Bibliographic Details
| 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] |
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| Database: |
Engineering Source |
