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The reaction of Cu(Hm-dtc)2 (H2m-dtc is azepane-1-carbodi-thioic acid), CuBr2 and methyl iso-thio-cyanate yielded the title mixed-valence nona-nuclear Cu(I)/Cu(II) compound, [Cu9Br5(C7H12NS2)5] or [Cu(I) 8Cu(II)Br5(Hm-dtc)5], encapsulating a bromide anion in the center of the Cu9Br4S10 cluster cage. The cage consists of a mononuclear Cu(II) unit [Cu(Hm-dtc)2], three μ4-bridging Hm-dtc(-) ligands, eight Cu(I) ions with distorted tetra-hedral or trigonal pyramidal coordination geometries and four μ2-bridging bromide anions. The incorporated central bromide anion inter-acts with nine Cu ions with shorter Cu-Br separations than the sum of the van der Waals radii for Cu and Br.

acta crystallographica. section e

Tris(μ4-azepane-1-carbodithioato)bis(μ3-azepane-1-carbodithioato)-μ9-bromido-tetra-μ2-bromido-octacopper(I)copper(II)