N′-(2,4-Dichloro­benzyl­idene)-4-methoxy­benzohydrazide methanol solvate

Liang, M.; Zou, D.-H.

doi:10.1107/S1600536809022624

organic compounds

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Volume 65| Part 7| July 2009| Page o1609

doi:10.1107/S1600536809022624

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N′-(2,4-Dichlorobenzylidene)-4-methoxybenzohydrazide methanol solvate

Min Liang ^a ^* and Dong-Hui Zou ^b

^aCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, People's Republic of China, and ^bCollege of Life Science and Engineering, Qiqihar University, Qiqihar 161006, People's Republic of China
^*Correspondence e-mail: liangmin09@163.com

(Received 11 June 2009; accepted 12 June 2009; online 17 June 2009)

In the title compound, C₁₅H₁₂Cl₂N₂O₂·CH₃OH, the hydrazone molecule displays an E configuration about the C=N bond. The dihedral angle between the two benzene rings is 4.6 (2)°. In the crystal structure, the hydrazone and methanol molecules are linked into a chain propagating along the a axis via N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the biological properties of hydrazone compounds, see: Küçükgüzel et al. (2003 ); Charkoudian et al. (2007 ). For the crystal structures of hydrazone compounds, see: Fun et al. (2008 ); Lo & Ng (2009 ); Ren (2009 ); Zhang (2009 ). For related structures, see: Wu (2009 ); Peng & Hou (2008 ); Mohd Lair et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₂Cl₂N₂O₂·CH₄O
M_r = 355.21
Triclinic, $[P \overline 1]$
a = 6.7401 (11) Å
b = 8.9583 (14) Å
c = 14.567 (2) Å
α = 75.085 (2)°
β = 81.570 (2)°
γ = 83.445 (2)°
V = 838.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.924, T_max = 0.931
4896 measured reflections
3557 independent reflections
2461 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.128
S = 1.03
3557 reflections
214 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.893 (10)	2.013 (12)	2.889 (3)	167 (3)
O3—H3⋯O1ⁱⁱ	0.82	1.99	2.780 (2)	163
Symmetry codes: (i) x, y, z+1; (ii) x-1, y, z-1.

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/S1600536809022624/ci2826sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022624/ci2826Isup2.hkl

checkCIF report

Comment top

Hydrazones possess excellent antibacterial, antifungal, and antitumor activities (Küçükgüzel et al., 2003; Charkoudian et al., 2007). Recently, the crystal structures of some hydrazone compounds have been reported (Fun et al., 2008; Lo & Ng, 2009; Ren, 2009; Zhang, 2009). We report herein the crystal structure of the title new hydrazone compound.

The asymmetric unit of the title compound contains a hydrazone molecule and a methanol molecule. In the hydrazone molecule, the dihedral angle between the two benzene rings is 4.6 (2)°. The hydrazone molecule exists in an E configuration with respect to the methylidene group. All the bond lengths are normal and comparable to those in similar hydrazone compounds (Wu, 2009; Peng & Hou, 2008; Mohd Lair et al., 2009).

In the crystal structure of the title compound, the hydrazone molecules are linked by the methanol molecules through N—H···O and O—H···O hydrogen bonds (Table 1), forming chains propagating along the a axis (Fig. 2).

Related literature top

For the biological properties of hydrazone compounds, see: Küçükgüzel et al. (2003); Charkoudian et al. (2007). For the crystal structures of hydrazone compounds, see: Fun et al. (2008); Lo & Ng (2009); Ren (2009); Zhang (2009). For related structures, see: Wu (2009); Peng & Hou (2008); Mohd Lair et al. (2009).

Experimental top

Equimolar quantities (1.0 mmol each) of 2,4-dichlorobenzaldehyde and 4-methoxybenzohydrazide were mixed and refluxed in methanol. The reaction mixture was cooled to room temperature to give a clear colourless solution. Colourless single crystals of the title compound were formed by slow evaporation of the solution in air.

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 asymmetric unit of the title compound, showing 30% probability displacement ellipsoids for the non-H atoms. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. The packing diagram, viewed along the b axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

