(E)-N′-(2-Bromo­benzyl­idene)-2-fluoro­benzohydrazide

Zhang, D.-F.; Liu, D.-Y.; Li, C.-X.; Huang, S.-S.; Zhang, B.-J.

doi:10.1107/S1600536811009937

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o940

doi:10.1107/S1600536811009937

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(E)-N′-(2-Bromobenzylidene)-2-fluorobenzohydrazide

Dong-Fang Zhang,^a ^* Da-Yong Liu,^b Chuan-Xun Li,^c Shan-Shan Huang ^c and Bao-Jing Zhang ^c

^aCollege of Pharmaceutical Science, China Medical University, Shenyang 110001, People's Republic of China, ^bDepartment of Chemistry and Chemical Engineering, Huanghuai University, Henan 463000, People's Republic of China, and ^cSchool of Pharmacy, Dalian Medical University, Dalian 116044, People's Republic of China
^*Correspondence e-mail: changeliuhao@126.com

(Received 3 March 2011; accepted 16 March 2011; online 23 March 2011)

The title compound, C₁₄H₁₀BrFN₂O, adopts an E geometry about the C=N bond. The dihedral angle between the mean planes of the two benzene rings is 81.5 (6)°. In the crystal, molecules are linked through intermolecular N—H⋯O hydrogen bonds, forming chains running along the b axis.

Related literature

For general background to the biological activity of Schiff bases, see: Bernardino et al. (2006 ); Ganjali et al. (2006 ). For related structures, see: Jiang (2006 ); Wardell et al. (2007 ); Zhu & He (2008 ); Li et al. (2009 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₀BrFN₂O
M_r = 321.14
Orthorhombic, P b c a
a = 11.853 (2) Å
b = 9.6507 (18) Å
c = 22.921 (4) Å
V = 2621.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 3.14 mm⁻¹
T = 295 K
0.44 × 0.12 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.633, T_max = 0.798
15028 measured reflections
3111 independent reflections
1892 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.096
S = 1.00
2094 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.80	2.04	2.827 (3)	167
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009937/zq2093sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009937/zq2093Isup2.hkl

checkCIF report

Comment top

Schiff bases have attracted much attention due to their diverse range of bioactivities in pharmaceutical and agrochemical field (e.g. Bernardino et al., 2006; Ganjali et al., 2006). We now report the synthesis and crystal structure of the title compound (Fig. 1).

In the title compound, the Schiff base molecule adopts an E geometry with respect to the C=N bond, as shown in Fig. 1.The bond lengths and bond angles for (I) are within normal ranges (Allen et al., 1987). The dihedral angle between the mean planes of the two benzene rings is 98.5 (6)°. The Schiff base moieties through intermolecular N—H···O hydrogen bonds form chains along the b axis, which helps to consolidate the crystal packing (Fig 2).

Related literature top

For general background to the biological activity of Schiff bases, see: Bernardino et al. (2006); Ganjali et al. (2006). For related structures, see: Jiang (2006); Wardell et al. (2007); Zhu & He (2008); Li et al. (2009). For standard bond lengths, see: Allen et al. (1987).

Experimental top

2-Fluorobenzohydrazide (0.1 mmol,15.4 mg) and 2-bromobenzaldehyde (0.1 mmol, 18.4 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 1 h and filtered. After keeping the filtrate in air for three days, colorless block-like crystals were formed.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 the title compound (thermal ellipsoids are shown at the 30% probability level).
	Fig. 2. The crystal packing of the title compound viewed down the b axis. The dashed lines represent the hydrogen bonding interactions. Hydrogen atoms have been omitted for clarity.

(E)-N'-(2-Bromobenzylidene)-2-fluorobenzohydrazide top

Crystal data top

C₁₄H₁₀BrFN₂O	F(000) = 1280
M_r = 321.14	D_x = 1.627 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2094 reflections
a = 11.853 (2) Å	θ = 2.5–21.5°
b = 9.6507 (18) Å	µ = 3.14 mm⁻¹
c = 22.921 (4) Å	T = 295 K
V = 2621.9 (8) Å³	Block, yellow
Z = 8	0.44 × 0.12 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3111 independent reflections
Radiation source: fine-focus sealed tube	1892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 27.8°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→15
T_min = 0.633, T_max = 0.798	k = −12→12
15028 measured reflections	l = −30→23

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0385P)² + 0.3692P] where P = (F_o² + 2F_c²)/3
2094 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₁₄H₁₀BrFN₂O	V = 2621.9 (8) Å³
M_r = 321.14	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.853 (2) Å	µ = 3.14 mm⁻¹
b = 9.6507 (18) Å	T = 295 K
c = 22.921 (4) Å	0.44 × 0.12 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3111 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1892 reflections with I > 2σ(I)
T_min = 0.633, T_max = 0.798	R_int = 0.064
15028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.00	Δρ_max = 0.31 e Å⁻³
2094 reflections	Δρ_min = −0.57 e Å⁻³
172 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
Br1	0.71246 (3)	−0.03729 (4)	1.026973 (15)	0.05866 (15)
F1	0.93107 (15)	0.5216 (2)	0.78445 (10)	0.0708 (6)
O1	0.71146 (17)	0.5201 (2)	0.83914 (9)	0.0438 (5)
N1	0.69850 (17)	0.2891 (2)	0.85414 (10)	0.0328 (5)
H1A	0.7221	0.2150	0.8442	0.039*
N2	0.64592 (18)	0.3061 (2)	0.90719 (9)	0.0328 (5)
C1	0.7828 (2)	0.3676 (3)	0.76568 (12)	0.0348 (7)
C2	0.8798 (3)	0.4319 (3)	0.74739 (15)	0.0463 (8)
C3	0.9276 (3)	0.4075 (4)	0.69309 (17)	0.0674 (11)
H3	0.9928	0.4534	0.6815	0.081*
C4	0.8758 (4)	0.3137 (5)	0.65694 (17)	0.0805 (13)
H4	0.9065	0.2961	0.6203	0.097*
C5	0.7808 (4)	0.2461 (4)	0.67351 (16)	0.0708 (11)
H5	0.7473	0.1818	0.6487	0.085*
C6	0.7341 (3)	0.2737 (3)	0.72758 (13)	0.0503 (9)
H6	0.6683	0.2281	0.7386	0.060*
C7	0.7291 (2)	0.4011 (3)	0.82290 (12)	0.0313 (6)
C8	0.6410 (2)	0.1979 (3)	0.93891 (12)	0.0343 (7)
H8	0.6714	0.1148	0.9257	0.041*
C9	0.5869 (2)	0.2055 (3)	0.99638 (12)	0.0323 (6)
C10	0.5124 (2)	0.3127 (3)	1.00943 (12)	0.0396 (7)
H10	0.4954	0.3779	0.9809	0.047*
C11	0.6079 (2)	0.1080 (3)	1.03970 (12)	0.0365 (7)
C12	0.5580 (3)	0.1179 (4)	1.09390 (13)	0.0493 (8)
H12	0.5728	0.0514	1.1223	0.059*
C13	0.4864 (2)	0.2259 (4)	1.10586 (14)	0.0503 (9)
H13	0.4533	0.2329	1.1425	0.060*
C14	0.4631 (2)	0.3244 (3)	1.06384 (13)	0.0459 (8)
H14	0.4147	0.3978	1.0721	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0711 (3)	0.0520 (2)	0.0528 (2)	0.02188 (19)	0.01343 (18)	0.01330 (17)
F1	0.0498 (11)	0.0695 (14)	0.0930 (16)	−0.0141 (10)	0.0000 (11)	0.0123 (13)
O1	0.0615 (14)	0.0263 (12)	0.0437 (12)	−0.0043 (10)	0.0116 (10)	−0.0023 (10)
N1	0.0453 (13)	0.0249 (13)	0.0281 (13)	0.0038 (10)	0.0084 (11)	−0.0023 (10)
N2	0.0380 (13)	0.0312 (14)	0.0292 (13)	−0.0003 (11)	0.0066 (11)	−0.0022 (11)
C1	0.0383 (16)	0.0328 (16)	0.0334 (16)	0.0023 (14)	0.0075 (14)	0.0047 (13)
C2	0.0417 (18)	0.043 (2)	0.054 (2)	0.0023 (15)	0.0002 (16)	0.0109 (16)
C3	0.047 (2)	0.085 (3)	0.070 (3)	0.014 (2)	0.029 (2)	0.029 (2)
C4	0.087 (3)	0.111 (4)	0.044 (2)	0.032 (3)	0.022 (2)	0.006 (2)
C5	0.087 (3)	0.083 (3)	0.043 (2)	0.013 (2)	0.012 (2)	−0.012 (2)
C6	0.061 (2)	0.050 (2)	0.040 (2)	0.0027 (16)	0.0093 (16)	−0.0049 (16)
C7	0.0342 (15)	0.0264 (16)	0.0332 (16)	−0.0022 (12)	0.0005 (13)	0.0016 (13)
C8	0.0373 (16)	0.0333 (17)	0.0324 (16)	0.0012 (14)	0.0028 (13)	−0.0018 (13)
C9	0.0356 (15)	0.0326 (17)	0.0288 (15)	−0.0048 (13)	0.0056 (13)	−0.0037 (13)
C10	0.0430 (17)	0.0382 (18)	0.0375 (18)	0.0015 (15)	0.0023 (14)	0.0005 (14)
C11	0.0377 (16)	0.0353 (17)	0.0364 (17)	−0.0014 (13)	0.0061 (13)	0.0010 (13)
C12	0.054 (2)	0.056 (2)	0.0378 (19)	−0.0018 (17)	0.0098 (16)	0.0104 (16)
C13	0.0483 (19)	0.065 (2)	0.0377 (19)	−0.0014 (18)	0.0157 (16)	−0.0007 (17)
C14	0.0407 (17)	0.051 (2)	0.046 (2)	0.0024 (16)	0.0131 (15)	−0.0069 (16)

