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The reaction between CuSO(4)·5H(2)O and [NMe(2)H(2)]Cl in N,N'-dimethylformamide (DMF) at 95 °C yielded green crystals of (NMe(2)H(2))(4)[Cu(6)O(2)(SO(4))(6)(DMF)(4)] 1. The discrete [Cu(6)(μ(4)-O)(2)(μ(3)-SO(4))(4)(μ(2)-SO(4))(2)(DMF)(4)](4-) anions present in 1 contain two edge-sharing Cu(4)(μ(4)-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 [NMe(2)H(2)]Cl, yellow-green crystals of (NMe(2)H(2))(4)[Cu(6)O(2)(SO(4))(6)(DMF)(2)] 2 were obtained. The anions in 2 contain similar Cu(6)O(2)(SO(4))(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 Cu(6)O(2)(SO(4))(6) aggregates observed in 1 and 2 are related to those present in the rare copper sulfate mineral fedotovite, K(2)Cu(3)O(SO(4))(3), and in common with this mineral both 1 and 2 decompose in the presence of moisture. The reaction between CuSO(4)·5H(2)O and [NMe(2)H(2)]Cl in DMF at room temperature gave (NMe(2)H(2))[Cu(2)(OH)(SO(4))(2)(H(2)O)(2)] 3, the structure of which contains triangular Cu(3)(OH)(SO(4)) 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.

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