of moisture. The reaction between CuSO₄·5H₂O and [NMe₂H₂]Cl in DMF at room temperature gave (NMe₂H₂)[Cu₂(OH)-(SO₄)₂(H₂O)₂] 3, the structure of which contains triangular Cu₃(OH)(SO₄) units that share vertices to form tapes. Magnetic measurements revealed that 1 and 3 are both spin-canting metamagnetic systems. Field-induced responses were observed below 5 K, with the critical field indicating metamagnetic behavior from antiferromagnetic to ferromagnetic equal to 110 Oe for both compounds. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/ic301478x
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      – Code: eng
        Text: English
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        PageCount: 7
        StartPage: 10983
    Subjects:
      – SubjectFull: Clustering of particles
        Type: general
      – SubjectFull: Molecular structure
        Type: general
      – SubjectFull: Copper sulfate
        Type: general
      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: Hydrogen bonding
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      – SubjectFull: Ligands (Chemistry)
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      – SubjectFull: Amides
        Type: general
      – SubjectFull: Coordination compounds
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      – TitleFull: Synthesis, Structures, And Magnetic Behavior of New Anionic Copper(II) Sulfate Aggregates and Chains.
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              Text: 10/15/2012
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              Y: 2012
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