(E)-N′-(3,5-Dichloro-2-hy­droxy­benzyl­idene)-2-meth­oxy­benzohydrazide

Li, X.-Y.

doi:10.1107/S160053681102366X

organic compounds

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Volume 67| Part 7| July 2011| Page o1798

doi:10.1107/S160053681102366X

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(E)-N′-(3,5-Dichloro-2-hydroxybenzylidene)-2-methoxybenzohydrazide

Xiao-Yan Li ^a ^*

^aZibo Vocational Institute, Zibo 255314, People's Republic of China
^*Correspondence e-mail: lixiaoyan_zb@126.com

(Received 6 June 2011; accepted 17 June 2011; online 25 June 2011)

In the title compound, C₁₅H₁₂Cl₂N₂O₃, the dihedral angle between the two substituted aromatic rings is 5.4 (4)°. Intramolecular O—H⋯N and N—H⋯O hydrogen bonds affect the planarity of the molcular conformation, with a mean deviation from the plane defined by the non-H atoms of 0.062 (2) Å. The molecule exists in a trans configuration with respect to the methylidene unit. In the crystal, molecules are linked by N—H⋯O interactions.

Related literature

For the crystal structures of hydrazone compounds, see: Li (2011 ); Hashemian et al. (2011 ); Lei (2011 ); Shalash et al. (2010 ).

Experimental

Crystal data

C₁₅H₁₂Cl₂N₂O₃
M_r = 339.17
Monoclinic, C c
a = 10.845 (7) Å
b = 12.771 (8) Å
c = 10.856 (7) Å
β = 96.683 (7)°
V = 1493.4 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 298 K
0.18 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.924, T_max = 0.928
4586 measured reflections
2978 independent reflections
2011 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.133
S = 1.02
2978 reflections
204 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 1272 Friedel pairs
Flack parameter: 0.10 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.82	2.543 (4)	146
N2—H2⋯O3	0.90 (1)	2.02 (5)	2.624 (4)	123 (5)
N2—H2⋯O1ⁱ	0.90 (1)	2.63 (4)	3.271 (5)	129 (5)
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102366X/om2438sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102366X/om2438Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102366X/om2438Isup3.cml

checkCIF report

Comment top

In the last few years, hydrazones have been attracted much attention for their crystal structures (Li, 2011; Hashemian et al., 2011; Lei, 2011; Shalash et al., 2010).

In the crystal structure of the title hydrazone molecule, as shown in Fig. 1, the dihedral angle between the two substituted aromatic rings is 5.4 (4)°. The intramolecular O—H···N and N—H···O hydrogen bonds (Table 1) affect the planarity of the conformation of the molecule. The molecule exists in a trans configuration with respect to the methylidene unit.

Related literature top

For the crystal structures of hydrazone compounds, see: Li (2011); Hashemian et al. (2011); Lei (2011); Shalash et al. (2010).

Experimental top

A mixture of 2-methoxybenzhydrazide (0.166 g, 1 mmol) and 3,5-dichlorosalicylaldehyde (0.190 g, 1 mmol) in 30 ml of ethanol containing a few drops of acetic acid was refluxed for about 1 h. On cooling to room temperature, a solid precipitate was formed. The solid was filtered and then recrystallized from methanol. Colorless crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure with displacement parameters drawn at the 30% probability level. Hydrogen bonds are indicated by dashed lines.

(E)-N'-(3,5-Dichloro-2-hydroxybenzylidene)-2- methoxybenzohydrazide top

Crystal data top

C₁₅H₁₂Cl₂N₂O₃	F(000) = 696
M_r = 339.17	D_x = 1.508 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 816 reflections
a = 10.845 (7) Å	θ = 2.4–24.3°
b = 12.771 (8) Å	µ = 0.45 mm⁻¹
c = 10.856 (7) Å	T = 298 K
β = 96.683 (7)°	Block, colorless
V = 1493.4 (16) Å³	0.18 × 0.18 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2978 independent reflections
Radiation source: fine-focus sealed tube	2011 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
T_min = 0.924, T_max = 0.928	k = −16→12
4586 measured reflections	l = −13→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0425P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2978 reflections	Δρ_max = 0.28 e Å⁻³
204 parameters	Δρ_min = −0.28 e Å⁻³
4 restraints	Absolute structure: Flack (1983), 1272 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (10)

Crystal data top

C₁₅H₁₂Cl₂N₂O₃	V = 1493.4 (16) Å³
M_r = 339.17	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 10.845 (7) Å	µ = 0.45 mm⁻¹
b = 12.771 (8) Å	T = 298 K
c = 10.856 (7) Å	0.18 × 0.18 × 0.17 mm
β = 96.683 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2978 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2011 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.928	R_int = 0.050
4586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.133	Δρ_max = 0.28 e Å⁻³
S = 1.02	Δρ_min = −0.28 e Å⁻³
2978 reflections	Absolute structure: Flack (1983), 1272 Friedel pairs
204 parameters	Absolute structure parameter: 0.10 (10)
4 restraints

