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In the title compound, C20H18B2F4N6, the bis(5,7-dimethyl-1,8-naphthyridin-2-yl)diazene molecule is bisected by a symmetry centre midway between the central N atoms of the diazene group. Each of the symmetry-related halves of the molecule binds to a B atom through an N,N′-bite. Two terminal F ions complete the distorted BN2F2 tetrahedral geometry around each B atom. The BF2 plane is almost perpendicular to the boron–naphthyridine ring plane, with a dihedral angle of 87.8 (2)°. The main interactions in the crystal structure are some C—H...F hydrogen bonds and π–π contacts between 1,8-naphthyridine rings [centroid–centroid distance = 4.005 (1) Å].