organic compounds
1-Fluoro-3,3-dimethyl-1,3-dihydro-1λ3-benzo[d][1,2]iodoxole
aUniversité de Sherbrooke, Département de chimie, 2500 boul. de l'Université, Sherbrooke, Québec, Canada J1K 2R1
*Correspondence e-mail: claude.legault@usherbrooke.ca
The 9H10FIO, contains two independent molecules which are weakly bound by intermolecular O⋯I interactions [3.046 (4) and 2.947 (4) Å]. The two covalent I—F bonds are slightly longer than the two I—O bonds.
of the title compound, CRelated literature
For information on the chemistry of hypervalent compounds, see: Zhdankin & Stang (2002); Wirth (2005). For the synthesis and structural analysis of the bromo analog of the title compound, see: Braddock et al. (2006). For the synthesis and structural analysis of the chloro analog of the title compound, see: Amey & Martin (1979); Niedermann et al. (2010). For related information on the trans effect in hypervalent iodine compounds, see: Ochiai et al. (2006).
Experimental
Crystal data
|
Refinement
|
|
Data collection: DIFRAC (Flack et al., 1992); cell DIFRAC; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812012822/lh5436sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: 10.1107/S1600536812012822/lh5436Isup2.cdx
Structure factors: contains datablock I. DOI: 10.1107/S1600536812012822/lh5436Isup3.hkl
Supporting information file. DOI: 10.1107/S1600536812012822/lh5436Isup4.cml
2-(2-Iodophenyl)-propan-2-ol (164 mg, 0.63 mmol) was dissolved in MeCN (3 ml) and SelectFluor (289 mg, 0.81 mmol) was added in one portion. The reaction was then stirred at room temperature for 16 h. The mixture was concentrated under reduced pressure. The crude product was dissolved in CH2Cl2 (10 ml), washed once with water (10 ml), and concentrated under reduced pressure. The crude product was dried by coevaporation with benzene. Crystals were grown by slow diffusion of a pentane solution on a CH2Cl2 solution of the title compound at room temperature.
The hydrogen atoms were placed at idealized calculated geometric positions and refined isotropically using a riding model.
Hypervalent iodine compounds have received a growing attention in recent years. This is not surprising considering that these reagents are polyvalent electrophiles and mild oxidants (Zhdankin & Stang, 2002; Wirth, 2005). In this family, haloiodanes are interesting yet under exploited electrophilic halogen sources. A research project currently underway in our group aims to exploit haloiodanes as electrophilic halogen sources. We developed a synthesis to obtain the title compound in order to evaluate and compare its reactivity with its chloro and bromo analogs. This is the first reported synthesis of the title compound.
In the λ3-iodane compounds (Ochiai et al., 2006). In contrast to the bromo analog, the title compound was found to be completely unreactive for the fluorination of anisole. While the title compound is a stable solid, caution must be taken when drying the crude solution. The use of anhydrous MgSO4 to dry the solution results in the displacement of the fluorine by a sulfate dianion. Drying by co-evaporation with benzene prevents this side reaction. A more in-depth study of the reactivity of this novel fluoroiodane is currently underway.
two independent molecules, as shown in Fig. 1, are weakly bound by O···I interactions [3.046 (4) and 2.947 (4)Å]. The two I—O bonds observed measure 2.022 (3) Å and 2.017 (3) Å, respectively. These are shorter than the corresponding I—O bonds found in the chloro (2.042 (2) Å) (Amey & Martin, 1979; Niedermann et al., 2010) and bromo (2.050 (5) Å) (Braddock et al., 2006) analogs. This is consistent with the trans effect behavior described in a variety of hypervalentFor information on the chemistry of hypervalent compounds, see: Zhdankin & Stang (2002); Wirth (2005). For the synthesis and structural analysis of the bromo analog of the title compound, see: Braddock et al. (2006). For the synthesis and structural analysis of the chloro analog of the title compound, see: Amey & Martin (1979); Niedermann et al. (2010). For related information on the trans effect in hypervalent iodine compounds, see: Ochiai et al. (2006).
Data collection: DIFRAC (Flack et al., 1992); cell
DIFRAC (Flack et al., 1992); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C9H10FIO | Z = 4 |
Mr = 280.07 | F(000) = 536 |
Triclinic, P1 | Dx = 2.043 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.983 (6) Å | Cell parameters from 20 reflections |
b = 10.188 (8) Å | θ = 10–12.5° |
c = 11.691 (5) Å | µ = 3.48 mm−1 |
α = 83.13 (5)° | T = 193 K |
β = 79.01 (5)° | Prism, white |
γ = 78.27 (6)° | 0.4 × 0.4 × 0.3 mm |
V = 910.6 (11) Å3 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0 |
Graphite monochromator | θmax = 25.6°, θmin = 1.8° |
ω scans | h = −9→9 |
Absorption correction: ψ scan (NRCVAX; Gabe et al., 1989] | k = 0→12 |
Tmin = 0.337, Tmax = 0.422 | l = −13→14 |
3408 measured reflections | 1 standard reflections every 100 reflections |
3408 independent reflections | intensity decay: none |
2833 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0443P)2 + 0.462P] where P = (Fo2 + 2Fc2)/3 |
3408 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −1.22 e Å−3 |
C9H10FIO | γ = 78.27 (6)° |
Mr = 280.07 | V = 910.6 (11) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.983 (6) Å | Mo Kα radiation |
b = 10.188 (8) Å | µ = 3.48 mm−1 |
c = 11.691 (5) Å | T = 193 K |
α = 83.13 (5)° | 0.4 × 0.4 × 0.3 mm |
β = 79.01 (5)° |
Enraf–Nonius CAD-4 diffractometer | 2833 reflections with I > 2σ(I) |
Absorption correction: ψ scan (NRCVAX; Gabe et al., 1989] | Rint = 0 |
Tmin = 0.337, Tmax = 0.422 | 1 standard reflections every 100 reflections |
3408 measured reflections | intensity decay: none |
3408 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.64 e Å−3 |
3408 reflections | Δρmin = −1.22 e Å−3 |
217 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. The DIFRAC(Flack, 1992) program was used for centering, indexing, and data collection. One standard reflection was measured every 100 reflections, no decay was observed during data collection. The data were corrected for absorption by empirical methods based on psi scans and reduced with the NRCVAX (Gabe, 1989) programs. They were solved using SHELXS97(Sheldrick, 2008) and refined by full-matrix least squares on F2 with SHELXL97(Sheldrick, 2008). The non-hydrogen atoms were refined anisotropically. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5725 (6) | 0.6621 (4) | 0.4130 (4) | 0.0211 (9) | |
C2 | 0.7221 (6) | 0.5801 (5) | 0.4421 (4) | 0.0272 (10) | |
H2 | 0.8038 | 0.5305 | 0.3853 | 0.033* | |
C3 | 0.7484 (7) | 0.5727 (5) | 0.5550 (5) | 0.0339 (12) | |
H3 | 0.849 | 0.5164 | 0.5777 | 0.041* | |
C4 | 0.6295 (6) | 0.6467 (5) | 0.6364 (4) | 0.0288 (11) | |
H4 | 0.6489 | 0.6399 | 0.7148 | 0.035* | |
C5 | 0.4833 (6) | 0.7300 (5) | 0.6056 (4) | 0.0270 (10) | |