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	0.40120 (15)	0.77322 (10)	0.22803 (13)	0.0652 (4)
Cl2	0.47525 (14)	0.96477 (10)	0.67126 (14)	0.0658 (4)
N1	0.6075 (4)	0.4977 (3)	0.5532 (3)	0.0389 (9)
N2	0.6498 (4)	0.4042 (3)	0.6052 (3)	0.0436 (10)
O1	0.5144 (3)	0.5940 (2)	0.3592 (3)	0.0461 (8)
H1	0.5450	0.5443	0.3998	0.069*
O2	0.6238 (4)	0.3303 (2)	0.4167 (3)	0.0581 (10)
O3	0.7634 (3)	0.2894 (3)	0.7842 (3)	0.0535 (10)
C1	0.5091 (4)	0.6771 (3)	0.4333 (4)	0.0353 (10)
C2	0.4584 (4)	0.7706 (4)	0.3839 (4)	0.0436 (12)
C3	0.4487 (4)	0.8590 (4)	0.4551 (5)	0.0464 (12)
H3	0.4142	0.9202	0.4198	0.056*
C4	0.4913 (5)	0.8547 (4)	0.5798 (4)	0.0450 (12)
C5	0.5424 (4)	0.7637 (4)	0.6342 (4)	0.0418 (12)
H5	0.5708	0.7621	0.7184	0.050*
C6	0.5504 (4)	0.6748 (3)	0.5611 (4)	0.0360 (10)
C7	0.6003 (4)	0.5782 (4)	0.6203 (4)	0.0421 (11)
H7	0.6261	0.5760	0.7050	0.051*
C8	0.6559 (4)	0.3220 (3)	0.5280 (4)	0.0376 (11)
C9	0.7044 (4)	0.2206 (3)	0.5831 (4)	0.0374 (11)
C10	0.6993 (5)	0.1355 (4)	0.5042 (5)	0.0476 (12)
H10	0.6651	0.1447	0.4223	0.057*
C11	0.7425 (5)	0.0378 (4)	0.5408 (5)	0.0595 (15)
H11	0.7356	−0.0183	0.4859	0.071*
C12	0.7965 (5)	0.0254 (4)	0.6618 (6)	0.0646 (16)
H12	0.8266	−0.0400	0.6882	0.077*
C13	0.8063 (5)	0.1080 (4)	0.7436 (5)	0.0548 (14)
H13	0.8445	0.0990	0.8242	0.066*
C14	0.7587 (4)	0.2053 (4)	0.7049 (4)	0.0427 (12)
C15	0.8242 (5)	0.2795 (5)	0.9067 (5)	0.0705 (18)
H15A	0.7862	0.2242	0.9488	0.106*
H15B	0.8173	0.3441	0.9505	0.106*
H15C	0.9103	0.2634	0.9035	0.106*
H2	0.667 (5)	0.404 (5)	0.6884 (9)	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0949 (10)	0.0518 (8)	0.0441 (7)	0.0028 (8)	−0.0130 (6)	0.0124 (6)
Cl2	0.0854 (10)	0.0383 (6)	0.0762 (10)	−0.0036 (7)	0.0194 (7)	−0.0199 (7)
N1	0.053 (2)	0.033 (2)	0.0301 (19)	0.0056 (18)	−0.0001 (17)	0.0040 (16)
N2	0.059 (3)	0.035 (2)	0.034 (2)	0.0087 (19)	−0.005 (2)	0.0070 (18)
O1	0.074 (2)	0.0319 (18)	0.0310 (17)	0.0013 (16)	−0.0010 (16)	−0.0017 (14)
O2	0.086 (3)	0.048 (2)	0.0353 (19)	0.0129 (19)	−0.0132 (18)	0.0007 (17)
O3	0.066 (2)	0.054 (2)	0.038 (2)	0.0143 (18)	−0.0076 (17)	0.0048 (17)
C1	0.041 (3)	0.033 (2)	0.032 (2)	−0.0051 (19)	0.005 (2)	0.0042 (19)
C2	0.055 (3)	0.038 (3)	0.037 (3)	−0.006 (2)	0.001 (2)	0.001 (2)
C3	0.052 (3)	0.030 (3)	0.057 (3)	−0.003 (2)	0.005 (2)	0.004 (2)
C4	0.054 (3)	0.032 (3)	0.051 (3)	−0.008 (2)	0.014 (3)	−0.007 (2)
C5	0.049 (3)	0.039 (3)	0.037 (3)	−0.002 (2)	0.003 (2)	−0.004 (2)
C6	0.042 (3)	0.032 (2)	0.034 (3)	0.000 (2)	0.006 (2)	0.0013 (19)
C7	0.051 (3)	0.043 (3)	0.032 (2)	−0.003 (2)	0.002 (2)	0.001 (2)
C8	0.040 (3)	0.035 (2)	0.037 (3)	0.002 (2)	0.000 (2)	0.003 (2)
C9	0.041 (3)	0.030 (3)	0.041 (3)	0.0035 (19)	0.007 (2)	0.0096 (19)
C10	0.053 (3)	0.040 (3)	0.051 (3)	−0.003 (2)	0.011 (2)	−0.001 (2)
C11	0.072 (4)	0.035 (3)	0.072 (4)	0.001 (2)	0.011 (3)	−0.003 (3)
C12	0.063 (4)	0.038 (3)	0.094 (5)	0.017 (3)	0.015 (3)	0.022 (3)
C13	0.056 (3)	0.055 (3)	0.054 (3)	0.010 (3)	0.008 (3)	0.024 (3)
C14	0.043 (3)	0.042 (3)	0.043 (3)	0.007 (2)	0.007 (2)	0.011 (2)
C15	0.070 (4)	0.096 (5)	0.042 (3)	0.020 (3)	−0.010 (3)	0.007 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.734 (5)	C5—H5	0.9300
Cl2—C4	1.741 (5)	C6—C7	1.465 (6)
N1—C7	1.268 (5)	C7—H7	0.9300
N1—N2	1.377 (5)	C8—C9	1.496 (6)
N2—C8	1.350 (5)	C9—C10	1.381 (6)
N2—H2	0.900 (7)	C9—C14	1.397 (6)
O1—C1	1.337 (5)	C10—C11	1.375 (7)
O1—H1	0.8200	C10—H10	0.9300
O2—C8	1.223 (5)	C11—C12	1.383 (8)
O3—C14	1.373 (6)	C11—H11	0.9300
O3—C15	1.420 (6)	C12—C13	1.376 (8)
C1—C2	1.396 (6)	C12—H12	0.9300
C1—C6	1.407 (5)	C13—C14	1.392 (6)
C2—C3	1.379 (7)	C13—H13	0.9300
C3—C4	1.380 (6)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.390 (6)	C15—H15C	0.9600
C5—C6	1.394 (6)

