The data in this article are related to research article ‘‘Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium (III) reagents (Koseki et al., 2019). For the title compound, phenyl(2,4,6-trimethoxyphenyl)iodonium(III) acetate (Ph(TMP)IOAc), the single-crystal X-ray diffraction measurement together with NMR analysis, like also the method of synthesis and crystallization are presented. The X-ray structure analysis has revealed that the two types of geometries regarding the acetate anion attached to phenyl (TMP)iodonium (III) cation are found in the crystal states. Keywords: Hypervalent iodine compound, Iodonium(III) salt, Acetate ligand, Two geometrical states