H5 | 0.4045 | 0.7827 | 0.6617 | 0.032* | |
C6 | 0.4513 (6) | 0.7368 (4) | 0.4917 (4) | 0.0227 (9) | |
C7 | 0.2966 (6) | 0.8263 (4) | 0.4478 (4) | 0.0227 (9) | |
C8 | 0.3279 (7) | 0.9700 (5) | 0.4218 (4) | 0.0299 (11) | |
H8A | 0.2272 | 1.0273 | 0.3935 | 0.045* | |
H8B | 0.4316 | 0.9723 | 0.3618 | 0.045* | |
H8C | 0.3451 | 1.0031 | 0.4933 | 0.045* | |
C9 | 0.1276 (6) | 0.8183 (5) | 0.5324 (4) | 0.0309 (11) | |
H9A | 0.0311 | 0.8776 | 0.5008 | 0.046* | |
H9B | 0.1353 | 0.8467 | 0.6081 | 0.046* | |
H9C | 0.1077 | 0.7255 | 0.5426 | 0.046* | |
C10 | −0.0885 (6) | 0.8468 (4) | 0.0402 (4) | 0.0215 (9) | |
C11 | −0.2429 (6) | 0.9114 (5) | 0.0057 (5) | 0.0320 (12) | |
H11 | −0.3264 | 0.9704 | 0.0542 | 0.038* | |
C12 | −0.2712 (6) | 0.8866 (5) | −0.1023 (5) | 0.0308 (11) | |
H12 | −0.3758 | 0.9292 | −0.1291 | 0.037* | |
C13 | −0.1484 (6) | 0.8006 (5) | −0.1711 (4) | 0.0302 (11) | |
H13 | −0.1687 | 0.7844 | −0.2452 | 0.036* | |
C14 | 0.0050 (6) | 0.7373 (4) | −0.1332 (4) | 0.0245 (10) | |
H14 | 0.0887 | 0.678 | −0.1814 | 0.029* | |
C15 | 0.0367 (6) | 0.7600 (4) | −0.0255 (4) | 0.0212 (9) | |
C16 | 0.1966 (6) | 0.6918 (4) | 0.0259 (4) | 0.0204 (9) | |
C17 | 0.3625 (6) | 0.6881 (5) | −0.0644 (4) | 0.0267 (10) | |
H17A | 0.4625 | 0.6434 | −0.0281 | 0.04* | |
H17B | 0.3763 | 0.7802 | −0.0937 | 0.04* | |
H17C | 0.3554 | 0.6384 | −0.1296 | 0.04* | |
C18 | 0.1750 (6) | 0.5513 (4) | 0.0787 (4) | 0.0274 (10) | |
H18A | 0.2784 | 0.5075 | 0.1118 | 0.041* | |
H18B | 0.1601 | 0.4985 | 0.0178 | 0.041* | |
H18C | 0.0726 | 0.5574 | 0.1406 | 0.041* | |
F1 | 0.7418 (4) | 0.5802 (3) | 0.1913 (3) | 0.0372 (7) | |
F2 | −0.2633 (4) | 0.9676 (3) | 0.2491 (3) | 0.0437 (8) | |
I1 | 0.50006 (4) | 0.68702 (3) | 0.24847 (2) | 0.02221 (10) | |
I2 | −0.01657 (4) | 0.86419 (3) | 0.20011 (2) | 0.02531 (10) | |
O1 | 0.2750 (4) | 0.7761 (3) | 0.3428 (3) | 0.0283 (7) | |
O2 | 0.2131 (4) | 0.7722 (3) | 0.1146 (3) | 0.0250 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.025 (2) | 0.018 (2) | 0.022 (2) | −0.0066 (18) | −0.0071 (18) | 0.0021 (17) |
C2 | 0.022 (2) | 0.027 (2) | 0.031 (3) | 0.000 (2) | −0.004 (2) | −0.0025 (19) |
C3 | 0.031 (3) | 0.032 (3) | 0.041 (3) | −0.005 (2) | −0.018 (2) | 0.005 (2) |
C4 | 0.037 (3) | 0.030 (3) | 0.023 (2) | −0.010 (2) | −0.015 (2) | 0.0036 (19) |
C5 | 0.038 (3) | 0.027 (2) | 0.018 (2) | −0.012 (2) | −0.005 (2) | −0.0010 (18) |
C6 | 0.024 (2) | 0.020 (2) | 0.024 (2) | −0.0023 (18) | −0.0066 (19) | 0.0019 (17) |
C7 | 0.022 (2) | 0.025 (2) | 0.020 (2) | −0.0004 (18) | −0.0024 (18) | −0.0050 (18) |
C8 | 0.036 (3) | 0.024 (2) | 0.026 (2) | 0.000 (2) | −0.003 (2) | 0.0009 (19) |
C9 | 0.027 (3) | 0.034 (3) | 0.027 (3) | −0.002 (2) | 0.005 (2) | −0.003 (2) |
C10 | 0.020 (2) | 0.022 (2) | 0.021 (2) | −0.0058 (18) | 0.0004 (18) | −0.0009 (17) |
