N′-(2,4-Dichloro­benzyl­idene)-2-fluoro­benzohydrazide

Wang, H.-T.; Yuan, L.; Nan, Y.; Wang, R.; Zhou, L.; Niu, Y.

doi:10.1107/S1600536810053249

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o252

doi:10.1107/S1600536810053249

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N′-(2,4-Dichlorobenzylidene)-2-fluorobenzohydrazide

Hai-Tao Wang,^a Ling Yuan,^b,^c Yi Nan,^d Rong Wang,^d Li Zhou ^b and Yang Niu ^d ^*

^aThe Second Hospital of Jilin University, Changchun Jilin 130041, People's Republic of China, ^bPharmacy College of Ningxia Medical University, Yinchuan Ningxia 750004, People's Republic of China, ^cMinority Traditional Medical Center of Minzu University of China, Beijing 100081, People's Republic of China, and ^dTraditional Chinese Medicine College of Ningxia Medical University, Yinchuan Ningxia 750004, People's Republic of China
^*Correspondence e-mail: niuyang750@126.com

(Received 17 December 2010; accepted 18 December 2010; online 8 January 2011)

The molecule of the title compound, C₁₄H₉Cl₂FN₂O, exists in a trans configuration with respect to the methylidene unit and the benzene rings form a dihedral angle of 8.1 (2)°. In the crystal, molecules are linked through N—H⋯O hydrogen bonds into C(4) chains propagating in [100].

Related literature

For related structures and background to the pharmacological properties of hydrazone compounds, see: Xu et al. (2011a ,b ). For reference bond-length values, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₉Cl₂FN₂O
M_r = 311.13
Monoclinic, P 2₁ /n
a = 7.2310 (14) Å
b = 26.145 (5) Å
c = 8.0590 (16) Å
β = 115.033 (3)°
V = 1380.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 298 K
0.23 × 0.21 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.898, T_max = 0.911
9842 measured reflections
2963 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.163
S = 1.05
2963 reflections
184 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.89 (1)	2.19 (1)	3.054 (3)	162 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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/S1600536810053249/hb5775sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810053249/hb5775Isup2.hkl

checkCIF report

Comment top

As a continuation of our recent work on the structures of hydrazone compounds (Xu et al., 2011a,b), the title compound, (I), is reported.

The molecule of the compound, Fig. 1, exists in a trans configuration with respect to the methylidene unit. The molecule is twisted, with the dihedral angle between the two benzene rings of 8.1 (2)°. The torsion angle C7—N1—N2—C8 is 9.0 (3)°. The bond lengths are within normal ranges (Allen et al., 1987).

In the crystal structure, molecules are linked through intermolecular N—H···O hydrogen bonds (Table 1), to form chains down the a axis (Fig. 2).

Related literature top

For related structures and background to the pharmacological properties of hydrazone compounds, see: Xu et al. (2011a,b). For reference bond-length values, see: Allen et al. (1987).

Experimental top

2,4-Dichlorobenzaldehyde (0.1 mmol, 17.4 mg) and 2-fluorobenzohydrazide (0.1 mmol, 15.4 mg) were mixed in ethanol (20 ml). The mixture was stirred at room temperature to give a clear colorless solution. Colorless well shaped blocks of the title compound were formed by gradual evaporation of the solvent over a period of five days at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The one-dimensional chains structure along a axis. The intermolecular hydrogen bonds are shown as dashed lines.

N'-(2,4-Dichlorobenzylidene)-2-fluorobenzohydrazide top

Crystal data top

C₁₄H₉Cl₂FN₂O	F(000) = 632
M_r = 311.13	D_x = 1.497 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2459 reflections
a = 7.2310 (14) Å	θ = 2.7–25.0°
b = 26.145 (5) Å	µ = 0.48 mm⁻¹
c = 8.0590 (16) Å	T = 298 K
β = 115.033 (3)°	Block, colorless
V = 1380.5 (5) Å³	0.23 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2963 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.898, T_max = 0.911	k = −33→33
9842 measured reflections	l = −10→10

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0831P)² + 0.4914P] where P = (F_o² + 2F_c²)/3
2963 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.66 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₉Cl₂FN₂O	V = 1380.5 (5) Å³
M_r = 311.13	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2310 (14) Å	µ = 0.48 mm⁻¹
b = 26.145 (5) Å	T = 298 K
c = 8.0590 (16) Å	0.23 × 0.21 × 0.20 mm
β = 115.033 (3)°