Geometric parameters (Å, º) top

Br1—C11	1.894 (3)	C5—C6	1.383 (4)
F1—C2	1.356 (4)	C5—H5	0.9300
O1—C7	1.226 (3)	C6—H6	0.9300
N1—C7	1.346 (3)	C8—C9	1.467 (4)
N1—N2	1.376 (3)	C8—H8	0.9300
N1—H1A	0.8011	C9—C11	1.390 (4)
N2—C8	1.274 (3)	C9—C10	1.393 (4)
C1—C2	1.372 (4)	C10—C14	1.382 (4)
C1—C6	1.385 (4)	C10—H10	0.9300
C1—C7	1.494 (4)	C11—C12	1.379 (4)
C2—C3	1.387 (5)	C12—C13	1.372 (4)
C3—C4	1.372 (5)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.381 (4)
C4—C5	1.355 (6)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300

C7—N1—N2	119.7 (2)	O1—C7—C1	122.8 (3)
C7—N1—H1A	118.1	N1—C7—C1	114.1 (2)
N2—N1—H1A	121.1	N2—C8—C9	119.4 (3)
C8—N2—N1	115.3 (2)	N2—C8—H8	120.3
C2—C1—C6	116.9 (3)	C9—C8—H8	120.3
C2—C1—C7	121.9 (3)	C11—C9—C10	117.6 (3)
C6—C1—C7	121.1 (3)	C11—C9—C8	122.0 (3)
F1—C2—C1	118.2 (3)	C10—C9—C8	120.5 (3)
F1—C2—C3	119.2 (3)	C14—C10—C9	121.5 (3)
C1—C2—C3	122.6 (3)	C14—C10—H10	119.2
C4—C3—C2	118.1 (3)	C9—C10—H10	119.2
C4—C3—H3	121.0	C12—C11—C9	121.3 (3)
C2—C3—H3	121.0	C12—C11—Br1	118.1 (2)
C5—C4—C3	121.3 (4)	C9—C11—Br1	120.5 (2)
C5—C4—H4	119.3	C13—C12—C11	119.8 (3)
C3—C4—H4	119.3	C13—C12—H12	120.1
C4—C5—C6	119.4 (4)	C11—C12—H12	120.1
C4—C5—H5	120.3	C12—C13—C14	120.5 (3)
C6—C5—H5	120.3	C12—C13—H13	119.8
C5—C6—C1	121.6 (3)	C14—C13—H13	119.8
C5—C6—H6	119.2	C13—C14—C10	119.2 (3)
C1—C6—H6	119.2	C13—C14—H14	120.4
O1—C7—N1	123.0 (2)	C10—C14—H14	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.80	2.04	2.827 (3)	167

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀BrFN₂O
M_r	321.14
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	11.853 (2), 9.6507 (18), 22.921 (4)
V (Å³)	2621.9 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.14
Crystal size (mm)	0.44 × 0.12 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.633, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	15028, 3111, 1892
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.096, 1.00
No. of reflections	2094
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.57

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.80	2.04	2.827 (3)	167

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

This work was supported in part by a grant from China Medical University.

References

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