(5-Fluoro-4′-methyl­biphenyl-3-yl)(2,4,6-tri­methyl­phen­yl)iodo­nium tri­fluoro­methane­sulfonate

Ying Shao; Xiao-Long Liu; Zhu-Hong Wu; Yong-An Xia

doi:10.1107/S160053681400720X

. 2014 Apr 5;70(Pt 5):o522. doi: 10.1107/S160053681400720X

(5-Fluoro-4′-methylbiphenyl-3-yl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate

Ying Shao ^a,^*, Xiao-Long Liu ^a, Zhu-Hong Wu ^a, Yong-An Xia ^a

PMCID: PMC4011304 PMID: 24860336

Abstract

In the title molecular salt, C₂₂H₂₁FI⁺·CF₃SO₃ ⁻, the dihedral angle between the rings of the biphenyl group is 65.6 (1)°. The ring of the mesitylene group is inclined to the fluorobenzene ring at an angle of 86.1 (3)° and the C—I—C bond angle is 97.0 (2)°. In the crystal, extremely short I⋯O contacts of 2.862 (5) and 2.932 (5) Å occur, due to the strong electrostatic interactions between the I atom and two adjacent trifluoromethanesulfonate counter-ions. There are also C—H⋯F and C—H⋯π interactions present: together with the I⋯O bonds, these result in a three-dimensional network.

Related literature

For background to diaryliodonium salts, see: Grushin (2000 ▶); Merritt & Olofsson (2009 ▶).

Experimental

Crystal data

C₂₂H₂₁FI⁺·CF₃O₃S⁻
M _r = 580.37
Monoclinic,
a = 9.8987 (8) Å
b = 24.374 (2) Å
c = 10.0794 (9) Å
β = 105.820 (2)°
V = 2339.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 296 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.732, T _max = 0.772
13544 measured reflections
4341 independent reflections
3405 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.142
S = 1.14
4341 reflections
293 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S160053681400720X/hb7213sup1.cif

e-70-0o522-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400720X/hb7213Isup2.hkl

e-70-0o522-Isup2.hkl^{(212.7KB, hkl)}

Click here for additional data file.^{(4.1KB, cdx)}

Supporting information file. DOI: 10.1107/S160053681400720X/hb7213Isup3.cdx

Click here for additional data file.^{(8.3KB, cml)}

Supporting information file. DOI: 10.1107/S160053681400720X/hb7213Isup4.cml

CCDC reference: 994798

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg3 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯F1ⁱ	0.96	2.36	3.193 (9)	145
C22—H22C⋯Cg3ⁱⁱ	0.96	2.76	3.648 (7)	154

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the National Natural Science Foundation of China (grant No. 21302015), and the Natural Science Fundation for Colleges and Universities of Jiangsu Province (grant No. 12KJB150005) for financial support.

supplementary crystallographic information

1. Comment

The use of diaryliodonium salts has recently gained considerable attention in organic synthesis for arylation of organic bases (Merritt et al., 2009; Grushin et al., 2000). The title compound (Fig. 1) is an important representative of such reagents. In the molecule of the compound, the iodine atom lies almost in the plane of both attached benzene rings with r.m.s. deviations of 0.012 (2) Å and 0.028 (1) Å from the C1—C6 and C7—C12 mean planes respectively. The dihedral angle between the rings of the biphenyl group is 65.6 (1)°. The ring of the mesitylene group is inclined to the phenyl rings of the biphenyl group by 93.9 (2)° (for fluorobenzene ring) and 22.4 (2)° (for toluene ring). Extremely short intermolecular I···O contacts [2.93 (5) and 2.86 (6) Å] occur, due to strong electrostatic interactions between the I atom and two adjacent trifluoromethanesulfonate counter-ions. There are also C—H···F and C—H···π hydrogen bonds present (contact distances are shown in Table 1), which combined with the other inter-actions, form a three-dimensional network (Fig. 2).

2. Experimental

m-CPBA10 (85%, 2.5 mmol), 3-fluoro-5-iodo-4'-methylbiphenyl (2.0 mmol), and mesitylene (3.0 mmol) were dissolved in CH₂Cl₂ (5 ml). Then, TfOH (5.0 mmol) was added to the solution dropwise at 0 °C and the mixture was stirred at room temperature for 2 h and the solution was concentrated in vacuo. Et₂O (1 ml) was added and the mixture was stirred at r.t. for 10 min to precipitate out an yellow solid. The precipitate was filtered off, washed with Et₂O, and dried under vacuum to give the salt. Yield 76%. Yellow blocks were obtained by slow evaporation of a petroleum / CH₂Cl₂ solution.