Data collection top

Bruker SMART CCD diffractometer	2963 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2236 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.911	R_int = 0.029
9842 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	1 restraint
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.66 e Å⁻³
2963 reflections	Δρ_min = −0.27 e Å⁻³
184 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
Cl1	0.86585 (15)	0.06215 (3)	0.64036 (10)	0.0753 (3)
Cl2	0.71562 (15)	0.01533 (3)	−0.04771 (12)	0.0778 (3)
F1	0.7577 (4)	0.25674 (8)	0.9556 (3)	0.0964 (7)
N1	0.7523 (3)	0.21787 (8)	0.4805 (3)	0.0482 (5)
N2	0.7956 (3)	0.24975 (8)	0.6285 (3)	0.0506 (6)
O1	0.5927 (3)	0.31235 (8)	0.4527 (3)	0.0707 (6)
C1	0.7912 (4)	0.13485 (10)	0.3799 (3)	0.0439 (6)
C2	0.8097 (4)	0.08305 (11)	0.4195 (3)	0.0482 (6)
C3	0.7842 (4)	0.04630 (10)	0.2903 (4)	0.0523 (6)
H3	0.7953	0.0117	0.3203	0.063*
C4	0.7417 (4)	0.06205 (11)	0.1141 (4)	0.0526 (7)
C5	0.7245 (4)	0.11280 (11)	0.0675 (4)	0.0540 (7)
H5	0.6977	0.1228	−0.0513	0.065*
C6	0.7475 (4)	0.14872 (11)	0.1991 (4)	0.0517 (6)
H6	0.7336	0.1832	0.1675	0.062*
C7	0.8217 (4)	0.17291 (10)	0.5209 (3)	0.0479 (6)
H7	0.8938	0.1640	0.6434	0.058*
C8	0.7067 (4)	0.29579 (10)	0.6032 (3)	0.0479 (6)
C9	0.7558 (4)	0.32662 (10)	0.7740 (3)	0.0475 (6)
C10	0.7779 (4)	0.30700 (12)	0.9386 (4)	0.0581 (7)
C11	0.8167 (5)	0.33677 (16)	1.0910 (4)	0.0761 (10)
H11	0.8316	0.3221	1.2011	0.091*
C12	0.8328 (5)	0.38854 (17)	1.0753 (5)	0.0832 (11)
H12	0.8592	0.4095	1.1762	0.100*
C13	0.8106 (5)	0.40961 (14)	0.9143 (6)	0.0796 (10)
H13	0.8231	0.4448	0.9066	0.096*
C14	0.7696 (4)	0.37967 (11)	0.7614 (5)	0.0615 (8)
H14	0.7514	0.3947	0.6510	0.074*
H2	0.886 (4)	0.2381 (12)	0.736 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1180 (7)	0.0635 (5)	0.0493 (4)	0.0186 (4)	0.0401 (5)	0.0144 (3)
Cl2	0.1043 (7)	0.0760 (6)	0.0646 (5)	−0.0129 (5)	0.0469 (5)	−0.0227 (4)
F1	0.143 (2)	0.0761 (14)	0.0794 (14)	0.0124 (13)	0.0558 (14)	0.0170 (11)
N1	0.0445 (12)	0.0506 (13)	0.0370 (11)	0.0004 (10)	0.0050 (9)	−0.0031 (9)
N2	0.0505 (13)	0.0511 (13)	0.0332 (11)	0.0077 (10)	0.0012 (9)	−0.0017 (9)
O1	0.0788 (14)	0.0604 (12)	0.0421 (11)	0.0151 (11)	−0.0044 (10)	0.0048 (9)
C1	0.0374 (12)	0.0507 (14)	0.0375 (13)	0.0004 (11)	0.0099 (10)	0.0028 (11)
C2	0.0493 (14)	0.0553 (15)	0.0397 (13)	0.0055 (12)	0.0186 (11)	0.0053 (11)
C3	0.0584 (16)	0.0474 (15)	0.0552 (16)	−0.0029 (12)	0.0281 (14)	−0.0016 (12)
C4	0.0500 (15)	0.0631 (17)	0.0470 (15)	−0.0085 (12)	0.0227 (12)	−0.0117 (12)
C5	0.0581 (16)	0.0636 (17)	0.0360 (13)	−0.0107 (13)	0.0158 (12)	−0.0011 (12)
C6	0.0510 (15)	0.0538 (15)	0.0430 (14)	−0.0041 (12)	0.0127 (12)	0.0047 (12)
C7	0.0445 (14)	0.0536 (15)	0.0369 (13)	0.0043 (12)	0.0087 (11)	0.0011 (11)
C8	0.0409 (13)	0.0505 (15)	0.0410 (14)	0.0012 (11)	0.0064 (11)	0.0019 (11)
C9	0.0321 (12)	0.0548 (15)	0.0437 (14)	0.0054 (11)	0.0044 (10)	−0.0010 (11)
C10	0.0510 (16)	0.0625 (18)	0.0527 (16)	0.0142 (13)	0.0140 (13)	0.0033 (14)
C11	0.063 (2)	0.109 (3)	0.0447 (17)	0.0231 (19)	0.0124 (14)	−0.0059 (17)
C12	0.062 (2)	0.096 (3)	0.072 (2)	0.0140 (19)	0.0088 (18)	−0.035 (2)
C13	0.061 (2)	0.064 (2)	0.099 (3)	0.0019 (16)	0.0197 (19)	−0.025 (2)
C14	0.0491 (16)	0.0514 (16)	0.073 (2)	0.0019 (12)	0.0147 (14)	−0.0084 (14)