C11 | 0.021 (2) | 0.025 (2) | 0.045 (3) | −0.001 (2) | 0.000 (2) | 0.002 (2) |
C12 | 0.021 (2) | 0.032 (3) | 0.040 (3) | −0.007 (2) | −0.012 (2) | 0.008 (2) |
C13 | 0.033 (3) | 0.027 (2) | 0.034 (3) | −0.013 (2) | −0.012 (2) | 0.007 (2) |
C14 | 0.032 (3) | 0.023 (2) | 0.021 (2) | −0.009 (2) | −0.0069 (19) | −0.0009 (18) |
C15 | 0.022 (2) | 0.018 (2) | 0.024 (2) | −0.0076 (18) | −0.0021 (18) | 0.0011 (17) |
C16 | 0.017 (2) | 0.024 (2) | 0.018 (2) | −0.0022 (18) | 0.0009 (17) | −0.0054 (17) |
C17 | 0.025 (2) | 0.029 (2) | 0.024 (2) | −0.002 (2) | −0.0009 (19) | −0.0056 (19) |
C18 | 0.030 (3) | 0.024 (2) | 0.027 (2) | −0.002 (2) | −0.007 (2) | −0.0010 (19) |
F1 | 0.0276 (16) | 0.0464 (18) | 0.0335 (16) | 0.0017 (13) | 0.0032 (13) | −0.0155 (13) |
F2 | 0.0304 (17) | 0.0502 (19) | 0.0433 (18) | 0.0012 (14) | 0.0115 (14) | −0.0189 (15) |
I1 | 0.02218 (17) | 0.02611 (17) | 0.01820 (16) | −0.00355 (12) | −0.00138 (12) | −0.00623 (11) |
I2 | 0.02468 (18) | 0.02723 (17) | 0.02327 (17) | −0.00611 (13) | 0.00320 (12) | −0.00869 (12) |
O1 | 0.0204 (17) | 0.0395 (19) | 0.0243 (17) | 0.0040 (14) | −0.0070 (14) | −0.0113 (14) |
O2 | 0.0195 (16) | 0.0316 (17) | 0.0235 (16) | −0.0007 (13) | −0.0009 (13) | −0.0122 (14) |
C1—C6 | 1.374 (6) | C10—I2 | 2.094 (5) |
C1—C2 | 1.386 (6) | C11—H11 | 0.950 |
C1—I1 | 2.085 (4) | C11—C12 | 1.385 (7) |
C2—C3 | 1.367 (7) | C12—C13 | 1.377 (7) |
C2—H2 | 0.950 | C13—C14 | 1.389 (7) |
C3—C4 | 1.382 (7) | C14—C15 | 1.385 (6) |
C4—C5 | 1.378 (7) | C15—C16 | 1.519 (6) |
C5—C6 | 1.394 (6) | C16—O2 | 1.437 (5) |
C6—C7 | 1.514 (6) | C16—C18 | 1.519 (6) |
C7—O1 | 1.437 (5) | C16—C17 | 1.525 (6) |
C7—C8 | 1.521 (6) | F1—I1 | 2.045 (3) |
C7—C9 | 1.523 (6) | F2—I2 | 2.046 (3) |
C10—C15 | 1.372 (6) | I1—O1 | 2.022 (3) |
C10—C11 | 1.382 (6) | I2—O2 | 2.017 (3) |
C6—C1—C2 | 123.2 (4) | H11—C11—C10 | 121.3 |
C6—C1—I1 | 111.5 (3) | C13—C12—C11 | 120.3 (5) |
C2—C1—I1 | 125.3 (4) | C12—C13—C14 | 120.6 (5) |
C3—C2—C1 | 117.9 (5) | C15—C14—C13 | 120.4 (4) |
H2—C2—C1 | 121.0 | C10—C15—C14 | 117.3 (4) |
C2—C3—C4 | 120.4 (5) | C10—C15—C16 | 118.2 (4) |
C5—C4—C3 | 120.9 (4) | C14—C15—C16 | 124.5 (4) |
C4—C5—C6 | 119.7 (5) | O2—C16—C15 | 107.5 (3) |
C1—C6—C5 | 117.7 (4) | O2—C16—C18 | 110.3 (4) |
C1—C6—C7 | 118.1 (4) | C15—C16—C18 | 109.6 (4) |
C5—C6—C7 | 124.2 (4) | O2—C16—C17 | 106.0 (3) |
O1—C7—C6 | 108.1 (4) | C15—C16—C17 | 111.9 (4) |
O1—C7—C8 | 109.8 (4) | C18—C16—C17 | 111.3 (4) |
C6—C7—C8 | 109.9 (4) | O1—I1—F1 | 166.40 (12) |
O1—C7—C9 | 104.8 (4) | O1—I1—C1 | 80.58 (16) |
C6—C7—C9 | 112.1 (4) | F1—I1—C1 | 86.21 (16) |
C8—C7—C9 | 111.8 (4) | O2—I2—F2 | 166.81 (13) |
C15—C10—C11 | 124.0 (4) | O2—I2—C10 | 80.30 (16) |
C15—C10—I2 | 111.0 (3) | F2—I2—C10 | 87.13 (16) |
