3-Chloro-N′-(2,4-dichloro­benzyl­idene)benzohydrazide

Lei, Y.

doi:10.1107/S1600536810051913

organic compounds

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Volume 67| Part 1| January 2011| Page o162

https://doi.org/10.1107/S1600536810051913

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3-Chloro-N′-(2,4-dichlorobenzylidene)benzohydrazide

Yan Lei ^a ^*

^aSchool of Chemistry & Environmental Engineering, Chongqing Three Gorges University, Chongqing 404000, People's Republic of China
^*Correspondence e-mail: leiyan222@yahoo.cn

(Received 10 December 2010; accepted 10 December 2010; online 18 December 2010)

The title compound, C₁₄H₉Cl₃N₂O, adopts an E configuration about the methylidene unit and the two aromatic rings form a dihedral angle of 6.6 (2)°. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming C(4) chains propagating in [001]. C—H⋯O interactions reinforce the chains.

Related literature

For background to hydrazones, see: El-Asmy et al. (2010 ); El-Sherif (2009 ); Singh et al. (2009 ); El-Tabl et al. (2007 ). For structures of hydrazone compounds, see: Qiao et al. (2010 ); Hussain et al. (2010 ); Han & Zhao (2010 ); Ahmad et al. (2010 ).

Experimental

Crystal data

C₁₄H₉Cl₃N₂O
M_r = 327.58
Monoclinic, P 2₁ /c
a = 12.372 (3) Å
b = 14.071 (2) Å
c = 8.332 (2) Å
β = 97.582 (3)°
V = 1437.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 298 K
0.30 × 0.27 × 0.27 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.833, T_max = 0.848
7125 measured reflections
3081 independent reflections
1776 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.129
S = 1.02
3081 reflections
184 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.90 (1)	2.08 (2)	2.900 (3)	152 (3)
C7—H7⋯O1ⁱ	0.93	2.35	3.155 (3)	145
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: https://doi.org/10.1107/S1600536810051913/hb5766sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051913/hb5766Isup2.hkl

checkCIF report

Comment top

Significant attention has been attracted on the hydrazones for their biological properties, coordinative capability, and applications in analytical chemistry (El-Asmy et al., 2010; El-Sherif, 2009; Singh et al., 2009; El-Tabl et al., 2007). Recently, a number of hydrazones have been prepared and investigated for their structures (Qiao et al., 2010; Hussain et al., 2010; Han & Zhao, 2010; Ahmad et al., 2010). As a continuation of hydrazones, the author reports herein the title new compound.

The molecule of the title compound, Fig. 1, adopts an E configuration about the methylidene unit. The two aromatic rings form a dihedral angle of 6.6 (2)°. In the crystal, the molecules are linked via intermolecular N—H···O and C—H···O hydrogen bonds (Table 1), to form chains at the c-axis direction (Fig. 2).

Related literature top

For background to hydrazones, see: El-Asmy et al. (2010); El-Sherif (2009); Singh et al. (2009); El-Tabl et al. (2007). For structures of hydrazone compounds, see: Qiao et al. (2010); Hussain et al. (2010); Han & Zhao (2010); Ahmad et al. (2010).

Experimental top

3-Chlorobenzohydrazide (1 mmol, 0.170 g) was dissolved in methanol (50 ml), then 2,4-dichlorobenzaldehyde (1 mmol, 0.174 g) was added into the solution. The reaction mixture was heated under reflux for 1 h and cooled to room temperature. Colourless needle-shaped crystals were formed by slow evaporation of the solvent for a week.

Structure description top

For background to hydrazones, see: El-Asmy et al. (2010); El-Sherif (2009); Singh et al. (2009); El-Tabl et al. (2007). For structures of hydrazone compounds, see: Qiao et al. (2010); Hussain et al. (2010); Han & Zhao (2010); Ahmad et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 30% probability displacement ellipsoids.
	Fig. 2. The packing of the title compound. Hydrogen bonding is shown in dashed lines.

3-Chloro-N'-(2,4-dichlorobenzylidene)benzohydrazide top

Crystal data top

C₁₄H₉Cl₃N₂O	F(000) = 664
M_r = 327.58	D_x = 1.513 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.372 (3) Å	Cell parameters from 1072 reflections
b = 14.071 (2) Å	θ = 2.3–25.1°
c = 8.332 (2) Å	µ = 0.63 mm⁻¹
β = 97.582 (3)°	T = 298 K
V = 1437.9 (5) Å³	Cut from needle, colourless
Z = 4	0.30 × 0.27 × 0.27 mm

