Dataset on synthesis and crystallographic structure of phenyl(TMP)iodonium(III) acetate

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.

work, the aryl (TMP)iodonium (III) salts were applied as the efficient arylating agents for the coppercatalyzed N-arylation of azole compounds, which turned out that these iodonium (III) salts have high reactivities even in the metal-catalyzed coupling together with the reported exclusive aryl-group transfer behavior [1]. Therefore, the synthesis and structural information for Ph(TMP)IOAc are very important. The first example of the X-ray structural analysis is worth to notice. Our original method for preparation of the diaryliodonium (III) salts [12] enables to obtain the studied compound of high purity suitable for single-crystal growth (see Tables 1e4). Ph(TMP)IOAc was synthesized by direct condensation between phenyliodine (III) diacetate (PIDA) and 1,3,5-trimethoxybenzene (TMP) in fluoroalcohol medium under mild conditions (Scheme 1). The structure of Ph(TMP)IOAc was determined by two-dimensional NMR analyses (Figs. 3 and 4). The 1 H NMR spectrum in Fig. 1 supports the high purity of Ph(TMP)IOAc obtained in this study. X-ray structural analysis have suggested that two geometrical states for Ph(TMP)IOAc appear in a crystal in the threedimensional structure (Figs. 5 and 6).

Materials
The solvents, starting materials, and reagents were purchased from Nacalai tesque and Tokyo Chemical Industry CO. Ltd.

Synthesis of Ph(TMP)IOAc
Ph(TMP)IOAc was prepared according to our reported procedure [12]. Thus, to a solution of 1,3,5trimethoxybenzene (TMP, 168 mg, 1.0 mmol) in 2,2,2-trifluoroethanol (TFE, 2 mL) was added Specifications Value of the data The X-ray structural information for phenyl(2,4,6-trimethoxyphenyl)iodonium (III) acetate (Ph(TMP)IOAc) presented in this work is the first data for an organic iodonium (III) salt with two geometrical states in a crystal. Convenient synthetic method for preparing Ph(TMP)IOAc with high purity, which is applicable to the synthesis of other analogues is presented. Our dataset is useful for organic chemists and physicists who study organic hypervalent iodine compounds. The structural data of Ph(TMP)IOAc has additional value as an important intermediate in the metal-free esterification reactions.

General information for NMR analyses
The 1 H and 13 C NMR spectra were recorded on an ECS 400 NMR spectrometer (JEOL Ltd., Tokyo, Japan) at 400 MHz and 100 MHz, respectively, using CDCl 3 as the solvent. The chemical shifts (d) are expressed in ppm relative to tetramethylsilane (TMS) as an internal standard. Coupling constants (J) are expressed in Hz. Signal multiplicities are represented as singlet (s), doublet (d), and triplet (t). Assignments of the proton and carbon positions in the compound were performed by PFG-HMQC and PFG-HMBC analyses.

Crystallization
The crystals were obtained at room temperature from chloroform/hexane mixture under a shading condition. Ph(TMP)IOAc was dissolved in chloroform and the insoluble material was removed by  filtration. Hexane was added to the filtrate in sample bottle to reach the chloroform/hexane ratio 2/5. After standing for 1 day, the several crystals suitable for the X-ray structural analysis were obtained.

X-ray
The single-crystal X-ray diffraction experiment was performed on the HPC diffractometer (Rigaku XtaLAB P200)). The two types of geometries for Ph(TMP)IOAc in a crystal state are shown in Fig. 5. In Fig. 5(A), it was found that the distance between the iodine atom in the cation and an oxygen atom in the anion is 2.77 Å. On the other hand, the distances between the iodine atom in the cation and oxygen atoms in the anion were 2.59 Å and 3.37 Å, respectively (Fig. 5(B)). In both geometries, the distances between the iodine atom in the cation and two oxygen atoms in the methoxy group were 3.10 Å (Fig. 5(A) and (B)).