2-Bromo-1-(4-methoxy­phen­yl)ethanone

Zhang, J.; Zhuang, L.; Wang, G.

doi:10.1107/S1600536809033303

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2245

doi:10.1107/S1600536809033303

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2-Bromo-1-(4-methoxyphenyl)ethanone

Jian Zhang,^a Ling-hua Zhuang ^a and Guo-wei Wang ^a ^*

^aDepartment of Light Chemical Engineering, College of Food Science and Light Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kingwell2004@sina.com.cn

(Received 13 August 2009; accepted 21 August 2009; online 26 August 2009)

The title compound, C₉H₉BrO₂, prepared by the reaction of 4-methoxyacetophenone and cupric bromide, , is approximately planar (r.m.s. deviation 0.0008 Å). In the crystal, weak intermolecular aromatic C—H⋯O_carbonyl hydrogen-bonding interactions result in a one-dimensional chain structure.

Related literature

For background to hydrazone compounds, see: Domiano et al. (1984 ); Li et al. (1988 ); Sadik et al. (2004 ). For background to thiazole compounds, see: Shinagawa et al. (1997 ); Shivarama et al.(2003 ); Dinçer et al. (2005 ); Zhang et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉BrO₂
M_r = 229.06
Monoclinic, P 2₁ /c
a = 7.7360 (15) Å
b = 12.441 (3) Å
c = 10.048 (2) Å
β = 111.42 (3)°
V = 900.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.52 mm⁻¹
T = 305 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.465, T_max = 0.661
1634 measured reflections
1634 independent reflections
924 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.116
S = 1.01
1634 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1ⁱ	0.93	2.58	3.505 (7)	171
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033303/zs2006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033303/zs2006Isup2.hkl

checkCIF report

Comment top

The chemistry of hydrazones, owing to their coordinating capability, pharmacological activity, antibacterial and antifungal properties, and their use in analytical chemistry as highly selective extractants, has been intensively investigated (Domiano et al., 1984; Li et al., 1988; Sadık et al., 2004). In addition, many thiazole compounds are of considerable importance because of their antibacterial and anti-inflammatory activity (Shinagawa et al., 1997; Shivarama et al., 2003; Dinçer et al., 2005). We have focused our synthetic and structural studies on new derivatives of thiazole-substituted hydrazones (Zhang et al., 2009). We report here the crystal structure of a bromo-substituted methoxyacetophenone, the title compound C₉H₉BrO₂ (I), which is a very important intermediate for the synthesis of thiazole-substituted hydrazones.

In (I), all bond lengths are within normal ranges (Allen et al., 1987). The presence of a strong intramolecular aromatic C8–H···O1_carbonyl hydrogen bond (Table 1) forms a pseudo five-membered ring [O1/C2/C3/C8/H8A with an r.m.s. deviation 0.0069 Å], maintaining essential coplanarity of the ketone side chain with the benzene ring (Fig. 1) [torsion angle: C1–C2–C3–C8, -178.0 (5)°]. The methoxy group is similarly essentially coplanar [torsion angle: C5–C6–O2–C9, 172.0 (6)°].

The molecules of (I) associate through weak intermolecular aromatic C—H···O_carbonyl hydrogen bonds forming one-dimensional chains which extend along the b axial direction in the unit cell (Fig.2).

Related literature top

For background to hydrazone compounds, see: Domiano et al. (1984); Li et al. (1988); Sadik et al. (2004). For background to thiazole compounds, see: Shinagawa et al. (1997); Shivarama et al.(2003); Dinçer et al. (2005); Zhang et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

4-Methoxyacetophenone (1.50 g, 0.01 mol) was dissolved in 50 ml ethyl acetate, cupric bromide (3.36 g, 0.015 mol) was added and the mixture was refluxed for ca. 3 h. On cooling, the solid which separated was filtered and recrystallized from ethyl acetate. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of ethyl acetate. ¹H NMR (CDCl₃, δ, p.p.m.) 8.17 (d, 2 H), 7.49 (d, 2 H), 4.5 (s, 2 H), 3.81 (s,3 H).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme with non-H atoms drawn as 30% displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal packing of (I) showing hydrogen bonds as dashed lines.

