2-Chloro-1-(3-fluoro­benz­yloxy)-4-nitro­benzene

Yu, H.

doi:10.1107/S160053680903431X

organic compounds

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Volume 65| Part 10| October 2009| Page o2327

doi:10.1107/S160053680903431X

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2-Chloro-1-(3-fluorobenzyloxy)-4-nitrobenzene

Hui-ling Yu ^a ^*

^aYibin Vocational & Technical College, Si chuan, People's Republic of China
^*Correspondence e-mail: cnyhl@tom.com

(Received 14 August 2009; accepted 27 August 2009; online 5 September 2009)

In the title compound, C₁₃H₉ClFNO₃, the benzene rings are oriented at a dihedral angle of 41.23 (5)°. In the crystal structure, intermolecular C—H⋯O interactions link the molecules in a herring-bone arrangement along the b axis and weak π–π contacts between the benzene rings [centroid–centroid distance = 3.881 (1) Å] may further stabilize the structure.

Related literature

The title compound is a dual ErbB-1/ErbB-2 tyrosine kinase inhibitor, see: Petrov et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₉ClFNO₃
M_r = 281.66
Monoclinic, P 2₁ /c
a = 8.3290 (17) Å
b = 12.640 (3) Å
c = 11.875 (2) Å
β = 96.94 (3)°
V = 1241.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.909, T_max = 0.968
2411 measured reflections
2248 independent reflections
1340 reflections with I > 2σ(I)
R_int = 0.028
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.149
S = 1.01
2248 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O2ⁱ	0.97	2.49	3.423 (4)	162
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903431X/hk2758sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903431X/hk2758Isup2.hkl

checkCIF report

Comment top

The title compound is one kind of important pharmaceutical intermediates, which is dual ErbB-1/ErbB-2 tyrosine kinase inhibitior (Petrov et al., 2006). We report herein its crystal structure.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C8-C13) are, of course, planar and they are oriented at a dihedral angle of A/B = 41.23 (5)°. Atom C7 is -0.061 (3) Å away from the plane of ring A, while atoms Cl, O1, N and C7 are -0.007 (3), 0.001 (3), 0.018 (3) and 0.029 (3) Å away from the plane of ring B, respectively.

In the crystal structure, intermolecular C-H···O interactions link the molecules in herring-bone arrangement along the b axis and π–π contact between the benzene rings, Cg1—Cg2ⁱ, [symmetry code: (i) x, 1/2 - y, 1/2 + z, where Cg1 and Cg2 are centroids of the rings A (C1-C6) and B (C8-C13), respectively] may further stabilize the structure, with centroid-centroid distance of 3.881 (1) Å.

Related literature top

The title compound is a dual ErbB-1/ErbB-2 tyrosine kinase inhibitor, see: Petrov et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, in the presence of sodium carbonate (10 g), 2-chloro-4-nitrophenol (1 mmol) and 1-(bromomethyl)-3-fluorobenzene (1 mmol) in acetonitrile (25 ml) were stirred at 313 K for 8 h. Sodium carbonate was filtered off and the filtrate was washed with brine. The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to give the crude product, which was crystallized from ethyl acetate to give the title compound. Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.1 g) in ethyl acetate (10 ml) and evaporating the solvent slowly at room temperature for 3 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

2-Chloro-1-(3-fluorobenzyloxy)-4-nitrobenzene top

Crystal data top

C₁₃H₉ClFNO₃	F(000) = 576
M_r = 281.66	D_x = 1.508 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.3290 (17) Å	θ = 9–12°
b = 12.640 (3) Å	µ = 0.32 mm⁻¹
c = 11.875 (2) Å	T = 294 K
β = 96.94 (3)°	Block, yellow
V = 1241.0 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1340 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.909, T_max = 0.968	l = −14→14
2411 measured reflections	3 standard reflections every 120 min
2248 independent reflections	intensity decay: 1%

