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In the title benzene-solvated heteroleptic lithium complex, [Li(C25H21P2S2)(C10H8N2)]·C6H6, the LiI ion is four-coordinated in a distorted tetra­hedral geometry by two S atoms and two N atoms of the two chelating ligands, viz. bis­(diphenyl­thio­phosphino­yl)methyl and 2,2′-bipyridine. The 2,2′-bipyridine mol­ecule is slightly twisted with a dihedral angle between the pyridine rings of 7.35 (12)°. Intra­molecular C—H...S hydrogen bonds are present. In the crystal, mol­ecules are stacked along the c axis by π–π inter­actions, with centroid–centroid distances of 3.6021 (15) and 3.6401 (16) Å. The crystal structure also features weak C—H...π inter­actions.
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