3-Chloro-N′-(2-chloro­benzyl­idene)benzohydrazide

Lei, Y.; Fu, C.

doi:10.1107/S1600536811001656

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o410

doi:10.1107/S1600536811001656

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3-Chloro-N′-(2-chlorobenzylidene)benzohydrazide

Yan Lei ^a ^* and Chuan Fu ^a

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

(Received 8 January 2011; accepted 11 January 2011; online 15 January 2011)

The title compound, C₁₄H₁₀Cl₂N₂O, was prepared from the reaction of 2-chlorobenzaldehyde with 3-chlorobenzohydrazide in methanol. The molecule adopts an E configuration about the methylidene unit and the two aromatic rings form a dihedral angle of 13.8 (2)°. In the crystal, molecules are linked via intermolecular N—H⋯O and C—H⋯O hydrogen bonds, forming chains along the c axis.

Related literature

For background to hydrazones, see: El-Asmy et al. (2010 ); El-Sherif (2009 ); Singh et al. (2009 ); El-Tabl et al. (2007 ); Lei (2011 ). For structures of hydrazone compounds, see: Qiao et al. (2010 ); Hussain et al. (2010 ); Han & Zhao (2010 ); Ahmad et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₀Cl₂N₂O
M_r = 293.14
Monoclinic, P 2₁ /c
a = 13.106 (3) Å
b = 12.588 (3) Å
c = 8.347 (2) Å
β = 97.578 (2)°
V = 1365.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 298 K
0.32 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.865, T_max = 0.873
6893 measured reflections
2954 independent reflections
1936 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.130
S = 1.01
2954 reflections
175 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.48 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)	1.98 (1)	2.854 (2)	164 (2)
C7—H7⋯O1ⁱ	0.93	2.51	3.254 (2)	137 (2)
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: 10.1107/S1600536811001656/qm2001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001656/qm2001Isup2.hkl

checkCIF report

Comment top

In recent years, much effort has been devoted for developing the hydrazones, due to 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; Lei, 2011). 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 13.8 (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); Lei (2011). 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-chlorobenzaldehyde (1 mmol, 0.140 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.

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 molecular packing of the title compound. Hydrogen bonding is shown in dashed lines.

