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Magnetic properties of 4,4′-bipiperidinediium tetrahalocuprates: crystal structures of 4,4′-bipiperidinediium tetrabromocuprate(II) monohydrate and bis(4,4′-bipiperidinediium) hexabromodicuprate(I)

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Reaction of 4,4′-bipiperidine (bipip) with copper(II) bromide in aqueous HBr yielded the salts (H2bipip)CuBr4·H2O (2) and (H2bipip)2Cu2Br6 (3). Compound 2 crystallizes in the space group P2 1 /m and forms alternating layers of the H2bipip cations and CuBr4 anions with the water molecules located in the anionic layer. Compound 3 contains Cu(I) and crystallizes in the space group P2 1 /c and comprises stacks of H2bipip cations alternating with stacks of anions. Temperature-dependent magnetic measurements on 2 and its chloride analog, 1, show distinctly different behaviors supported by the two-halide superexchange pathway. The chloride compound (1) is best described as weakly interacting antiferromagnetic dimers (J ~ −13 K), while the bromide compound (2) exhibits very weak ferromagnetic interactions best modeled as a uniform chain with J = 2.45 (9) K (using the H = −J ABΣS A·S B Hamiltonian).
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Keywords: 4,4′-Bipiperidine; Cu(I) Halide; Tetrahalocuprate(II); crystal structure; magnetism

Document Type: Research Article

Affiliations: 1: Department of Chemistry, University of Canterbury, Christchurch, New Zealand 2: Department of Chemistry, Howard University, Washington, DC, USA 3: School of Chemical Technology, Aalto University, Aalto, Finland 4: Carlson School of Chemistry and Biochemistry, Clark University, Worcester, MA, USA

Publication date: January 2, 2016

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