2-Bromo-2-(5-bromo-1H-1,2,4-triazol-1-yl)-1-(2,4-difluoro­phen­yl)ethanone

Wan, K.; Fang, B.; Wang, G.-Z.; Zhou, C.-H.

doi:10.1107/S1600536810011359

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o986

doi:10.1107/S1600536810011359

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2-Bromo-2-(5-bromo-1H-1,2,4-triazol-1-yl)-1-(2,4-difluorophenyl)ethanone

Kun Wan,^a Bo Fang,^a Guang-Zhou Wang ^a and Cheng-He Zhou ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: zhouch@swu.edu.cn

(Received 20 March 2010; accepted 25 March 2010; online 31 March 2010)

In the title compound, C₁₀H₅Br₂F₂N₃O, the mean planes of the benzene and triazole rings form a dihedral angle of 84.86 (2)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link molecules into extended chains propagating along the c axis.

Related literature

For general properties of 1,2,4-triazole derivatives, see: Garfunkle et al. (2008 ); Yu et al. (2009 ). For their antimicrobial activity, see: Luo et al. (2009 ); Zhang et al. (2010 ).

Experimental

Crystal data

C₁₀H₅Br₂F₂N₃O
M_r = 380.99
Monoclinic, P 2₁ /c
a = 9.273 (2) Å
b = 9.375 (2) Å
c = 14.982 (3) Å
β = 104.916 (3)°
V = 1258.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 6.46 mm⁻¹
T = 298 K
0.26 × 0.25 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.199, T_max = 0.203
6096 measured reflections
2206 independent reflections
1577 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 1.04
2206 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.55	3.229 (5)	130
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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: 10.1107/S1600536810011359/lh5016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810011359/lh5016Isup2.hkl

checkCIF report

Comment top

1,2,4-Triazole derivatives are important types of nitrogen-containing aromatic heterocyclic compounds with excellent safety profiles, favorable pharmacokinetic characteristics and a wide range of biological activities (Garfunkle et al., 2008; Yu et al., 2009). Our attention has been focused on the discovery of novel 1,2,4-triazole compounds as antimicrobial agents, and we found that some reported 1,2,4-triazole compounds display significant antimicrobial activities (Luo et al., 2009; Zhang et al., 2010). As part of our research research, we report herein structure of the title compound (I).

The molecular structure of the title compound is shown in Fig. 1. The mean planes of the benzene and triazole rings form a dihedral angle of 84.86 (2) °. In the crystal structure weak intermolecular C—H···O hydrogen bonds link molecules into extended chains along the c axis.

Related literature top

For general properties of 1,2,4-triazole derivatives, see: Garfunkle et al. (2008); Yu et al. (2009). For their antimicrobial activity, see: Luo et al. (2009); Zhang et al. (2010).

Experimental top

To a solution of 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone (1.0 g, 4.4 mmol), sodium acetate (1.4 g, 4.4 mmol) and acetic acid (4 ml) was added the mixture of Br₂(0.45 ml) and acetic acid (2.5 ml) dropwise, and stirred at 338-348 K. The progress of the reaction was monitored by TLC. Upon completion, the reaction was extracted with chloroform (15 ml × 3). The filtrate was concentrated and then directly purified by chromatographic column (chloroform) to afford the title compound (I). A crystal suitable for X-ray analysis was grown from a solution of (I) in a mixture of petroleum and chloroform by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

2-Bromo-2-(5-bromo-1H-1,2,4-triazol-1-yl)-1-(2,4-difluorophenyl)ethanone top

Crystal data top

C₁₀H₅Br₂F₂N₃O	F(000) = 728
M_r = 380.99	D_x = 2.011 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1838 reflections
a = 9.273 (2) Å	θ = 2.3–22.5°
b = 9.375 (2) Å	µ = 6.46 mm⁻¹
c = 14.982 (3) Å	T = 298 K
β = 104.916 (3)°	Block, colourless
V = 1258.5 (5) Å³	0.26 × 0.25 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2206 independent reflections
Radiation source: fine-focus sealed tube	1577 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.199, T_max = 0.203	k = −10→11
6096 measured reflections	l = −15→17

