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The complete molecule of the title compound, [Cu2(C2H3O2)2(CF3O3S)2(C12H8N2)2], is completed by the application of a twofold rotation and comprises two CuII ions, each of which is penta­coordinated by two N atoms from a bidentate 1,10-phenanthroline (phen) ligand, two O atoms from acetate ligands and an O atom from a tri­fluoro­methane­sulfonate anion, forming a (4 + 1) distorted square-pyramidal coordination geometry. The CuII ions are connected by two acetate bridges in a synsyn configuration. The F atoms of the tri­fluoro­methane­sulfonate ligands are disordered, with site-occupation factors of 70 and 30. The molecular structure is stabilized by intra­molecular face-to-face π–π inter­actions with centroid–centroid distances in the range 3.5654 (12)–3.8775(12) Å. The crystal structure is stabilized by C—H...O interactions, leading to a three-dimensional lattice structure.
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