C7—N1—N2	120.5 (4)	O2—C8—N2	121.2 (4)
C8—N2—N1	117.2 (3)	O2—C8—C9	121.1 (4)
C8—N2—H2	127 (4)	N2—C8—C9	117.7 (4)
N1—N2—H2	116 (4)	C10—C9—C14	117.3 (4)
C1—O1—H1	109.5	C10—C9—C8	116.5 (4)
C14—O3—C15	119.8 (4)	C14—C9—C8	126.1 (4)
O1—C1—C2	119.4 (4)	C11—C10—C9	123.1 (5)
O1—C1—C6	123.0 (4)	C11—C10—H10	118.4
C2—C1—C6	117.6 (4)	C9—C10—H10	118.4
C3—C2—C1	122.5 (4)	C10—C11—C12	118.1 (5)
C3—C2—Cl1	119.3 (4)	C10—C11—H11	121.0
C1—C2—Cl1	118.2 (4)	C12—C11—H11	121.0
C2—C3—C4	118.6 (4)	C13—C12—C11	121.2 (5)
C2—C3—H3	120.7	C13—C12—H12	119.4
C4—C3—H3	120.7	C11—C12—H12	119.4
C3—C4—C5	121.4 (4)	C12—C13—C14	119.4 (5)
C3—C4—Cl2	118.9 (4)	C12—C13—H13	120.3
C5—C4—Cl2	119.6 (4)	C14—C13—H13	120.3
C4—C5—C6	119.2 (4)	O3—C14—C13	121.5 (4)
C4—C5—H5	120.4	O3—C14—C9	117.7 (4)
C6—C5—H5	120.4	C13—C14—C9	120.8 (5)
C5—C6—C1	120.7 (4)	O3—C15—H15A	109.5
C5—C6—C7	118.7 (4)	O3—C15—H15B	109.5
C1—C6—C7	120.6 (4)	H15A—C15—H15B	109.5
N1—C7—C6	118.3 (4)	O3—C15—H15C	109.5
N1—C7—H7	120.8	H15A—C15—H15C	109.5
C6—C7—H7	120.8	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.82	2.543 (4)	146
N2—H2···O3	0.90 (1)	2.02 (5)	2.624 (4)	123 (5)
N2—H2···O1ⁱ	0.90 (1)	2.63 (4)	3.271 (5)	129 (5)

Symmetry code: (i) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂Cl₂N₂O₃
M_r	339.17
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	10.845 (7), 12.771 (8), 10.856 (7)
β (°)	96.683 (7)
V (Å³)	1493.4 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.18 × 0.18 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.924, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	4586, 2978, 2011
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.133, 1.02
No. of reflections	2978
No. of parameters	204
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28
Absolute structure	Flack (1983), 1272 Friedel pairs
Absolute structure parameter	0.10 (10)

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
O1—H1···N1	0.82	1.82	2.543 (4)	146
N2—H2···O3	0.900 (7)	2.02 (5)	2.624 (4)	123 (5)
N2—H2···O1ⁱ	0.900 (7)	2.63 (4)	3.271 (5)	129 (5)

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

The author acknowledges the Zibo Vocational Institute for supporting the work.

References

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