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The title compound, 2C14H12S·C12N4F4, was obtained by using 4,6-di­methyl­dibenzo­thio­phene (DMDBT) as an electron donor and 7,7,8,8-tetra­cyano-2,3,5,6-tetra­fluoro­quinodi­methane (F4TCNQ) as an electron acceptor. The asymmetric unit consists of one DMDBT mol­ecule and one half of an F4TCNQ mol­ecule, which lies on an inversion centre. In the crystal, the DMDBT and F4TCNQ mol­ecules form a 2:1 unit via a charge-transfer inter­action, with a centroid–centroid distance of 3.3681 (15) A between the five-membered ring of DMDBT and the six-membered ring of F4TCNQ. An F⋯F contact [2.911 (1) A] is also observed.

The 2:1 charge-transfer complex of 4,6-dimethyldibenzothiophene and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane