The title compound,6, a novel 1∶1 complex of 1-chloro-1,2-benziodoxolin-3(1H)-one (5) andtetra-n-butylammonium chloride, was prepared from tetra-n-butylammoniumo-iodoxybenzoate (7) and acetyl chloride. A single crystal of6 was subjected to X-ray analysis: triclinic, space group\(P\bar 1;\)a=10.239(2),b=11.518(2),c=11.523(3)Å; α=73.20(2); β=87.85(2), γ=87.72(2)°; R1=0.0326. The most notable structural feature of crystalline6 is the existence of a “secondary” bond [I· ·Cl(2), 2.943(1)Å] between the chloride ion and the iodine atom of the chlorobenziodoxolinone moiety. Further coordination at iodine includes three primary bonds: I−C [2.115(4) Å], I−O [2.145(3) Å], I−Cl(1) [2.454(1) Å]. The entire 1-chlorobenziodoxolinone-chloride sub-structure is planar and exhibits iodine-centered bond angles of 78.8(1)° [C−I−O], 92.0(1)° [C−I−Cl(1)], 97.6(1)° [Cl(2)−I−O] and 91.6(1)° [Cl(2)−I−Cl(1)]. The unit cell of6 contains two loosely packed formula units. The chlorobenziodoxolinone-chloride sub-structures occupy a common plane and exhibit a centrosymmetric relationship, while the tetra-n-butylammonium ions are situated one above and one below the plane. Bonding at the iodine atom in6 is more consistent with a 10-I-3 species electrostatically associated with the chloride ion than a 12-I-4 species such as the tetrachloroiodate ion.