1-[2-(3,5-Difluoro­benz­yloxy)phen­yl]ethanone

Ma, Y.-T.; Shi, X.-W.; Shuai, Q.; Gao, J.-M.

doi:10.1107/S160053681003120X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2293

https://doi.org/10.1107/S160053681003120X

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1-[2-(3,5-Difluorobenzyloxy)phenyl]ethanone

Ya-Tuan Ma,^a Xin-Wei Shi,^a Qi Shuai ^a and Jin-Ming Gao ^a ^*

^aCollege of Science, Northwest A&F University, Yangling 712100, People's Republic of China
^*Correspondence e-mail: jinminggaocn@yahoo.com.cn

(Received 22 July 2010; accepted 4 August 2010; online 11 August 2010)

In the title compound, C₁₅H₁₂F₂O₂, the dihedral angle between the aromatic rings is 70.43 (4)°. The crystal packing exhibits no significantly short intermolecular contacts.

Related literature

For background to the Williamson reaction in organic synthesis, see: Dermer (1934 ). For a related structure, see: Ma et al. (2010 ).

Experimental

Crystal data

C₁₅H₁₂F₂O₂
M_r = 262.25
Triclinic, $[P \overline 1]$
a = 7.2808 (7) Å
b = 7.9734 (8) Å
c = 11.6466 (12) Å
α = 91.587 (1)°
β = 106.559 (2)°
γ = 95.343 (1)°
V = 644.22 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.42 × 0.38 × 0.20 mm

Data collection

Bruker SMART CD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.956, T_max = 0.979
3373 measured reflections
2239 independent reflections
1402 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.153
S = 1.03
2239 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1996 ); cell refinement: SAINT (Bruker, 1996); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681003120X/zs2054sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681003120X/zs2054Isup2.hkl

checkCIF report

Comment top

The Williamson reaction is a very useful transformation in organic synthesis since the products are of value in both industrial and academic applications. It usually involves the reaction of an alkali-metal salt of a hydroxy compound and an alkyl halide (Dermer, 1934). In the present paper, we present the structure of the title compound, C₁₅H₁₂F₂O₂ (I), which was synthesized by the reaction of 1-(2-hydroxyphenyl)ethanone, potassium carbonate and 3,5-difluorobenzyl bromide. We have previously reported the structure of a compound of this type (Ma et al., 2010). In (I) (Fig. 1), the ethanone group is close to coplanar with the benzene ring [torsion angle C4–C3–C2–O1, 178.8 (2)°] while the dihedral angle between the aromatic rings is 70.43 (4)°. The crystal packing exhibits no significantly short intermolecular contacts.

Related literature top

For background to the Williamson reaction in organic synthesis, see: Dermer (1934). For a related structure, see: Ma et al. (2010).

Experimental top

1-(2-Hydroxyphenyl)ethanone (4 mmol), potassium carbonate (8 mmol), 3,5-difluorobenzyl bromide (4 mmol), and 40 ml acetone were mixed in a 100 ml flask. After 3 h stirring at 331 K, the crude product was obtained. Crystals of (I) were obtained by recrystallization from n-hexane/ethyl acetate.

Structure description top

For background to the Williamson reaction in organic synthesis, see: Dermer (1934). For a related structure, see: Ma et al. (2010).

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with atom labels, and displacement ellipsoids drawn at the 30% probability level.

1-[2-(3,5-Difluorobenzyloxy)phenyl]ethanone top

Crystal data top

C₁₅H₁₂F₂O₂	Z = 2
M_r = 262.25	F(000) = 272
Triclinic, P1	D_x = 1.352 Mg m⁻³
Hall symbol: -P 1	Melting point = 347–348 K
a = 7.2808 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9734 (8) Å	Cell parameters from 1136 reflections
c = 11.6466 (12) Å	θ = 2.9–24.8°
α = 91.587 (1)°	µ = 0.11 mm⁻¹
β = 106.559 (2)°	T = 298 K
γ = 95.343 (1)°	Plate, colorless
V = 644.22 (11) Å³	0.42 × 0.38 × 0.20 mm

