N′-(2-Chloro­benzyl­idene)-2-methyl­benzohydrazide

Zhang, W.-G.

doi:10.1107/S1600536812000463

organic compounds

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Volume 68| Part 2| February 2012| Page o357

doi:10.1107/S1600536812000463

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N′-(2-Chlorobenzylidene)-2-methylbenzohydrazide

Wei-Guang Zhang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, People's Republic of China
^*Correspondence e-mail: zhangweiguang1230@163.com

(Received 24 December 2011; accepted 5 January 2012; online 11 January 2012)

The title hydrazone compound, C₁₅H₁₃ClN₂O, adopts an E configuration about the C=N double bond. The dihedral angle between the two benzene rings is 13.1 (2)°. In the crystal, molecules are linked through N—H⋯O hydrogen bonds, forming chains parallel to [101].

Related literature

For the biological properties of hydrazone compounds, see: Ajani et al. (2010 ); Angelusiu et al. (2010 ); Zhang et al. (2010 ); Horiuchi et al. (2009 ). For the crystal structures of similar hydrazone comounds, see: Ban (2010 ); Hussain et al. (2010 ); Shalash et al. (2010 ); Khaledi et al. (2009 ). For the crystal structure of the 2-fluorobenzohydrazide analoque, reported on recently by the author, see: Zhang (2011 ).

Experimental

Crystal data

C₁₅H₁₃ClN₂O
M_r = 272.72
Monoclinic, P 2₁ /n
a = 7.4305 (17) Å
b = 25.596 (2) Å
c = 7.7926 (18) Å
β = 113.505 (2)°
V = 1359.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.947, T_max = 0.947
7513 measured reflections
2516 independent reflections
1870 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.141
S = 1.08
2516 reflections
176 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.33 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)	2.00 (1)	2.876 (3)	164 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536812000463/qm2047sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000463/qm2047Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000463/qm2047Isup3.cml

checkCIF report

Comment top

Benzoylhydrazones are a kind of special Schiff bases bearing the –C(O)—NH—N=CH– groups. The hydrazone compounds have been received much attention for their excellent biological properties (Ajani et al., 2010; Angelusiu et al., 2010; Zhang et al., 2010; Horiuchi et al., 2009) as well as their crystal structures (Ban, 2010; Hussain et al., 2010; Shalash et al., 2010; Khaledi et al., 2009). Recently, the author has reported a hydrazone compound derived from the reaction of 2-chlorobenzaldehyde with 2-fluorobenzohydrazide (Zhang, 2011). In the present paper, the title new hydrazone compound, derived from the reaction of 2-chlorobenzaldehyde with 2-methylbenzohydrazide, is reported.

The compound adopts an E configuration about the C═N double bond (Fig. 1). The dihedral angle between the two substituted benzene rings is 13.1 (2)°. In the crystal structure, molecules are linked through intermolecular N—H···O hydrogen bonds (Table 1), forming chains parallel to the ac diagonal (Fig. 2).

Related literature top

For the biological properties of hydrazone compounds, see: Ajani et al. (2010); Angelusiu et al. (2010); Zhang et al. (2010); Horiuchi et al. (2009). For the crystal structures of similar hydrazone comounds, see: Ban (2010); Hussain et al. (2010); Shalash et al. (2010); Khaledi et al. (2009). For the compound the author reported recently, see: Zhang (2011).

Experimental top

2-Chlorobenzaldehyde (0.140 g, 1 mmol) and 2-methylbenzohydrazide (0.150 g, 1 mmol) were mixed in 50 ml me thanol. The mixture was stirred and refluxed for 30 min and cooled to room temperature to give a colorless solution. Colorless block-shaped single crystals were obtained on slow evaporation of the solution in air.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The molecular packing of the title compound viewed along the c axis. Hydrogen bonds are shown as dashed lines. H-atoms not involved in hydrogen bonding have been omitted for clarity.

N'-(2-Chlorobenzylidene)-2-methylbenzohydrazide top

Crystal data top

C₁₅H₁₃ClN₂O	F(000) = 568
M_r = 272.72	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4305 (17) Å	Cell parameters from 2213 reflections
b = 25.596 (2) Å	θ = 2.7–24.5°
c = 7.7926 (18) Å	µ = 0.27 mm⁻¹
β = 113.505 (2)°	T = 298 K
V = 1359.1 (5) Å³	Block, colorless
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2516 independent reflections
Radiation source: fine-focus sealed tube	1870 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
T_min = 0.947, T_max = 0.947	k = −25→31
7513 measured reflections	l = −9→9

