The mixed ligand complexes of di-/tri-organotin 4-fluoroanthranilates with 1,10-phenanthroline (phen), viz. [R2Sn(FA)2.phen] {R=Bu (1), Oct (2), Me (3)} and benzimidazole (bz), viz. [R3Sn(FA).bz] {R=Me (4), Ph (5)} have been synthesized and satisfactorily characterized by analytical and spectroscopic techniques, especially FT-IR, NMR (1H, 13C, and 119Sn NMR) spectroscopy and ESI-MS spectrometry. Single crystal-Xray diffraction measurements (Sc-XRD) confirmed a distorted pentagonal-bipyramidal geometry for complex (1), where one carboxylate group is monodentate, and the second (–COO) group behaves as a bidentate, while complex (4) affirms trigonal–bipyramidal geometry around the tin centre. The bond angles, especially ∠C–Sn–C obtained by optimizing complexes’ gaseous phase geometry showed significant conformity with the data obtained from Sc-XRD and NMR. The Kb (binding constant) and Ksv (Stern-Volmer quenching constant) values, ranging from 103 to 107, have been obtained through UV–visible absorption and fluorescence titrations with CT-DNA. These results strongly indicate partial minor groove binding/electrostatic interactions between the complex and CT-DNA, which has also been evidenced by circular dichroism studies. The studied complexes cleaved efficiently pBR322 plasmid DNA in NC (nicked circular form), SC (supercoiled form), and linear form.