Data collection top

Bruker SMART CD area-detector diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1402 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.956, T_max = 0.979	k = −9→5
3373 measured reflections	l = −13→13

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0702P)² + 0.1465P] where P = (F_o² + 2F_c²)/3
2239 reflections	(Δ/σ)_max = 0.001
173 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₅H₁₂F₂O₂	γ = 95.343 (1)°
M_r = 262.25	V = 644.22 (11) Å³
Triclinic, P1	Z = 2
a = 7.2808 (7) Å	Mo Kα radiation
b = 7.9734 (8) Å	µ = 0.11 mm⁻¹
c = 11.6466 (12) Å	T = 298 K
α = 91.587 (1)°	0.42 × 0.38 × 0.20 mm
β = 106.559 (2)°

Data collection top

Bruker SMART CD area-detector diffractometer	2239 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1402 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.979	R_int = 0.014
3373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
2239 reflections	Δρ_min = −0.20 e Å⁻³
173 parameters

Special details top

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. 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 (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.1438 (3)	0.8789 (4)	0.0404 (2)	0.1646 (11)
F2	0.6758 (4)	0.6785 (4)	−0.0348 (2)	0.1880 (13)
O1	0.7550 (3)	0.2045 (2)	0.54230 (18)	0.0964 (7)
O2	0.7176 (2)	0.67975 (18)	0.41603 (13)	0.0629 (5)
C1	0.6631 (4)	0.3400 (3)	0.3629 (2)	0.0627 (7)
H1A	0.6321	0.2260	0.3292	0.094*
H1B	0.7598	0.3965	0.3321	0.094*
H1C	0.5495	0.3981	0.3416	0.094*
C2	0.7371 (3)	0.3388 (3)	0.4951 (2)	0.0564 (6)
C3	0.7914 (3)	0.4967 (3)	0.57422 (19)	0.0471 (5)
C4	0.7837 (3)	0.6620 (3)	0.53600 (19)	0.0481 (5)
C5	0.8396 (3)	0.7987 (3)	0.6196 (2)	0.0583 (6)
H5	0.8355	0.9080	0.5938	0.070*
C6	0.9010 (4)	0.7728 (3)	0.7398 (2)	0.0659 (7)
H6	0.9379	0.8650	0.7950	0.079*
C7	0.9086 (4)	0.6135 (3)	0.7795 (2)	0.0674 (7)
H7	0.9501	0.5966	0.8612	0.081*
C8	0.8540 (3)	0.4786 (3)	0.6971 (2)	0.0590 (6)
H8	0.8592	0.3703	0.7247	0.071*