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0445P)² + 1.1147P] where P = (F_o² + 2F_c²)/3
2516 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₅H₁₃ClN₂O	V = 1359.1 (5) Å³
M_r = 272.72	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4305 (17) Å	µ = 0.27 mm⁻¹
b = 25.596 (2) Å	T = 298 K
c = 7.7926 (18) Å	0.20 × 0.20 × 0.20 mm
β = 113.505 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2516 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1870 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.947	R_int = 0.043
7513 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	1 restraint
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.24 e Å⁻³
2516 reflections	Δρ_min = −0.33 e Å⁻³
176 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	0.29514 (17)	0.04920 (3)	0.54672 (14)	0.0790 (4)
N1	0.1795 (3)	0.21108 (8)	0.4023 (3)	0.0380 (5)
N2	0.2213 (3)	0.24341 (8)	0.5565 (3)	0.0388 (6)
O1	0.0050 (3)	0.30528 (7)	0.3860 (2)	0.0468 (5)
C1	0.2276 (4)	0.12767 (10)	0.2918 (4)	0.0374 (6)
C2	0.2488 (4)	0.07402 (11)	0.3250 (4)	0.0465 (7)
C3	0.2323 (5)	0.03896 (12)	0.1830 (5)	0.0581 (9)
H3	0.2448	0.0033	0.2069	0.070*
C4	0.1976 (5)	0.05753 (14)	0.0072 (5)	0.0611 (9)
H4	0.1865	0.0343	−0.0882	0.073*
C5	0.1791 (5)	0.11049 (13)	−0.0288 (4)	0.0546 (8)
H5	0.1573	0.1229	−0.1476	0.066*
C6	0.1931 (4)	0.14482 (11)	0.1120 (4)	0.0442 (7)
H6	0.1792	0.1804	0.0863	0.053*
C7	0.2488 (4)	0.16495 (10)	0.4419 (4)	0.0386 (6)
H7	0.3131	0.1549	0.5664	0.046*
C8	0.1263 (4)	0.28972 (10)	0.5363 (3)	0.0331 (6)
C9	0.1778 (4)	0.31909 (10)	0.7153 (4)	0.0349 (6)
C10	0.2087 (4)	0.37314 (11)	0.7235 (4)	0.0432 (7)
C11	0.2488 (5)	0.39768 (14)	0.8949 (5)	0.0634 (10)
H11	0.2718	0.4335	0.9046	0.076*
C12	0.2553 (5)	0.37064 (17)	1.0496 (5)	0.0728 (11)
H12	0.2811	0.3883	1.1612	0.087*
C13	0.2242 (5)	0.31800 (17)	1.0403 (4)	0.0663 (10)
H13	0.2282	0.2997	1.1450	0.080*
C14	0.1869 (4)	0.29217 (12)	0.8746 (4)	0.0475 (7)
H14	0.1673	0.2562	0.8686	0.057*
C15	0.2020 (5)	0.40465 (12)	0.5579 (5)	0.0598 (9)
H15A	0.2780	0.3874	0.4998	0.090*
H15B	0.2554	0.4388	0.5990	0.090*
H15C	0.0685	0.4078	0.4693	0.090*
H2	0.312 (4)	0.2342 (13)	0.669 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1180 (9)	0.0447 (5)	0.0724 (6)	0.0103 (5)	0.0360 (6)	0.0145 (4)
N1	0.0397 (13)	0.0355 (12)	0.0320 (11)	0.0014 (10)	0.0069 (10)	−0.0057 (9)
N2	0.0427 (14)	0.0341 (12)	0.0288 (11)	0.0062 (10)	0.0031 (10)	−0.0042 (9)
O1	0.0516 (12)	0.0383 (10)	0.0342 (10)	0.0068 (9)	−0.0002 (9)	−0.0008 (8)
C1	0.0312 (14)	0.0343 (14)	0.0432 (15)	−0.0029 (11)	0.0111 (12)	−0.0065 (12)
C2	0.0450 (18)	0.0389 (16)	0.0532 (18)	0.0018 (13)	0.0172 (14)	−0.0017 (13)
C3	0.058 (2)	0.0368 (17)	0.082 (2)	−0.0037 (14)	0.0298 (19)	−0.0161 (16)
C4	0.060 (2)	0.061 (2)	0.066 (2)	−0.0093 (17)	0.0283 (18)	−0.0288 (18)
C5	0.0511 (19)	0.070 (2)	0.0457 (17)	−0.0116 (16)	0.0223 (15)	−0.0140 (15)
C6	0.0418 (16)	0.0439 (16)	0.0436 (16)	−0.0045 (13)	0.0134 (13)	−0.0057 (13)
C7	0.0382 (16)	0.0374 (15)	0.0344 (14)	0.0021 (12)	0.0084 (12)	0.0002 (12)
C8	0.0316 (14)	0.0319 (13)	0.0313 (13)	−0.0028 (11)	0.0078 (11)	0.0004 (11)
C9	0.0266 (14)	0.0389 (15)	0.0357 (14)	0.0043 (11)	0.0087 (11)	−0.0038 (11)
C10	0.0307 (15)	0.0389 (15)	0.0531 (17)	0.0001 (12)	0.0096 (13)	−0.0090 (13)
C11	0.050 (2)	0.054 (2)	0.074 (2)	0.0003 (15)	0.0113 (18)	−0.0291 (18)
C12	0.062 (2)	0.097 (3)	0.0458 (19)	0.013 (2)	0.0072 (17)	−0.033 (2)
C13	0.057 (2)	0.103 (3)	0.0362 (17)	0.022 (2)	0.0159 (15)	−0.0005 (18)
C14	0.0462 (18)	0.0549 (18)	0.0384 (15)	0.0074 (14)	0.0137 (13)	0.0003 (13)
C15	0.054 (2)	0.0391 (17)	0.085 (2)	−0.0032 (15)	0.0269 (18)	0.0055 (16)