Geometric parameters (Å, º) top

Cl1—C2	1.738 (3)	C5—C6	1.373 (4)
Cl2—C4	1.738 (3)	C5—H5	0.9300
F1—C10	1.336 (4)	C6—H6	0.9300
N1—C7	1.265 (3)	C7—H7	0.9300
N1—N2	1.379 (3)	C8—C9	1.503 (4)
N2—C8	1.339 (3)	C9—C10	1.367 (4)
N2—H2	0.893 (10)	C9—C14	1.397 (4)
O1—C8	1.222 (3)	C10—C11	1.379 (4)
C1—C2	1.385 (4)	C11—C12	1.369 (6)
C1—C6	1.401 (4)	C11—H11	0.9300
C1—C7	1.455 (3)	C12—C13	1.355 (6)
C2—C3	1.371 (4)	C12—H12	0.9300
C3—C4	1.382 (4)	C13—C14	1.382 (5)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.370 (4)	C14—H14	0.9300

C7—N1—N2	114.8 (2)	N1—C7—H7	119.3
C8—N2—N1	119.5 (2)	C1—C7—H7	119.3
C8—N2—H2	124 (2)	O1—C8—N2	123.3 (2)
N1—N2—H2	116 (2)	O1—C8—C9	121.2 (2)
C2—C1—C6	116.8 (2)	N2—C8—C9	115.5 (2)
C2—C1—C7	121.4 (2)	C10—C9—C14	117.4 (3)
C6—C1—C7	121.9 (2)	C10—C9—C8	125.0 (3)
C3—C2—C1	122.8 (2)	C14—C9—C8	117.5 (2)
C3—C2—Cl1	117.1 (2)	F1—C10—C9	119.7 (3)
C1—C2—Cl1	120.1 (2)	F1—C10—C11	117.0 (3)
C2—C3—C4	118.1 (3)	C9—C10—C11	123.3 (3)
C2—C3—H3	120.9	C12—C11—C10	118.0 (3)
C4—C3—H3	120.9	C12—C11—H11	121.0
C5—C4—C3	121.7 (2)	C10—C11—H11	121.0
C5—C4—Cl2	120.4 (2)	C13—C12—C11	120.7 (3)
C3—C4—Cl2	117.9 (2)	C13—C12—H12	119.7
C4—C5—C6	118.9 (2)	C11—C12—H12	119.7
C4—C5—H5	120.5	C12—C13—C14	121.1 (3)
C6—C5—H5	120.5	C12—C13—H13	119.4
C5—C6—C1	121.8 (3)	C14—C13—H13	119.4
C5—C6—H6	119.1	C13—C14—C9	119.5 (3)
C1—C6—H6	119.1	C13—C14—H14	120.3
N1—C7—C1	121.4 (2)	C9—C14—H14	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.89 (1)	2.19 (1)	3.054 (3)	162 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉Cl₂FN₂O
M_r	311.13
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.2310 (14), 26.145 (5), 8.0590 (16)
β (°)	115.033 (3)
V (Å³)	1380.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.23 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.898, 0.911
No. of measured, independent and observed [I > 2σ(I)] reflections	9842, 2963, 2236
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.163, 1.05
No. of reflections	2963
No. of parameters	184
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
N2—H2···O1ⁱ	0.893 (10)	2.191 (14)	3.054 (3)	162 (3)

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

Acknowledgements

This project was supported by the 2008 Ningxia science and technology key projects (No. 222) and the 2009 Ningxia science and technology key projects (No. 232).

References

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