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.07P)²] where P = (F_o² + 2F_c²)/3
2248 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₉ClFNO₃	V = 1241.0 (4) Å³
M_r = 281.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3290 (17) Å	µ = 0.32 mm⁻¹
b = 12.640 (3) Å	T = 294 K
c = 11.875 (2) Å	0.30 × 0.20 × 0.10 mm
β = 96.94 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1340 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.028
T_min = 0.909, T_max = 0.968	3 standard reflections every 120 min
2411 measured reflections	intensity decay: 1%
2248 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	Δρ_max = 0.16 e Å⁻³
2248 reflections	Δρ_min = −0.25 e Å⁻³
172 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl	0.81771 (13)	0.51262 (7)	0.07511 (8)	0.0802 (4)
F	0.4335 (3)	1.00189 (17)	−0.29984 (19)	0.0996 (8)
O1	0.6878 (3)	0.72025 (15)	0.07000 (17)	0.0582 (6)
O2	1.1588 (3)	0.5447 (2)	0.4720 (2)	0.0846 (8)
O3	1.0836 (4)	0.6867 (3)	0.5501 (2)	0.1058 (10)
N	1.0804 (3)	0.6268 (3)	0.4700 (3)	0.0694 (8)
C1	0.3405 (4)	0.8293 (3)	−0.2781 (3)	0.0670 (10)
H1A	0.2801	0.8325	−0.3492	0.080*
C2	0.4320 (4)	0.9129 (3)	−0.2358 (3)	0.0629 (9)
C3	0.5233 (4)	0.9117 (2)	−0.1320 (3)	0.0550 (8)
H3A	0.5858	0.9700	−0.1069	0.066*
C4	0.5210 (4)	0.8224 (2)	−0.0653 (3)	0.0513 (8)
C5	0.4296 (4)	0.7364 (3)	−0.1061 (3)	0.0630 (9)
H5A	0.4279	0.6756	−0.0621	0.076*
C6	0.3407 (4)	0.7401 (3)	−0.2118 (3)	0.0707 (10)
H6A	0.2801	0.6815	−0.2386	0.085*
C7	0.6137 (4)	0.8219 (2)	0.0507 (3)	0.0587 (9)
H7A	0.6959	0.8767	0.0564	0.070*
H7B	0.5415	0.8358	0.1073	0.070*
C8	0.7811 (4)	0.7033 (2)	0.1694 (3)	0.0492 (8)
C9	0.8086 (4)	0.7766 (2)	0.2567 (3)	0.0564 (8)
H9A	0.7609	0.8431	0.2488	0.068*
C10	0.9064 (4)	0.7510 (3)	0.3551 (3)	0.0597 (9)
H10A	0.9250	0.8002	0.4135	0.072*
C11	0.9755 (4)	0.6531 (2)	0.3662 (3)	0.0531 (8)
C12	0.9495 (4)	0.5787 (3)	0.2808 (3)	0.0575 (8)
H12A	0.9970	0.5122	0.2896	0.069*
C13	0.8532 (4)	0.6039 (2)	0.1836 (3)	0.0530 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.1074 (8)	0.0574 (6)	0.0736 (7)	0.0078 (5)	0.0026 (5)	−0.0116 (4)
F	0.135 (2)	0.0791 (15)	0.0789 (15)	0.0098 (14)	−0.0083 (14)	0.0259 (11)
O1	0.0683 (14)	0.0475 (12)	0.0568 (14)	0.0075 (11)	−0.0005 (11)	0.0012 (10)
O2	0.0635 (17)	0.094 (2)	0.0931 (19)	0.0152 (16)	−0.0032 (14)	0.0228 (16)
O3	0.109 (2)	0.124 (3)	0.0751 (19)	0.014 (2)	−0.0258 (17)	−0.0135 (19)
N	0.0542 (18)	0.083 (2)	0.069 (2)	−0.0014 (18)	0.0016 (16)	0.0110 (18)
C1	0.061 (2)	0.083 (3)	0.055 (2)	0.011 (2)	−0.0022 (17)	−0.0035 (19)
C2	0.067 (2)	0.060 (2)	0.062 (2)	0.0124 (19)	0.0055 (18)	0.0090 (18)
C3	0.0521 (19)	0.0494 (18)	0.063 (2)	0.0055 (15)	0.0063 (16)	−0.0019 (15)
C4	0.0482 (18)	0.0511 (18)	0.0552 (19)	0.0061 (15)	0.0087 (15)	0.0009 (15)
C5	0.067 (2)	0.057 (2)	0.065 (2)	−0.0028 (18)	0.0075 (18)	0.0064 (17)
C6	0.061 (2)	0.075 (2)	0.074 (3)	−0.0052 (19)	0.001 (2)	−0.008 (2)
C7	0.068 (2)	0.0494 (19)	0.057 (2)	0.0020 (16)	0.0005 (17)	0.0031 (15)
C8	0.0461 (18)	0.0499 (18)	0.0515 (18)	−0.0016 (15)	0.0054 (15)	0.0030 (15)
C9	0.062 (2)	0.0480 (17)	0.060 (2)	0.0025 (16)	0.0068 (17)	0.0020 (16)
C10	0.060 (2)	0.063 (2)	0.056 (2)	−0.0072 (17)	0.0062 (17)	−0.0032 (16)
C11	0.0446 (18)	0.0566 (19)	0.058 (2)	−0.0012 (16)	0.0055 (15)	0.0078 (16)
C12	0.049 (2)	0.057 (2)	0.068 (2)	0.0068 (16)	0.0107 (17)	0.0077 (17)
C13	0.0534 (19)	0.0518 (19)	0.0548 (19)	−0.0026 (16)	0.0096 (16)	0.0017 (15)