2-Bromo-1-(4-methoxyphenyl)ethanone top

Crystal data top

C₉H₉BrO₂	F(000) = 456
M_r = 229.06	D_x = 1.690 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 7.7360 (15) Å	θ = 1–25°
b = 12.441 (3) Å	µ = 4.52 mm⁻¹
c = 10.048 (2) Å	T = 305 K
β = 111.42 (3)°	Block, colorless
V = 900.3 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 2.7°
ω/2θ scans	h = −9→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
T_min = 0.465, T_max = 0.661	l = 0→12
1634 measured reflections	3 standard reflections every 200 reflections
1634 independent reflections	intensity decay: 9%

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.048P)²] where P = (F_o² + 2F_c²)/3
1634 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₉H₉BrO₂	V = 900.3 (4) Å³
M_r = 229.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7360 (15) Å	µ = 4.52 mm⁻¹
b = 12.441 (3) Å	T = 305 K
c = 10.048 (2) Å	0.20 × 0.10 × 0.10 mm
β = 111.42 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	924 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.465, T_max = 0.661	3 standard reflections every 200 reflections
1634 measured reflections	intensity decay: 9%
1634 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
1634 reflections	Δρ_min = −0.53 e Å⁻³
109 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
Br	0.20597 (10)	0.66539 (6)	0.07859 (7)	0.0717 (3)
O1	0.3621 (7)	0.8754 (4)	0.2083 (5)	0.0848 (15)
C1	0.1809 (8)	0.8016 (5)	−0.0164 (6)	0.0576 (17)
H1A	0.2308	0.7957	−0.0918	0.069*
H1B	0.0500	0.8190	−0.0608	0.069*
O2	0.2187 (6)	1.3075 (4)	−0.1487 (5)	0.0689 (13)
C2	0.2781 (8)	0.8917 (5)	0.0820 (6)	0.0534 (16)
C3	0.2657 (7)	0.9994 (5)	0.0181 (6)	0.0478 (14)
C4	0.1597 (8)	1.0221 (5)	−0.1242 (6)	0.0593 (17)
H4A	0.0957	0.9671	−0.1849	0.071*
C5	0.1493 (9)	1.1250 (5)	−0.1751 (7)	0.0633 (18)
H5A	0.0780	1.1390	−0.2703	0.076*
C6	0.2432 (8)	1.2086 (5)	−0.0870 (7)	0.0538 (16)
C7	0.3497 (8)	1.1859 (5)	0.0560 (7)	0.0600 (17)
H7A	0.4138	1.2406	0.1172	0.072*
C8	0.3586 (8)	1.0831 (5)	0.1051 (6)	0.0564 (16)
H8A	0.4297	1.0688	0.2003	0.068*
C9	0.2906 (10)	1.3980 (6)	−0.0610 (8)	0.083 (2)
H9A	0.2625	1.4618	−0.1186	0.124*
H9B	0.4227	1.3908	−0.0151	0.124*
H9C	0.2353	1.4028	0.0102	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0721 (5)	0.0588 (5)	0.0722 (5)	0.0064 (4)	0.0121 (3)	0.0076 (4)
O1	0.104 (4)	0.067 (3)	0.050 (3)	0.002 (3)	−0.011 (3)	0.003 (2)
C1	0.054 (4)	0.060 (4)	0.050 (3)	0.002 (3)	0.008 (3)	−0.003 (3)
O2	0.079 (3)	0.054 (3)	0.070 (3)	−0.007 (2)	0.021 (2)	−0.002 (2)
C2	0.042 (3)	0.060 (4)	0.049 (4)	0.007 (3)	0.006 (3)	−0.005 (3)
C3	0.036 (3)	0.050 (4)	0.053 (4)	−0.001 (3)	0.011 (3)	−0.003 (3)
C4	0.060 (4)	0.056 (4)	0.049 (3)	−0.002 (3)	0.005 (3)	−0.012 (3)
C5	0.067 (4)	0.059 (4)	0.052 (4)	0.005 (4)	0.007 (3)	0.000 (3)
C6	0.047 (4)	0.056 (4)	0.058 (4)	−0.004 (3)	0.018 (3)	−0.007 (3)
C7	0.054 (4)	0.062 (5)	0.058 (4)	−0.011 (3)	0.013 (3)	−0.010 (3)
C8	0.044 (4)	0.064 (4)	0.049 (3)	−0.004 (3)	0.001 (3)	−0.005 (3)
C9	0.087 (5)	0.063 (5)	0.096 (5)	−0.012 (4)	0.031 (4)	−0.004 (4)

Geometric parameters (Å, º) top

Br—C1	1.920 (6)	C4—H4A	0.9300
O1—C2	1.213 (6)	C5—C6	1.387 (8)
C1—C2	1.502 (8)	C5—H5A	0.9300
C1—H1A	0.9700	C6—C7	1.400 (8)
C1—H1B	0.9700	C7—C8	1.363 (8)
O2—C6	1.359 (7)	C7—H7A	0.9300
O2—C9	1.412 (8)	C8—H8A	0.9300
C2—C3	1.474 (8)	C9—H9A	0.9600
C3—C8	1.380 (7)	C9—H9B	0.9600
C3—C4	1.393 (8)	C9—H9C	0.9600
C4—C5	1.370 (8)

C2—C1—Br	113.3 (4)	C4—C5—H5A	119.4
C2—C1—H1A	108.9	C6—C5—H5A	119.4
Br—C1—H1A	108.9	O2—C6—C5	115.8 (5)
C2—C1—H1B	108.9	O2—C6—C7	125.6 (6)
Br—C1—H1B	108.9	C5—C6—C7	118.6 (6)
H1A—C1—H1B	107.7	C8—C7—C6	119.6 (6)
C6—O2—C9	118.7 (5)	C8—C7—H7A	120.2
O1—C2—C3	122.1 (6)	C6—C7—H7A	120.2
O1—C2—C1	120.8 (6)	C7—C8—C3	122.2 (6)
C3—C2—C1	117.0 (5)	C7—C8—H8A	118.9
C8—C3—C4	118.2 (6)	C3—C8—H8A	118.9
C8—C3—C2	118.3 (5)	O2—C9—H9A	109.5
C4—C3—C2	123.4 (6)	O2—C9—H9B	109.5
C5—C4—C3	120.3 (6)	H9A—C9—H9B	109.5
C5—C4—H4A	119.9	O2—C9—H9C	109.5
C3—C4—H4A	119.9	H9A—C9—H9C	109.5
C4—C5—C6	121.2 (6)	H9B—C9—H9C	109.5

Br—C1—C2—O1	0.0 (8)	C9—O2—C6—C5	172.0 (6)
Br—C1—C2—C3	−179.8 (4)	C9—O2—C6—C7	−6.3 (9)
O1—C2—C3—C8	2.2 (9)	C4—C5—C6—O2	−178.5 (6)
C1—C2—C3—C8	−178.0 (5)	C4—C5—C6—C7	0.0 (9)
O1—C2—C3—C4	−175.3 (6)	O2—C6—C7—C8	178.3 (6)
C1—C2—C3—C4	4.5 (9)	C5—C6—C7—C8	0.0 (9)
C8—C3—C4—C5	0.1 (9)	C6—C7—C8—C3	0.0 (9)
C2—C3—C4—C5	177.6 (6)	C4—C3—C8—C7	−0.1 (9)
C3—C4—C5—C6	0.0 (10)	C2—C3—C8—C7	−177.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.93	2.47	2.780 (8)	100
C7—H7A···O1ⁱ	0.93	2.58	3.505 (7)	171

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

Experimental details

Crystal data
Chemical formula	C₉H₉BrO₂
M_r	229.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	305
a, b, c (Å)	7.7360 (15), 12.441 (3), 10.048 (2)
β (°)	111.42 (3)
V (Å³)	900.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.52
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.465, 0.661
No. of measured, independent and observed [I > 2σ(I)] reflections	1634, 1634, 924
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.116, 1.01
No. of reflections	1634
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.53

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.93	2.47	2.780 (8)	99.6
C7—H7A···O1ⁱ	0.93	2.58	3.505 (7)	171.1

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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