Data collection top

Bruker SMART CCD diffractometer	3081 independent reflections
Radiation source: fine-focus sealed tube	1776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→11
T_min = 0.833, T_max = 0.848	k = −17→17
7125 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0422P)² + 0.3462P] where P = (F_o² + 2F_c²)/3
3081 reflections	(Δ/σ)_max = 0.001
184 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₄H₉Cl₃N₂O	V = 1437.9 (5) Å³
M_r = 327.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.372 (3) Å	µ = 0.63 mm⁻¹
b = 14.071 (2) Å	T = 298 K
c = 8.332 (2) Å	0.30 × 0.27 × 0.27 mm
β = 97.582 (3)°

Data collection top

Bruker SMART CCD diffractometer	3081 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1776 reflections with I > 2σ(I)
T_min = 0.833, T_max = 0.848	R_int = 0.042
7125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	1 restraint
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.27 e Å⁻³
3081 reflections	Δρ_min = −0.34 e Å⁻³
184 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
Cl1	0.50321 (9)	1.17766 (6)	0.13090 (13)	0.0852 (4)
Cl2	0.27379 (8)	1.10398 (6)	0.61537 (13)	0.0791 (3)
Cl3	0.12211 (9)	0.31908 (6)	0.63795 (16)	0.1013 (5)
N1	0.27659 (18)	0.81292 (16)	0.4682 (3)	0.0403 (6)
N2	0.22918 (19)	0.74940 (16)	0.5631 (3)	0.0408 (6)
O1	0.20262 (17)	0.64606 (14)	0.3554 (2)	0.0544 (6)
C1	0.3473 (2)	0.96532 (19)	0.4329 (3)	0.0384 (7)
C2	0.3406 (2)	1.0619 (2)	0.4604 (4)	0.0456 (8)
C3	0.3859 (2)	1.1283 (2)	0.3661 (4)	0.0528 (8)
H3	0.3788	1.1930	0.3845	0.063*
C4	0.4413 (2)	1.0962 (2)	0.2456 (4)	0.0503 (8)
C5	0.4516 (2)	1.0012 (2)	0.2160 (4)	0.0503 (8)
H5	0.4903	0.9805	0.1342	0.060*
C6	0.4041 (2)	0.9370 (2)	0.3086 (3)	0.0435 (7)
H6	0.4102	0.8724	0.2874	0.052*
C7	0.2964 (2)	0.8950 (2)	0.5281 (4)	0.0418 (7)
H7	0.2790	0.9101	0.6302	0.050*
C8	0.1933 (2)	0.66637 (19)	0.4955 (4)	0.0396 (7)
C9	0.1403 (2)	0.59954 (19)	0.5991 (3)	0.0361 (6)
C10	0.1539 (2)	0.5032 (2)	0.5755 (4)	0.0475 (8)
H10	0.1974	0.4820	0.4999	0.057*
C11	0.1030 (3)	0.4393 (2)	0.6640 (4)	0.0582 (9)
C12	0.0359 (3)	0.4696 (3)	0.7725 (4)	0.0723 (11)
H12	0.0004	0.4258	0.8307	0.087*
C13	0.0219 (3)	0.5651 (3)	0.7939 (4)	0.0663 (10)
H13	−0.0235	0.5860	0.8671	0.080*
C14	0.0743 (2)	0.6307 (2)	0.7086 (3)	0.0490 (8)
H14	0.0650	0.6954	0.7250	0.059*
H2	0.227 (2)	0.763 (2)	0.6680 (15)	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1072 (8)	0.0612 (6)	0.0882 (8)	−0.0214 (5)	0.0174 (6)	0.0292 (5)
Cl2	0.0891 (7)	0.0575 (6)	0.0975 (8)	0.0031 (5)	0.0376 (6)	−0.0209 (5)
Cl3	0.1025 (8)	0.0464 (5)	0.1416 (11)	−0.0168 (5)	−0.0342 (7)	0.0293 (6)
N1	0.0504 (14)	0.0348 (13)	0.0360 (15)	−0.0021 (11)	0.0066 (11)	0.0053 (11)
N2	0.0556 (15)	0.0390 (13)	0.0290 (13)	−0.0088 (11)	0.0094 (12)	−0.0006 (12)
O1	0.0815 (15)	0.0482 (12)	0.0366 (13)	−0.0143 (11)	0.0201 (11)	−0.0062 (10)
C1	0.0382 (15)	0.0357 (16)	0.0393 (17)	−0.0020 (13)	−0.0017 (13)	0.0028 (13)
C2	0.0452 (17)	0.0405 (17)	0.050 (2)	0.0006 (13)	0.0034 (14)	−0.0049 (15)
C3	0.0559 (19)	0.0327 (16)	0.066 (2)	−0.0040 (14)	−0.0073 (17)	0.0029 (16)
C4	0.0522 (18)	0.0457 (18)	0.051 (2)	−0.0096 (15)	−0.0022 (16)	0.0176 (16)
C5	0.0604 (19)	0.049 (2)	0.042 (2)	−0.0016 (15)	0.0087 (15)	0.0100 (15)
C6	0.0555 (18)	0.0354 (15)	0.0388 (18)	−0.0012 (13)	0.0025 (14)	0.0029 (14)
C7	0.0488 (17)	0.0427 (17)	0.0336 (17)	−0.0007 (14)	0.0050 (13)	−0.0005 (14)
C8	0.0461 (17)	0.0397 (17)	0.0336 (18)	0.0025 (13)	0.0080 (13)	0.0014 (14)
C9	0.0393 (15)	0.0412 (16)	0.0267 (16)	−0.0059 (13)	0.0007 (12)	0.0022 (13)
C10	0.0417 (16)	0.0453 (18)	0.052 (2)	−0.0023 (13)	−0.0060 (14)	0.0035 (15)
C11	0.060 (2)	0.0458 (19)	0.061 (2)	−0.0173 (16)	−0.0191 (18)	0.0191 (17)
C12	0.074 (2)	0.090 (3)	0.049 (2)	−0.041 (2)	−0.0053 (19)	0.025 (2)
C13	0.058 (2)	0.099 (3)	0.043 (2)	−0.024 (2)	0.0126 (16)	−0.001 (2)
C14	0.0478 (17)	0.062 (2)	0.0370 (18)	−0.0102 (15)	0.0069 (14)	−0.0009 (16)