C11—C10—I2 | 124.9 (4) | C7—O1—I1 | 113.7 (3) |
C10—C11—C12 | 117.4 (5) | C16—O2—I2 | 113.6 (3) |
C6—C1—C2—C3 | 0.7 (7) | C13—C14—C15—C10 | −0.2 (6) |
I1—C1—C2—C3 | −178.5 (4) | C13—C14—C15—C16 | 177.5 (4) |
C1—C2—C3—C4 | −0.8 (7) | C10—C15—C16—O2 | −22.0 (5) |
C2—C3—C4—C5 | −0.6 (8) | C14—C15—C16—O2 | 160.3 (4) |
C3—C4—C5—C6 | 2.1 (7) | C10—C15—C16—C18 | 97.9 (5) |
C2—C1—C6—C5 | 0.8 (7) | C14—C15—C16—C18 | −79.8 (5) |
I1—C1—C6—C5 | −179.8 (3) | C10—C15—C16—C17 | −138.1 (4) |
C2—C1—C6—C7 | 177.8 (4) | C14—C15—C16—C17 | 44.3 (6) |
I1—C1—C6—C7 | −2.8 (5) | C6—C1—I1—O1 | −11.4 (3) |
C4—C5—C6—C1 | −2.2 (7) | C2—C1—I1—O1 | 168.0 (4) |
C4—C5—C6—C7 | −179.0 (4) | C6—C1—I1—F1 | 171.9 (3) |
C1—C6—C7—O1 | 21.8 (5) | C2—C1—I1—F1 | −8.8 (4) |
C5—C6—C7—O1 | −161.3 (4) | C15—C10—I2—O2 | 13.5 (3) |
C1—C6—C7—C8 | −98.0 (5) | C11—C10—I2—O2 | −167.8 (4) |
C5—C6—C7—C8 | 78.8 (5) | C15—C10—I2—F2 | −170.5 (3) |
C1—C6—C7—C9 | 136.9 (4) | C11—C10—I2—F2 | 8.2 (4) |
C5—C6—C7—C9 | −46.3 (6) | C6—C7—O1—I1 | −31.0 (4) |
C15—C10—C11—C12 | −0.3 (7) | C8—C7—O1—I1 | 89.0 (4) |
I2—C10—C11—C12 | −178.8 (3) | C9—C7—O1—I1 | −150.7 (3) |
C10—C11—C12—C13 | 0.0 (7) | F1—I1—O1—C7 | 38.2 (7) |
C11—C12—C13—C14 | 0.2 (7) | C1—I1—O1—C7 | 24.4 (3) |
C12—C13—C14—C15 | −0.1 (7) | C15—C16—O2—I2 | 33.1 (4) |
C11—C10—C15—C14 | 0.4 (6) | C18—C16—O2—I2 | −86.4 (4) |
I2—C10—C15—C14 | 179.0 (3) | C17—C16—O2—I2 | 153.0 (3) |
C11—C10—C15—C16 | −177.4 (4) | F2—I2—O2—C16 | −44.7 (7) |
I2—C10—C15—C16 | 1.2 (5) | C10—I2—O2—C16 | −26.9 (3) |
Experimental details
Crystal data | |
Chemical formula | C9H10FIO |
Mr | 280.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 7.983 (6), 10.188 (8), 11.691 (5) |
α, β, γ (°) | 83.13 (5), 79.01 (5), 78.27 (6) |
V (Å3) | 910.6 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.48 |
Crystal size (mm) | 0.4 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (NRCVAX; Gabe et al., 1989] |
Tmin, Tmax | 0.337, 0.422 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3408, 3408, 2833 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.607 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.073, 1.05 |
No. of reflections | 3408 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −1.22 |
Computer programs: DIFRAC (Flack et al., 1992), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
C1—I1 | 2.085 (4) | F2—I2 | 2.046 (3) |
C10—I2 | 2.094 (5) | I1—O1 | 2.022 (3) |
F1—I1 | 2.045 (3) | I2—O2 | 2.017 (3) |
Acknowledgements
This work was supported by the National Science and Engineering Research Council (NSERC) of Canada, the Fonds Québecois de Recherche – Nature et Technologies (FQRNT), the Canada Foundation for Innovation (CFI), the FQRNT Centre in Green Chemistry and Catalysis (CGCC), and the Université de Sherbrooke. We thank Daniel Fortin for the structural analysis.