3-Chloro-N'-(2-chlorobenzylidene)benzohydrazide top

Crystal data top

C₁₄H₁₀Cl₂N₂O	F(000) = 600
M_r = 293.14	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.106 (3) Å	Cell parameters from 1672 reflections
b = 12.588 (3) Å	θ = 2.2–25.0°
c = 8.347 (2) Å	µ = 0.47 mm⁻¹
β = 97.578 (2)°	T = 298 K
V = 1365.0 (6) Å³	Cut from needle, colourless
Z = 4	0.32 × 0.30 × 0.30 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2954 independent reflections
Radiation source: fine-focus sealed tube	1936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→8
T_min = 0.865, T_max = 0.873	k = −15→15
6893 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0682P)²] where P = (F_o² + 2F_c²)/3
2954 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.26 e Å⁻³
1 restraint	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₁₄H₁₀Cl₂N₂O	V = 1365.0 (6) Å³
M_r = 293.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.106 (3) Å	µ = 0.47 mm⁻¹
b = 12.588 (3) Å	T = 298 K
c = 8.347 (2) Å	0.32 × 0.30 × 0.30 mm
β = 97.578 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2954 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1936 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.873	R_int = 0.032
6893 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.26 e Å⁻³
2954 reflections	Δρ_min = −0.48 e Å⁻³
175 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	0.21684 (6)	1.16019 (5)	0.46800 (10)	0.0837 (3)
Cl2	0.53314 (6)	0.63298 (7)	0.15637 (9)	0.0856 (3)
N1	0.19380 (12)	0.83421 (13)	0.60855 (18)	0.0400 (4)
N2	0.24735 (13)	0.76623 (13)	0.51905 (19)	0.0427 (4)
O1	0.26043 (12)	0.63872 (10)	0.71199 (17)	0.0540 (4)
C1	0.12399 (14)	1.00751 (15)	0.6282 (2)	0.0385 (5)
C2	0.12993 (16)	1.11524 (18)	0.5925 (3)	0.0490 (5)
C3	0.06753 (19)	1.18886 (19)	0.6553 (3)	0.0611 (6)
H3	0.0727	1.2605	0.6301	0.073*
C4	−0.0017 (2)	1.1565 (2)	0.7544 (3)	0.0632 (7)
H4	−0.0443	1.2059	0.7952	0.076*
C5	−0.00819 (18)	1.0505 (2)	0.7936 (3)	0.0587 (6)
H5	−0.0545	1.0284	0.8622	0.070*
C6	0.05422 (16)	0.97729 (17)	0.7309 (2)	0.0481 (5)
H6	0.0494	0.9060	0.7581	0.058*
C7	0.18546 (15)	0.92841 (16)	0.5543 (2)	0.0421 (5)
H7	0.2187	0.9475	0.4668	0.050*
C8	0.27659 (15)	0.66994 (15)	0.5784 (2)	0.0395 (5)
C9	0.33107 (14)	0.60210 (16)	0.4702 (2)	0.0385 (5)
C10	0.39762 (14)	0.64550 (17)	0.3718 (2)	0.0434 (5)
H10	0.4085	0.7185	0.3701	0.052*
C11	0.44732 (15)	0.57875 (19)	0.2767 (2)	0.0491 (5)
C12	0.43214 (18)	0.4709 (2)	0.2764 (3)	0.0604 (6)
H12	0.4660	0.4271	0.2108	0.073*
C13	0.36611 (18)	0.4287 (2)	0.3747 (3)	0.0597 (6)
H13	0.3549	0.3558	0.3750	0.072*
C14	0.31610 (16)	0.49373 (16)	0.4730 (2)	0.0480 (5)
H14	0.2726	0.4645	0.5406	0.058*
H2	0.2558 (19)	0.784 (2)	0.4177 (15)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0797 (5)	0.0687 (5)	0.1097 (6)	0.0039 (3)	0.0387 (4)	0.0327 (4)
Cl2	0.0801 (5)	0.1113 (6)	0.0754 (5)	0.0101 (4)	0.0480 (4)	0.0065 (4)
N1	0.0445 (9)	0.0439 (10)	0.0329 (9)	0.0052 (7)	0.0100 (7)	−0.0031 (7)
N2	0.0552 (10)	0.0449 (10)	0.0309 (9)	0.0109 (8)	0.0159 (8)	0.0019 (7)
O1	0.0810 (11)	0.0488 (9)	0.0364 (8)	0.0073 (7)	0.0237 (7)	0.0049 (6)
C1	0.0390 (10)	0.0428 (12)	0.0332 (10)	0.0044 (8)	0.0028 (8)	−0.0010 (8)
C2	0.0436 (11)	0.0519 (14)	0.0509 (13)	0.0030 (10)	0.0043 (9)	0.0033 (10)
C3	0.0637 (14)	0.0438 (13)	0.0743 (17)	0.0098 (11)	0.0037 (13)	−0.0032 (12)
C4	0.0640 (15)	0.0614 (16)	0.0644 (16)	0.0179 (12)	0.0092 (13)	−0.0153 (12)
C5	0.0548 (13)	0.0700 (16)	0.0540 (14)	0.0091 (12)	0.0177 (11)	−0.0036 (12)
C6	0.0507 (12)	0.0467 (12)	0.0482 (13)	0.0017 (10)	0.0116 (10)	−0.0008 (10)
C7	0.0435 (11)	0.0482 (12)	0.0357 (11)	0.0037 (9)	0.0098 (8)	0.0013 (9)
C8	0.0427 (11)	0.0438 (12)	0.0331 (11)	0.0010 (9)	0.0092 (8)	0.0002 (9)
C9	0.0376 (10)	0.0452 (12)	0.0323 (10)	0.0052 (8)	0.0033 (8)	−0.0015 (8)
C10	0.0449 (11)	0.0507 (13)	0.0351 (11)	0.0046 (9)	0.0072 (9)	−0.0016 (9)
C11	0.0445 (11)	0.0647 (15)	0.0400 (12)	0.0093 (10)	0.0122 (9)	−0.0011 (10)
C12	0.0610 (14)	0.0699 (17)	0.0511 (14)	0.0208 (12)	0.0102 (12)	−0.0151 (12)
C13	0.0675 (15)	0.0473 (14)	0.0640 (16)	0.0079 (11)	0.0077 (12)	−0.0082 (11)
C14	0.0502 (12)	0.0478 (13)	0.0468 (13)	0.0037 (10)	0.0089 (10)	0.0005 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.735 (2)	C5—C6	1.380 (3)
Cl2—C11	1.743 (2)	C5—H5	0.9300
N1—C7	1.269 (2)	C6—H6	0.9300
N1—N2	1.386 (2)	C7—H7	0.9300
N2—C8	1.346 (2)	C8—C9	1.491 (3)
N2—H2	0.895 (10)	C9—C14	1.379 (3)
O1—C8	1.227 (2)	C9—C10	1.387 (3)
C1—C6	1.387 (3)	C10—C11	1.377 (3)
C1—C2	1.393 (3)	C10—H10	0.9300
C1—C7	1.467 (3)	C11—C12	1.372 (3)
C2—C3	1.384 (3)	C12—C13	1.375 (3)
C3—C4	1.368 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.384 (3)
C4—C5	1.379 (3)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300