Geometric parameters (Å, º) top

Cl1—C4	1.733 (3)	C5—C6	1.370 (4)
Cl2—C2	1.728 (3)	C5—H5	0.9300
Cl3—C11	1.726 (3)	C6—H6	0.9300
N1—C7	1.269 (3)	C7—H7	0.9300
N1—N2	1.375 (3)	C8—C9	1.487 (4)
N2—C8	1.347 (3)	C9—C14	1.374 (4)
N2—H2	0.896 (10)	C9—C10	1.383 (4)
O1—C8	1.222 (3)	C10—C11	1.368 (4)
C1—C2	1.382 (4)	C10—H10	0.9300
C1—C6	1.384 (4)	C11—C12	1.373 (5)
C1—C7	1.462 (4)	C12—C13	1.371 (5)
C2—C3	1.386 (4)	C12—H12	0.9300
C3—C4	1.365 (4)	C13—C14	1.377 (4)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.369 (4)	C14—H14	0.9300

C7—N1—N2	116.1 (2)	N1—C7—H7	120.7
C8—N2—N1	117.7 (2)	C1—C7—H7	120.7
C8—N2—H2	122.6 (19)	O1—C8—N2	122.4 (3)
N1—N2—H2	119.5 (19)	O1—C8—C9	120.8 (3)
C2—C1—C6	117.1 (3)	N2—C8—C9	116.8 (3)
C2—C1—C7	122.4 (3)	C14—C9—C10	120.1 (3)
C6—C1—C7	120.5 (3)	C14—C9—C8	122.0 (3)
C1—C2—C3	122.1 (3)	C10—C9—C8	117.8 (3)
C1—C2—Cl2	120.4 (2)	C11—C10—C9	119.6 (3)
C3—C2—Cl2	117.5 (2)	C11—C10—H10	120.2
C4—C3—C2	118.3 (3)	C9—C10—H10	120.2
C4—C3—H3	120.8	C10—C11—C12	120.8 (3)
C2—C3—H3	120.8	C10—C11—Cl3	119.7 (3)
C3—C4—C5	121.5 (3)	C12—C11—Cl3	119.5 (3)
C3—C4—Cl1	119.2 (2)	C13—C12—C11	119.2 (3)
C5—C4—Cl1	119.2 (3)	C13—C12—H12	120.4
C4—C5—C6	119.1 (3)	C11—C12—H12	120.4
C4—C5—H5	120.4	C12—C13—C14	120.9 (3)
C6—C5—H5	120.4	C12—C13—H13	119.5
C5—C6—C1	121.9 (3)	C14—C13—H13	119.5
C5—C6—H6	119.0	C9—C14—C13	119.3 (3)
C1—C6—H6	119.0	C9—C14—H14	120.3
N1—C7—C1	118.5 (3)	C13—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	0.90 (1)	2.08 (2)	2.900 (3)	152 (3)
C7—H7···O1ⁱ	0.93	2.35	3.155 (3)	145

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉Cl₃N₂O
M_r	327.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.372 (3), 14.071 (2), 8.332 (2)
β (°)	97.582 (3)
V (Å³)	1437.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.30 × 0.27 × 0.27

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.833, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	7125, 3081, 1776
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.129, 1.02
No. of reflections	3081
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)	0.27, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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	0.896 (10)	2.076 (16)	2.900 (3)	152 (3)
C7—H7···O1ⁱ	0.93	2.35	3.155 (3)	145

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The author acknowledges financial support from Chongqing Three Gorges University.

References

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