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0482P)² + 0.5764P] where P = (F_o² + 2F_c²)/3
2206 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₀H₅Br₂F₂N₃O	V = 1258.5 (5) Å³
M_r = 380.99	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.273 (2) Å	µ = 6.46 mm⁻¹
b = 9.375 (2) Å	T = 298 K
c = 14.982 (3) Å	0.26 × 0.25 × 0.25 mm
β = 104.916 (3)°

Data collection top

Bruker SMART CCD diffractometer	2206 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1577 reflections with I > 2σ(I)
T_min = 0.199, T_max = 0.203	R_int = 0.036
6096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.04	Δρ_max = 0.61 e Å⁻³
2206 reflections	Δρ_min = −0.49 e Å⁻³
163 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 > 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
Br1	0.88429 (6)	0.61973 (5)	0.21078 (5)	0.0741 (2)
Br2	0.65968 (6)	0.75021 (7)	0.40152 (3)	0.0777 (2)
C1	0.7324 (6)	1.0030 (5)	0.1617 (4)	0.0783 (17)
H1	0.7343	1.0949	0.1387	0.094*
C2	0.7921 (5)	0.7951 (5)	0.1945 (3)	0.0512 (11)
C3	0.5841 (4)	0.7348 (5)	0.2679 (3)	0.0426 (10)
H3	0.5927	0.6355	0.2496	0.051*
C4	0.4187 (5)	0.7796 (4)	0.2384 (3)	0.0426 (10)
C5	0.3310 (4)	0.7498 (4)	0.1425 (3)	0.0375 (9)
C6	0.3760 (5)	0.6720 (4)	0.0765 (3)	0.0424 (10)
C7	0.2865 (5)	0.6440 (5)	−0.0092 (3)	0.0502 (11)
H7	0.3205	0.5910	−0.0521	0.060*
C8	0.1455 (6)	0.6970 (5)	−0.0291 (3)	0.0576 (12)
C9	0.0924 (5)	0.7769 (6)	0.0313 (4)	0.0656 (14)
H9	−0.0044	0.8127	0.0152	0.079*
C10	0.1867 (5)	0.8030 (5)	0.1170 (3)	0.0553 (12)
H10	0.1525	0.8579	0.1591	0.066*
F1	0.5154 (3)	0.6180 (3)	0.09542 (17)	0.0645 (8)
F2	0.0553 (3)	0.6703 (4)	−0.11300 (19)	0.0911 (10)
N1	0.8368 (5)	0.9052 (4)	0.1564 (3)	0.0719 (13)
N2	0.6690 (4)	0.8238 (4)	0.2223 (2)	0.0450 (9)
N3	0.6279 (4)	0.9620 (4)	0.2011 (3)	0.0602 (10)
O1	0.3620 (4)	0.8357 (4)	0.2925 (2)	0.0640 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0500 (3)	0.0474 (3)	0.1299 (5)	0.0074 (2)	0.0324 (3)	−0.0047 (3)
Br2	0.0597 (4)	0.1177 (5)	0.0494 (3)	−0.0031 (3)	0.0025 (2)	−0.0060 (3)
C1	0.075 (4)	0.046 (3)	0.133 (5)	0.008 (3)	0.063 (4)	0.018 (3)
C2	0.039 (3)	0.041 (3)	0.075 (3)	−0.001 (2)	0.016 (2)	−0.010 (2)
C3	0.039 (2)	0.044 (2)	0.045 (2)	−0.0020 (19)	0.0114 (19)	−0.0029 (19)
C4	0.039 (2)	0.042 (2)	0.051 (2)	−0.0024 (19)	0.019 (2)	−0.0017 (19)
C5	0.034 (2)	0.038 (2)	0.044 (2)	−0.0016 (18)	0.0159 (17)	−0.0005 (18)
C6	0.034 (2)	0.047 (2)	0.049 (2)	0.012 (2)	0.016 (2)	0.004 (2)
C7	0.045 (3)	0.063 (3)	0.042 (2)	0.013 (2)	0.011 (2)	−0.003 (2)
C8	0.055 (3)	0.064 (3)	0.047 (3)	0.008 (3)	0.001 (2)	−0.003 (2)
C9	0.036 (3)	0.088 (4)	0.068 (3)	0.014 (3)	0.005 (2)	−0.013 (3)
C10	0.037 (3)	0.067 (3)	0.063 (3)	0.006 (2)	0.016 (2)	−0.020 (2)
F1	0.0477 (16)	0.085 (2)	0.0583 (16)	0.0246 (14)	0.0088 (12)	−0.0174 (14)
F2	0.067 (2)	0.136 (3)	0.0549 (17)	0.030 (2)	−0.0130 (15)	−0.0225 (18)
N1	0.065 (3)	0.048 (3)	0.120 (4)	0.000 (2)	0.056 (3)	0.006 (2)
N2	0.036 (2)	0.037 (2)	0.064 (2)	−0.0055 (16)	0.0180 (17)	−0.0069 (17)
N3	0.058 (3)	0.038 (2)	0.096 (3)	0.0038 (19)	0.039 (2)	0.006 (2)
O1	0.052 (2)	0.085 (2)	0.058 (2)	0.0053 (18)	0.0201 (16)	−0.0244 (18)