C7—N1—N2	114.25 (16)	N1—C7—H7	119.6
C8—N2—N1	119.83 (15)	C1—C7—H7	119.6
C8—N2—H2	120.5 (17)	O1—C8—N2	123.24 (18)
N1—N2—H2	119.3 (17)	O1—C8—C9	121.38 (18)
C6—C1—C2	117.34 (18)	N2—C8—C9	115.39 (16)
C6—C1—C7	121.13 (18)	C14—C9—C10	120.11 (19)
C2—C1—C7	121.46 (19)	C14—C9—C8	118.42 (18)
C3—C2—C1	121.2 (2)	C10—C9—C8	121.45 (18)
C3—C2—Cl1	118.42 (19)	C11—C10—C9	118.9 (2)
C1—C2—Cl1	120.35 (16)	C11—C10—H10	120.6
C4—C3—C2	120.1 (2)	C9—C10—H10	120.6
C4—C3—H3	119.9	C12—C11—C10	121.7 (2)
C2—C3—H3	119.9	C12—C11—Cl2	119.40 (17)
C3—C4—C5	119.9 (2)	C10—C11—Cl2	118.91 (18)
C3—C4—H4	120.1	C11—C12—C13	118.9 (2)
C5—C4—H4	120.1	C11—C12—H12	120.5
C4—C5—C6	119.9 (2)	C13—C12—H12	120.5
C4—C5—H5	120.1	C12—C13—C14	120.7 (2)
C6—C5—H5	120.1	C12—C13—H13	119.7
C5—C6—C1	121.6 (2)	C14—C13—H13	119.7
C5—C6—H6	119.2	C9—C14—C13	119.7 (2)
C1—C6—H6	119.2	C9—C14—H14	120.1
N1—C7—C1	120.73 (18)	C13—C14—H14	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.90 (1)	1.98 (1)	2.854 (2)	164 (2)
C7—H7···O1ⁱ	0.93	2.51	3.254 (2)	137 (2)

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀Cl₂N₂O
M_r	293.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.106 (3), 12.588 (3), 8.347 (2)
β (°)	97.578 (2)
V (Å³)	1365.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.32 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.865, 0.873
No. of measured, independent and observed [I > 2σ(I)] reflections	6893, 2954, 1936
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.01
No. of reflections	2954
No. of parameters	175
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)	0.26, −0.48

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	0.895 (10)	1.982 (12)	2.854 (2)	164 (2)
C7—H7···O1ⁱ	0.93	2.51	3.254 (2)	137 (2)

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge financial support from the Chongqing Three Gorges University.

References

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