C9	0.7050 (4)	0.8454 (3)	0.3733 (2)	0.0700 (7)
H9A	0.8327	0.9048	0.3882	0.084*
H9B	0.6320	0.9090	0.4138	0.084*
C10	0.6061 (4)	0.8257 (3)	0.2421 (2)	0.0587 (6)
C11	0.4210 (4)	0.8648 (3)	0.1996 (2)	0.0682 (7)
H11	0.3585	0.9069	0.2518	0.082*
C12	0.3289 (4)	0.8415 (4)	0.0801 (3)	0.0856 (9)
C13	0.4081 (5)	0.7794 (4)	−0.0002 (3)	0.0902 (9)
H13	0.3405	0.7632	−0.0811	0.108*
C14	0.5903 (6)	0.7418 (5)	0.0421 (3)	0.0977 (10)
C15	0.6927 (5)	0.7637 (4)	0.1624 (3)	0.0914 (9)
H15	0.8189	0.7365	0.1887	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0955 (15)	0.243 (3)	0.1260 (18)	0.0644 (17)	−0.0240 (13)	−0.0392 (17)
F2	0.187 (3)	0.284 (4)	0.1253 (19)	0.063 (2)	0.0883 (18)	−0.035 (2)
O1	0.163 (2)	0.0435 (11)	0.0898 (14)	0.0206 (11)	0.0447 (13)	0.0108 (10)
O2	0.0905 (12)	0.0383 (9)	0.0520 (10)	0.0087 (8)	0.0073 (8)	0.0027 (7)
C1	0.0713 (16)	0.0452 (13)	0.0708 (16)	0.0032 (11)	0.0215 (13)	−0.0080 (11)
C2	0.0622 (15)	0.0418 (13)	0.0717 (16)	0.0098 (10)	0.0285 (12)	0.0048 (11)
C3	0.0466 (12)	0.0453 (12)	0.0519 (13)	0.0099 (9)	0.0164 (10)	0.0051 (10)
C4	0.0481 (12)	0.0447 (12)	0.0507 (13)	0.0090 (9)	0.0117 (10)	0.0024 (10)
C5	0.0618 (15)	0.0463 (13)	0.0625 (15)	0.0097 (11)	0.0103 (12)	−0.0028 (11)
C6	0.0668 (16)	0.0672 (17)	0.0589 (16)	0.0124 (12)	0.0101 (12)	−0.0132 (12)
C7	0.0713 (17)	0.0807 (19)	0.0501 (14)	0.0160 (14)	0.0148 (12)	0.0049 (13)
C8	0.0598 (14)	0.0578 (15)	0.0646 (16)	0.0149 (11)	0.0227 (12)	0.0135 (12)
C9	0.0921 (19)	0.0431 (13)	0.0622 (15)	0.0051 (12)	0.0025 (13)	0.0081 (11)
C10	0.0715 (16)	0.0443 (13)	0.0597 (15)	0.0077 (11)	0.0166 (12)	0.0110 (11)
C11	0.0706 (18)	0.0718 (17)	0.0618 (16)	0.0081 (13)	0.0189 (13)	−0.0016 (12)
C12	0.0740 (19)	0.099 (2)	0.075 (2)	0.0192 (16)	0.0052 (16)	−0.0020 (16)
C13	0.102 (2)	0.106 (2)	0.0591 (18)	0.0128 (19)	0.0171 (17)	0.0042 (16)
C14	0.117 (3)	0.117 (3)	0.076 (2)	0.022 (2)	0.052 (2)	−0.0050 (18)
C15	0.082 (2)	0.105 (2)	0.091 (2)	0.0324 (17)	0.0235 (17)	0.0040 (18)