Geometric parameters (Å, º) top

Br1—C2	1.840 (4)	C5—C6	1.378 (5)
Br2—C3	1.948 (4)	C5—C10	1.387 (6)
C1—N3	1.314 (6)	C6—F1	1.348 (4)
C1—N1	1.351 (6)	C6—C7	1.362 (6)
C1—H1	0.9300	C7—C8	1.358 (6)
C2—N1	1.297 (6)	C7—H7	0.9300
C2—N2	1.339 (5)	C8—F2	1.342 (5)
C3—N2	1.435 (5)	C8—C9	1.361 (7)
C3—C4	1.541 (6)	C9—C10	1.376 (6)
C3—H3	0.9800	C9—H9	0.9300
C4—O1	1.196 (5)	C10—H10	0.9300
C4—C5	1.483 (6)	N2—N3	1.365 (5)

N3—C1—N1	116.8 (4)	F1—C6—C5	119.9 (4)
N3—C1—H1	121.6	C7—C6—C5	123.7 (4)
N1—C1—H1	121.6	C8—C7—C6	117.1 (4)
N1—C2—N2	111.8 (4)	C8—C7—H7	121.5
N1—C2—Br1	125.4 (3)	C6—C7—H7	121.5
N2—C2—Br1	122.8 (3)	F2—C8—C7	118.1 (4)
N2—C3—C4	109.4 (3)	F2—C8—C9	118.7 (4)
N2—C3—Br2	110.5 (3)	C7—C8—C9	123.2 (4)
C4—C3—Br2	110.1 (3)	C8—C9—C10	117.8 (4)
N2—C3—H3	108.9	C8—C9—H9	121.1
C4—C3—H3	108.9	C10—C9—H9	121.1
Br2—C3—H3	108.9	C9—C10—C5	122.0 (4)
O1—C4—C5	120.8 (4)	C9—C10—H10	119.0
O1—C4—C3	120.2 (4)	C5—C10—H10	119.0
C5—C4—C3	119.0 (3)	C2—N1—C1	101.5 (4)
C6—C5—C10	116.2 (4)	C2—N2—N3	109.1 (4)
C6—C5—C4	127.1 (4)	C2—N2—C3	130.4 (4)
C10—C5—C4	116.7 (4)	N3—N2—C3	120.5 (3)
F1—C6—C7	116.4 (3)	C1—N3—N2	100.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.55	3.229 (5)	130

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₅Br₂F₂N₃O
M_r	380.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.273 (2), 9.375 (2), 14.982 (3)
β (°)	104.916 (3)
V (Å³)	1258.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.46
Crystal size (mm)	0.26 × 0.25 × 0.25

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.199, 0.203
No. of measured, independent and observed [I > 2σ(I)] reflections	6096, 2206, 1577
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 1.04
No. of reflections	2206
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.49

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), 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
C7—H7···O1ⁱ	0.93	2.55	3.229 (5)	130

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

We thank Southwest University (SWUB2006018, XSGX0602 and SWUF2007023) and the Natural Science Foundation of Chongqing (2007BB5369) for financial support.

References

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