Geometric parameters (Å, º) top

Cl1—C2	1.742 (3)	C7—H7	0.9300
N1—C7	1.276 (3)	C8—C9	1.494 (3)
N1—N2	1.388 (3)	C9—C14	1.397 (4)
N2—C8	1.356 (3)	C9—C10	1.400 (4)
N2—H2	0.899 (10)	C10—C11	1.396 (4)
O1—C8	1.225 (3)	C10—C15	1.505 (4)
C1—C6	1.391 (4)	C11—C12	1.374 (5)
C1—C2	1.395 (4)	C11—H11	0.9300
C1—C7	1.468 (4)	C12—C13	1.364 (5)
C2—C3	1.392 (4)	C12—H12	0.9300
C3—C4	1.374 (5)	C13—C14	1.377 (4)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.380 (5)	C14—H14	0.9300
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.377 (4)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—H6	0.9300

C7—N1—N2	114.4 (2)	O1—C8—C9	123.1 (2)
C8—N2—N1	119.6 (2)	N2—C8—C9	113.8 (2)
C8—N2—H2	120 (2)	C14—C9—C10	119.9 (3)
N1—N2—H2	121 (2)	C14—C9—C8	119.0 (2)
C6—C1—C2	117.3 (2)	C10—C9—C8	121.0 (2)
C6—C1—C7	121.0 (2)	C11—C10—C9	117.2 (3)
C2—C1—C7	121.6 (2)	C11—C10—C15	120.0 (3)
C3—C2—C1	121.3 (3)	C9—C10—C15	122.8 (3)
C3—C2—Cl1	118.3 (2)	C12—C11—C10	122.1 (3)
C1—C2—Cl1	120.4 (2)	C12—C11—H11	118.9
C4—C3—C2	119.5 (3)	C10—C11—H11	118.9
C4—C3—H3	120.3	C13—C12—C11	120.3 (3)
C2—C3—H3	120.3	C13—C12—H12	119.8
C3—C4—C5	120.4 (3)	C11—C12—H12	119.8
C3—C4—H4	119.8	C12—C13—C14	119.4 (3)
C5—C4—H4	119.8	C12—C13—H13	120.3
C6—C5—C4	119.7 (3)	C14—C13—H13	120.3
C6—C5—H5	120.2	C13—C14—C9	121.1 (3)
C4—C5—H5	120.2	C13—C14—H14	119.4
C5—C6—C1	121.7 (3)	C9—C14—H14	119.4
C5—C6—H6	119.1	C10—C15—H15A	109.5
C1—C6—H6	119.1	C10—C15—H15B	109.5
N1—C7—C1	120.3 (2)	H15A—C15—H15B	109.5
N1—C7—H7	119.9	C10—C15—H15C	109.5
C1—C7—H7	119.9	H15A—C15—H15C	109.5
O1—C8—N2	123.1 (2)	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.90 (1)	2.00 (1)	2.876 (3)	164 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃ClN₂O
M_r	272.72
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.4305 (17), 25.596 (2), 7.7926 (18)
β (°)	113.505 (2)
V (Å³)	1359.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.947, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	7513, 2516, 1870
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.141, 1.08
No. of reflections	2516
No. of parameters	176
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)	0.24, −0.33

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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	0.899 (10)	2.000 (14)	2.876 (3)	164 (3)

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

Acknowledgements

Financial support from Qiqihar University is acknowledged.

References

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