Geometric parameters (Å, º) top

F1—C12	1.359 (3)	C6—H6	0.9300
F2—C14	1.340 (4)	C7—C8	1.372 (3)
O1—C2	1.218 (3)	C7—H7	0.9300
O2—C4	1.358 (2)	C8—H8	0.9300
O2—C9	1.426 (3)	C9—C10	1.489 (3)
C1—C2	1.480 (3)	C9—H9A	0.9700
C1—H1A	0.9600	C9—H9B	0.9700
C1—H1B	0.9600	C10—C11	1.365 (3)
C1—H1C	0.9600	C10—C15	1.368 (4)
C2—C3	1.491 (3)	C11—C12	1.361 (4)
C3—C8	1.389 (3)	C11—H11	0.9300
C3—C4	1.404 (3)	C12—C13	1.336 (4)
C4—C5	1.390 (3)	C13—C14	1.342 (5)
C5—C6	1.371 (3)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.384 (4)
C6—C7	1.365 (3)	C15—H15	0.9300

C4—O2—C9	118.86 (17)	C7—C8—H8	118.6
C2—C1—H1A	109.5	C3—C8—H8	118.6
C2—C1—H1B	109.5	O2—C9—C10	106.94 (18)
H1A—C1—H1B	109.5	O2—C9—H9A	110.3
C2—C1—H1C	109.5	C10—C9—H9A	110.3
H1A—C1—H1C	109.5	O2—C9—H9B	110.3
H1B—C1—H1C	109.5	C10—C9—H9B	110.3
O1—C2—C1	119.4 (2)	H9A—C9—H9B	108.6
O1—C2—C3	118.1 (2)	C11—C10—C15	118.4 (2)
C1—C2—C3	122.6 (2)	C11—C10—C9	119.5 (2)
C8—C3—C4	116.9 (2)	C15—C10—C9	122.0 (3)
C8—C3—C2	117.04 (19)	C12—C11—C10	119.4 (3)
C4—C3—C2	126.04 (19)	C12—C11—H11	120.3
O2—C4—C5	122.9 (2)	C10—C11—H11	120.3
O2—C4—C3	116.96 (18)	C13—C12—F1	118.0 (3)
C5—C4—C3	120.2 (2)	C13—C12—C11	123.8 (3)
C6—C5—C4	120.2 (2)	F1—C12—C11	118.2 (3)
C6—C5—H5	119.9	C12—C13—C14	116.5 (3)
C4—C5—H5	119.9	C12—C13—H13	121.7
C7—C6—C5	120.9 (2)	C14—C13—H13	121.7
C7—C6—H6	119.6	F2—C14—C13	118.8 (3)
C5—C6—H6	119.6	F2—C14—C15	118.6 (4)
C6—C7—C8	118.9 (2)	C13—C14—C15	122.6 (3)
C6—C7—H7	120.5	C10—C15—C14	119.2 (3)
C8—C7—H7	120.5	C10—C15—H15	120.4
C7—C8—C3	122.9 (2)	C14—C15—H15	120.4

O1—C2—C3—C8	−1.7 (3)	C2—C3—C8—C7	179.8 (2)
C1—C2—C3—C8	178.3 (2)	C4—O2—C9—C10	−173.0 (2)
O1—C2—C3—C4	178.8 (2)	O2—C9—C10—C11	107.6 (3)
C1—C2—C3—C4	−1.2 (3)	O2—C9—C10—C15	−70.1 (3)
C9—O2—C4—C5	0.1 (3)	C15—C10—C11—C12	−0.2 (4)
C9—O2—C4—C3	179.2 (2)	C9—C10—C11—C12	−177.9 (2)
C8—C3—C4—O2	−178.31 (19)	C10—C11—C12—C13	1.0 (5)
C2—C3—C4—O2	1.2 (3)	C10—C11—C12—F1	179.0 (3)
C8—C3—C4—C5	0.8 (3)	F1—C12—C13—C14	−179.2 (3)
C2—C3—C4—C5	−179.7 (2)	C11—C12—C13—C14	−1.1 (5)
O2—C4—C5—C6	178.5 (2)	C12—C13—C14—F2	179.7 (3)
C3—C4—C5—C6	−0.6 (3)	C12—C13—C14—C15	0.6 (5)
C4—C5—C6—C7	0.1 (4)	C11—C10—C15—C14	−0.3 (4)
C5—C6—C7—C8	0.1 (4)	C9—C10—C15—C14	177.3 (3)
C6—C7—C8—C3	0.2 (4)	F2—C14—C15—C10	−179.0 (3)
C4—C3—C8—C7	−0.6 (3)	C13—C14—C15—C10	0.1 (5)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂F₂O₂
M_r	262.25
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.2808 (7), 7.9734 (8), 11.6466 (12)
α, β, γ (°)	91.587 (1), 106.559 (2), 95.343 (1)
V (Å³)	644.22 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.42 × 0.38 × 0.20

Data collection
Diffractometer	Bruker SMART CD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.956, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	3373, 2239, 1402
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.153, 1.03
No. of reflections	2239
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We would like to acknowledge funding support from the National Natural Science Foundation of China (grant No. 30971882) and the Program of Natural Science Basic Research in Shaanxi (No. 2009JM3010).

References

Bruker (1996). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dermer, O. C. (1934). Chem. Rev. 14, 385–430. CrossRef CAS Google Scholar
Ma, Y.-T., Wang, J.-J., Liu, X.-W., Yang, S.-X. & Gao, J.-M. (2010). Acta Cryst. E66, o52. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar