2,2-Dibromo-N-(4-fluoro­phen­yl)acetamide

Qian, X.; Fang, Z.; Bao, S.; Guo, K.; Wei, P.

doi:10.1107/S1600536812021174

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1824

doi:10.1107/S1600536812021174

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2,2-Dibromo-N-(4-fluorophenyl)acetamide

Xiangjun Qian,^a Zheng Fang,^a Shuxin Bao,^a Kai Guo ^b ^* and Ping Wei ^b

^aSchool of Pharmaceutical Sciences, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fzcpu@163.com

(Received 10 April 2012; accepted 10 May 2012; online 19 May 2012)

In the crystal structure of the title compound, C₈H₆Br₂FNO, C—H⋯O and N—H⋯O hydrogen bonding results in six-membered rings and links the molecules into chains running parallel to the c axis. The dihedral angle between the fluorophenyl ring and the acetamide group is 29.5 (5)°.

Related literature

For background information, see: Feng et al. (2012 ). For related crystal structures, see: Gowda et al. (2009 ); Feng et al. (2012).

Experimental

Crystal data

C₈H₆Br₂FNO
M_r = 310.96
Monoclinic, P 2₁ /c
a = 9.746 (2) Å
b = 10.980 (2) Å
c = 9.426 (2) Å
β = 96.33 (3)°
V = 1002.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 8.06 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Enraf–Nonious CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.975, T_max = 0.991
1937 measured reflections
1827 independent reflections
900 reflections with I > 2σ(I)
R_int = 0.068
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.094
S = 1.00
1827 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯Oⁱ	0.86	2.06	2.868 (7)	156
C1—H1A⋯Oⁱ	0.98	2.37	3.178 (9)	140
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021174/pv2533sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021174/pv2533Isup2.hkl

checkCIF report

Comment top

As a part of our studies on the synthesis of Ezetimibe (Fang et al., 2012), the title compound which is one of the derivates of an intermediate, has been synthesized and its crystal structure is reported in this paper.

In the title molecule (Fig. 1), the dihedral angle between fluorophenyl ring (F/C3–C8) and acetamide group (O/N/C1/C2) group is 29.5 (5)°. The carbonyl O atom is hydrogen bonded to hydrogen atoms at N and C1, resulting in six membered rings linking the molecules into chains running parallel to the c-axis (Fig. 2 and Tab. 1). The bond distances and angles in the title molecule are in excellent agreement with the corresponding bond distances and angles reported in closely related structures (Gowda et al., 2009; Feng et al., 2012).

Related literature top

For background information, see: Feng et al. (2012). For related crystal structures, see: Gowda et al. (2009); Fang et al. (2012).

Experimental top

To 3-ethoxy-N-(4-fluorophenyl)acrylamide (1 g) was added 1,4-dioxane (20 ml) and water (20 ml) in a 50 ml flask. The solution was cooled to 273 K in an ice bath and N-bromosuccinimide (1.6 g) was added after 30 minutes. The solution was stirred at room temperature for 3 h. Then, the solution was heated to 353 K, after 40 minutes, the resulting mixture was concentrated under vacuum, the solid was collected by vacuum filtration, washed with cold water. Finally, the product was separated by silica gel column (yield = 59%). Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.

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), ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the N—H···O and C—H···Ohydrogen bonds (dotted lines) in the crystal structure of the title compound.

2,2-Dibromo-N-(4-fluorophenyl)acetamide top

Crystal data top

C₈H₆Br₂FNO	F(000) = 592
M_r = 310.96	D_x = 2.060 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.746 (2) Å	θ = 9–12°
b = 10.980 (2) Å	µ = 8.06 mm⁻¹
c = 9.426 (2) Å	T = 293 K
β = 96.33 (3)°	Block, colorless
V = 1002.5 (3) Å³	0.10 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonious CAD-4 diffractometer	900 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = −11→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→13
T_min = 0.975, T_max = 0.991	l = −11→11
1937 measured reflections	3 standard reflections every 200 reflections
1827 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.024P)²] where P = (F_o² + 2F_c²)/3
1827 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₈H₆Br₂FNO	V = 1002.5 (3) Å³
M_r = 310.96	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.746 (2) Å	µ = 8.06 mm⁻¹
b = 10.980 (2) Å	T = 293 K
c = 9.426 (2) Å	0.10 × 0.10 × 0.10 mm
β = 96.33 (3)°

