1-Fluoro-3,3-dimethyl-1,3-dihydro-1λ³-benzo[d][1,2]iodoxole

Abstract

The asymmetric unit of the title compound, C₉H₁₀FIO, 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.

Related 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  

• C₉H₁₀FIO

• M _r = 280.07

• Triclinic,

• a = 7.983 (6) Å

• b = 10.188 (8) Å

• c = 11.691 (5) Å

• α = 83.13 (5)°

• β = 79.01 (5)°

• γ = 78.27 (6)°

• V = 910.6 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 3.48 mm⁻¹

• T = 193 K

• 0.4 × 0.4 × 0.3 mm

Data collection  

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (NRCVAX; Gabe et al., 1989 ▶] T _min = 0.337, T _max = 0.422

• 3408 measured reflections

• 3408 independent reflections

• 2833 reflections with I > 2σ(I)

• 1 standard reflections every 100 reflections intensity decay: none

Refinement  

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.073

• S = 1.05

• 3408 reflections

• 217 parameters

• H-atom parameters constrained

• Δρ_max = 0.64 e Å⁻³

• Δρ_min = −1.22 e Å⁻³

Data collection: DIFRAC (Flack et al., 1992 ▶); cell refinement: 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812012822/lh5436Isup2.cdx

Supplementary material file. DOI: 10.1107/S1600536812012822/lh5436Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

C1—I1	2.085 (4)
C10—I2	2.094 (5)
F1—I1	2.045 (3)
F2—I2	2.046 (3)
I1—O1	2.022 (3)
I2—O2	2.017 (3)

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The hydrogen atoms were placed at idealized calculated geometric positions and refined isotropically using a riding model.

Figures

Fig. 1.

The asymmetric unit of the title compound, showing 30% probability displacement ellipsoids. The I···O interactions are shown by dotted lines. H atoms are depicted as circles of arbitrary size.

Crystal data

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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)