References
Amey, R. L. & Martin, J. C. (1979). J. Org. Chem. 44, 1779–1784. CrossRef CAS Web of Science Google Scholar
Braddock, D. C., Cansell, G., Hermitage, S. A. & White, A. J. P. (2006). Chem. Commun. pp. 1442–1444. Web of Science CSD CrossRef Google Scholar
Flack, H. D., Blanc, E. & Schwarzenbach, D. (1992). J. Appl. Cryst. 25, 455–459. CrossRef Web of Science IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Niedermann, K., Welch, J. M., Koller, R., Cvengro, J., Santschi, N., Battaglia, P. & Togni, A. (2010). Tetrahedron, 66, 5753–5761. Web of Science CSD CrossRef CAS Google Scholar
Ochiai, M., Sueda, T., Miyamoto, K., Kiprof, P. & Zhdankin, V. V. (2006). Angew. Chem. Int. Ed. 45, 8203–8206. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wirth, T. (2005). Angew. Chem. Int. Ed. 44, 3656–3665. Web of Science CrossRef CAS Google Scholar
Zhdankin, V. V. & Stang, P. J. (2002). Chem. Rev. 102, 2523–2584. Web of Science CrossRef PubMed CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Hypervalent iodine compounds have received a growing attention in recent years. This is not surprising considering that these reagents are polyvalent electrophiles and mild oxidants (Zhdankin & Stang, 2002; Wirth, 2005). In this family, haloiodanes are interesting yet under exploited electrophilic halogen sources. A research project currently underway in our group aims to exploit haloiodanes as electrophilic halogen sources. We developed a synthesis to obtain the title compound in order to evaluate and compare its reactivity with its chloro and bromo analogs. This is the first reported synthesis of the title compound.
In the crystal structure, two independent molecules, as shown in Fig. 1, are weakly bound by O···I interactions [3.046 (4) and 2.947 (4)Å]. The two I—O bonds observed measure 2.022 (3) Å and 2.017 (3) Å, respectively. These are shorter than the corresponding I—O bonds found in the chloro (2.042 (2) Å) (Amey & Martin, 1979; Niedermann et al., 2010) and bromo (2.050 (5) Å) (Braddock et al., 2006) analogs. This is consistent with the trans effect behavior described in a variety of hypervalent λ3-iodane compounds (Ochiai et al., 2006). In contrast to the bromo analog, the title compound was found to be completely unreactive for the fluorination of anisole. While the title compound is a stable solid, caution must be taken when drying the crude solution. The use of anhydrous MgSO4 to dry the solution results in the displacement of the fluorine by a sulfate dianion. Drying by co-evaporation with benzene prevents this side reaction. A more in-depth study of the reactivity of this novel fluoroiodane is currently underway.