Data collection top

Enraf–Nonious CAD-4 diffractometer	900 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.068
T_min = 0.975, T_max = 0.991	3 standard reflections every 200 reflections
1937 measured reflections	intensity decay: 1%
1827 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.00	Δρ_max = 0.49 e Å⁻³
1827 reflections	Δρ_min = −0.50 e Å⁻³
118 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
F	0.4558 (5)	0.2056 (4)	0.4060 (6)	0.0868 (17)
Br1	0.27410 (10)	0.98435 (8)	0.42192 (10)	0.0675 (3)
Br2	−0.02715 (10)	0.90635 (10)	0.29891 (11)	0.0840 (4)
O	0.2133 (6)	0.7340 (5)	0.2350 (5)	0.0635 (17)
N	0.2193 (6)	0.6579 (5)	0.4588 (6)	0.0439 (17)
H0A	0.1995	0.6743	0.5434	0.053*
C1	0.1342 (8)	0.8605 (6)	0.4178 (8)	0.048 (2)
H1A	0.1111	0.8455	0.5149	0.058*
C2	0.1936 (8)	0.7438 (7)	0.3585 (8)	0.046 (2)
C3	0.2775 (8)	0.5405 (6)	0.4353 (8)	0.0390 (19)
C4	0.2452 (8)	0.4467 (7)	0.5254 (8)	0.052 (2)
H4A	0.1850	0.4610	0.5936	0.062*
C5	0.3007 (9)	0.3355 (8)	0.5140 (9)	0.059 (3)
H5A	0.2770	0.2713	0.5708	0.070*
C6	0.3943 (8)	0.3195 (8)	0.4150 (10)	0.054 (2)
C7	0.4260 (8)	0.4084 (8)	0.3246 (8)	0.056 (2)
H7A	0.4856	0.3933	0.2561	0.067*
C8	0.3694 (8)	0.5186 (7)	0.3364 (7)	0.046 (2)
H8A	0.3923	0.5815	0.2771	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F	0.081 (4)	0.047 (3)	0.135 (5)	0.008 (3)	0.025 (3)	−0.004 (3)
Br1	0.0902 (7)	0.0504 (6)	0.0640 (6)	−0.0033 (6)	0.0179 (5)	−0.0068 (5)
Br2	0.0681 (7)	0.1079 (10)	0.0749 (8)	0.0201 (7)	0.0034 (5)	0.0095 (7)
O	0.116 (5)	0.052 (4)	0.026 (3)	0.013 (4)	0.020 (3)	−0.002 (3)
N	0.067 (5)	0.037 (4)	0.030 (4)	−0.005 (4)	0.016 (3)	−0.003 (3)
C1	0.075 (6)	0.037 (5)	0.035 (5)	−0.001 (4)	0.017 (4)	0.007 (4)
C2	0.063 (6)	0.046 (5)	0.029 (5)	0.001 (5)	−0.002 (4)	−0.007 (5)
C3	0.050 (5)	0.036 (5)	0.028 (5)	−0.006 (4)	−0.010 (4)	−0.001 (4)
C4	0.079 (7)	0.042 (6)	0.036 (5)	−0.004 (5)	0.009 (5)	0.004 (4)
C5	0.063 (6)	0.039 (6)	0.075 (7)	−0.014 (5)	0.012 (5)	0.014 (5)
C6	0.043 (5)	0.040 (6)	0.078 (7)	0.004 (5)	0.007 (5)	−0.004 (5)
C7	0.064 (6)	0.054 (6)	0.051 (6)	−0.005 (5)	0.014 (5)	−0.011 (5)
C8	0.056 (5)	0.044 (5)	0.037 (5)	0.000 (5)	0.009 (4)	0.010 (4)

Geometric parameters (Å, º) top

F—C6	1.394 (8)	C3—C4	1.392 (9)
Br1—C1	1.923 (7)	C4—C5	1.344 (9)
Br2—C1	1.896 (7)	C4—H4A	0.9300
O—C2	1.205 (7)	C5—C6	1.386 (10)
N—C2	1.339 (8)	C5—H5A	0.9300
N—C3	1.436 (8)	C6—C7	1.354 (10)
N—H0A	0.8600	C7—C8	1.340 (9)
C1—C2	1.536 (10)	C7—H7A	0.9300
C1—H1A	0.9800	C8—H8A	0.9300
C3—C8	1.384 (9)

C2—N—C3	124.8 (6)	C5—C4—C3	120.2 (8)
C2—N—H0A	117.6	C5—C4—H4A	119.9
C3—N—H0A	117.6	C3—C4—H4A	119.9
C2—C1—Br2	109.1 (5)	C4—C5—C6	118.0 (8)
C2—C1—Br1	107.6 (5)	C4—C5—H5A	121.0
Br2—C1—Br1	111.3 (3)	C6—C5—H5A	121.0
C2—C1—H1A	109.6	C7—C6—C5	123.1 (8)
Br2—C1—H1A	109.6	C7—C6—F	118.6 (8)
Br1—C1—H1A	109.6	C5—C6—F	118.3 (8)
O—C2—N	125.6 (8)	C8—C7—C6	118.3 (8)
O—C2—C1	122.2 (7)	C8—C7—H7A	120.8
N—C2—C1	112.3 (6)	C6—C7—H7A	120.8
C8—C3—C4	119.3 (7)	C7—C8—C3	121.0 (7)
C8—C3—N	123.7 (7)	C7—C8—H8A	119.5
C4—C3—N	116.8 (7)	C3—C8—H8A	119.5

C3—N—C2—O	1.4 (13)	N—C3—C4—C5	−177.0 (7)
C3—N—C2—C1	−178.8 (6)	C3—C4—C5—C6	2.7 (13)
Br2—C1—C2—O	50.2 (9)	C4—C5—C6—C7	−3.8 (14)
Br1—C1—C2—O	−70.7 (9)	C4—C5—C6—F	177.9 (7)
Br2—C1—C2—N	−129.7 (6)	C5—C6—C7—C8	3.4 (13)
Br1—C1—C2—N	109.4 (6)	F—C6—C7—C8	−178.3 (7)
C2—N—C3—C8	30.9 (11)	C6—C7—C8—C3	−2.0 (12)
C2—N—C3—C4	−153.6 (7)	C4—C3—C8—C7	1.0 (11)
C8—C3—C4—C5	−1.4 (12)	N—C3—C8—C7	176.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Oⁱ	0.86	2.06	2.868 (7)	156
C1—H1A···Oⁱ	0.98	2.37	3.178 (9)	140
C8—H8A···O	0.93	2.42	2.916 (9)	113

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆Br₂FNO
M_r	310.96
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.746 (2), 10.980 (2), 9.426 (2)
β (°)	96.33 (3)
V (Å³)	1002.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.06
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonious CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.975, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	1937, 1827, 900
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.094, 1.00
No. of reflections	1827
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.50

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Oⁱ	0.86	2.06	2.868 (7)	156
C1—H1A···Oⁱ	0.98	2.37	3.178 (9)	140

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

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

References

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