Geometric parameters (Å, º) top

Cl—C13	1.728 (3)	C5—C6	1.379 (5)
F—C2	1.359 (4)	C5—H5A	0.9300
O1—C7	1.432 (3)	C6—H6A	0.9300
O1—C8	1.350 (4)	C7—H7A	0.9700
N—O2	1.225 (4)	C7—H7B	0.9700
N—O3	1.214 (4)	C8—C9	1.388 (4)
N—C11	1.460 (4)	C8—C13	1.394 (4)
C1—C2	1.363 (5)	C9—C10	1.380 (5)
C1—C6	1.375 (4)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.366 (4)
C2—C3	1.367 (4)	C10—H10A	0.9300
C3—C4	1.381 (4)	C11—C12	1.380 (4)
C3—H3A	0.9300	C12—C13	1.361 (4)
C4—C5	1.382 (4)	C12—H12A	0.9300
C4—C7	1.496 (4)

C8—O1—C7	118.3 (2)	O1—C7—H7A	110.0
O2—N—C11	118.2 (3)	C4—C7—H7A	110.0
O3—N—O2	123.5 (3)	O1—C7—H7B	110.0
O3—N—C11	118.3 (3)	C4—C7—H7B	110.0
C2—C1—C6	117.6 (3)	H7A—C7—H7B	108.4
C2—C1—H1A	121.2	O1—C8—C9	124.9 (3)
C6—C1—H1A	121.2	O1—C8—C13	116.3 (3)
F—C2—C1	118.5 (3)	C9—C8—C13	118.8 (3)
F—C2—C3	118.1 (3)	C10—C9—C8	120.3 (3)
C1—C2—C3	123.3 (3)	C10—C9—H9A	119.9
C2—C3—C4	118.7 (3)	C8—C9—H9A	119.9
C2—C3—H3A	120.6	C11—C10—C9	119.5 (3)
C4—C3—H3A	120.6	C11—C10—H10A	120.3
C3—C4—C5	119.2 (3)	C9—C10—H10A	120.3
C3—C4—C7	119.4 (3)	C10—C11—C12	121.3 (3)
C5—C4—C7	121.4 (3)	C10—C11—N	119.3 (3)
C6—C5—C4	120.3 (3)	C12—C11—N	119.4 (3)
C6—C5—H5A	119.8	C13—C12—C11	119.2 (3)
C4—C5—H5A	119.8	C13—C12—H12A	120.4
C1—C6—C5	120.8 (3)	C11—C12—H12A	120.4
C1—C6—H6A	119.6	C12—C13—C8	120.9 (3)
C5—C6—H6A	119.6	C12—C13—Cl	120.4 (3)
O1—C7—C4	108.4 (2)	C8—C13—Cl	118.6 (2)

C6—C1—C2—F	−180.0 (3)	C13—C8—C9—C10	0.3 (5)
C6—C1—C2—C3	0.3 (5)	C8—C9—C10—C11	−0.2 (5)
F—C2—C3—C4	179.1 (3)	C9—C10—C11—C12	−0.1 (5)
C1—C2—C3—C4	−1.2 (5)	C9—C10—C11—N	179.3 (3)
C2—C3—C4—C5	1.3 (5)	O3—N—C11—C10	11.0 (5)
C2—C3—C4—C7	−177.0 (3)	O2—N—C11—C10	−170.0 (3)
C3—C4—C5—C6	−0.5 (5)	O3—N—C11—C12	−169.6 (3)
C7—C4—C5—C6	177.7 (3)	O2—N—C11—C12	9.5 (4)
C2—C1—C6—C5	0.5 (5)	C10—C11—C12—C13	0.2 (5)
C4—C5—C6—C1	−0.4 (5)	N—C11—C12—C13	−179.2 (3)
C8—O1—C7—C4	178.5 (2)	C11—C12—C13—C8	−0.1 (4)
C3—C4—C7—O1	−140.2 (3)	C11—C12—C13—Cl	−179.9 (2)
C5—C4—C7—O1	41.6 (4)	O1—C8—C13—C12	−179.9 (3)
C7—O1—C8—C9	1.5 (4)	C9—C8—C13—C12	−0.2 (4)
C7—O1—C8—C13	−178.8 (3)	O1—C8—C13—Cl	−0.1 (4)
O1—C8—C9—C10	−180.0 (3)	C9—C8—C13—Cl	179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2ⁱ	0.97	2.49	3.423 (4)	162

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉ClFNO₃
M_r	281.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	8.3290 (17), 12.640 (3), 11.875 (2)
β (°)	96.94 (3)
V (Å³)	1241.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.909, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	2411, 2248, 1340
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.149, 1.01
No. of reflections	2248
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2ⁱ	0.97	2.49	3.423 (4)	162

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Petrov, K. G., Zhang, Y. M., Carter, M., Cockerill, G. S., Dickerson, S., Gauthier, C. A., Guo, Y., Mook, R. A., Rusnak, D. W., Walker, A. L., Wood, E. R. & Lackey, K. E. (2006). Bioorg. Med. Chem. Lett. 16, 4686–4691. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S160053680903431X

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