N'-(2,4-Dichlorobenzylidene)-4-methoxybenzohydrazide methanol solvate top

Crystal data top

C₁₅H₁₂Cl₂N₂O₂·CH₄O	Z = 2
M_r = 355.21	F(000) = 368
Triclinic, P1	D_x = 1.408 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7401 (11) Å	Cell parameters from 1307 reflections
b = 8.9583 (14) Å	θ = 2.3–26.7°
c = 14.567 (2) Å	µ = 0.40 mm⁻¹
α = 75.085 (2)°	T = 298 K
β = 81.570 (2)°	Block, colourless
γ = 83.445 (2)°	0.20 × 0.18 × 0.18 mm
V = 838.1 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3557 independent reflections
Radiation source: fine-focus sealed tube	2461 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.924, T_max = 0.931	k = −11→11
4896 measured reflections	l = −18→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.048P)² + 0.3404P] where P = (F_o² + 2F_c²)/3
3557 reflections	(Δ/σ)_max = 0.001
214 parameters	Δρ_max = 0.20 e Å⁻³
1 restraint	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₅H₁₂Cl₂N₂O₂·CH₄O	γ = 83.445 (2)°
M_r = 355.21	V = 838.1 (2) Å³
Triclinic, P1	Z = 2
a = 6.7401 (11) Å	Mo Kα radiation
b = 8.9583 (14) Å	µ = 0.40 mm⁻¹
c = 14.567 (2) Å	T = 298 K
α = 75.085 (2)°	0.20 × 0.18 × 0.18 mm
β = 81.570 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3557 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2461 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.931	R_int = 0.017
4896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.20 e Å⁻³
3557 reflections	Δρ_min = −0.31 e Å⁻³
214 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	0.24871 (10)	0.73959 (10)	1.31319 (5)	0.0692 (2)
Cl2	0.81448 (12)	0.99939 (9)	1.42996 (5)	0.0719 (3)
N1	0.6168 (3)	0.8075 (2)	1.04117 (13)	0.0442 (5)
N2	0.5388 (3)	0.7708 (2)	0.96816 (13)	0.0451 (5)
O1	0.8442 (2)	0.7876 (2)	0.88034 (12)	0.0582 (5)
O2	0.4029 (3)	0.5972 (2)	0.58129 (13)	0.0661 (5)
O3	0.1098 (3)	0.7492 (2)	0.01521 (13)	0.0613 (5)
H3	0.0183	0.7737	−0.0185	0.092*
C1	0.5714 (3)	0.8617 (3)	1.19309 (16)	0.0415 (5)
C2	0.4710 (3)	0.8331 (3)	1.28613 (17)	0.0451 (6)
C3	0.5433 (4)	0.8734 (3)	1.35947 (17)	0.0502 (6)
H3A	0.4748	0.8523	1.4210	0.060*
C4	0.7199 (4)	0.9456 (3)	1.33905 (17)	0.0501 (6)
C5	0.8244 (4)	0.9770 (3)	1.24829 (17)	0.0506 (6)
H5	0.9432	1.0262	1.2357	0.061*
C6	0.7498 (4)	0.9343 (3)	1.17690 (17)	0.0469 (6)
H6	0.8205	0.9544	1.1158	0.056*
C7	0.4950 (4)	0.8199 (3)	1.11445 (16)	0.0462 (6)
H7	0.3601	0.8029	1.1183	0.055*
C8	0.6669 (3)	0.7618 (3)	0.88846 (16)	0.0416 (5)
C9	0.5841 (3)	0.7173 (3)	0.81095 (15)	0.0411 (5)
C10	0.6995 (4)	0.7383 (3)	0.72207 (17)	0.0490 (6)
H10	0.8226	0.7809	0.7130	0.059*
C11	0.6354 (4)	0.6974 (3)	0.64766 (17)	0.0553 (7)
H11	0.7148	0.7129	0.5887	0.066*
C12	0.4530 (4)	0.6333 (3)	0.65966 (17)	0.0487 (6)
C13	0.3364 (4)	0.6112 (3)	0.74703 (18)	0.0557 (7)
H13	0.2135	0.5685	0.7559	0.067*
C14	0.4030 (4)	0.6528 (3)	0.82198 (17)	0.0542 (7)
H14	0.3238	0.6370	0.8810	0.065*
C15	0.2166 (5)	0.5339 (4)	0.5880 (2)	0.0752 (9)
H15A	0.2099	0.4415	0.6391	0.113*
H15B	0.2050	0.5092	0.5288	0.113*
H15C	0.1084	0.6081	0.6008	0.113*
C16	0.0604 (5)	0.6214 (3)	0.0907 (2)	0.0715 (8)
H16A	0.1791	0.5753	0.1196	0.107*
H16B	0.0061	0.5466	0.0666	0.107*
H16C	−0.0377	0.6547	0.1376	0.107*
H2	0.4070 (17)	0.761 (3)	0.973 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0488 (4)	0.1016 (6)	0.0583 (4)	−0.0229 (4)	0.0003 (3)	−0.0181 (4)
Cl2	0.0865 (5)	0.0888 (6)	0.0534 (4)	−0.0131 (4)	−0.0237 (4)	−0.0297 (4)
N1	0.0427 (11)	0.0564 (12)	0.0384 (10)	−0.0082 (9)	−0.0097 (8)	−0.0159 (9)
N2	0.0362 (10)	0.0655 (13)	0.0396 (10)	−0.0100 (10)	−0.0066 (8)	−0.0202 (9)
O1	0.0410 (10)	0.0925 (14)	0.0470 (10)	−0.0223 (9)	−0.0023 (7)	−0.0221 (9)
O2	0.0677 (12)	0.0936 (15)	0.0495 (11)	−0.0154 (11)	−0.0066 (9)	−0.0365 (10)
O3	0.0389 (10)	0.0899 (14)	0.0539 (11)	−0.0146 (9)	−0.0084 (8)	−0.0097 (10)
C1	0.0419 (13)	0.0438 (13)	0.0402 (12)	−0.0003 (10)	−0.0089 (10)	−0.0120 (10)
C2	0.0386 (12)	0.0523 (15)	0.0439 (13)	−0.0012 (11)	−0.0064 (10)	−0.0114 (11)
C3	0.0509 (15)	0.0626 (16)	0.0381 (13)	−0.0006 (12)	−0.0054 (10)	−0.0158 (11)
C4	0.0601 (16)	0.0531 (15)	0.0432 (13)	0.0014 (12)	−0.0188 (11)	−0.0183 (11)
C5	0.0531 (15)	0.0544 (15)	0.0494 (14)	−0.0124 (12)	−0.0117 (11)	−0.0152 (12)
C6	0.0495 (14)	0.0539 (15)	0.0386 (12)	−0.0110 (11)	−0.0029 (10)	−0.0121 (11)
C7	0.0399 (13)	0.0586 (15)	0.0442 (13)	−0.0076 (11)	−0.0088 (10)	−0.0164 (11)
C8	0.0399 (13)	0.0474 (14)	0.0384 (12)	−0.0083 (10)	−0.0066 (10)	−0.0089 (10)
C9	0.0392 (12)	0.0472 (13)	0.0384 (12)	−0.0056 (10)	−0.0057 (9)	−0.0116 (10)
C10	0.0406 (13)	0.0641 (16)	0.0443 (13)	−0.0132 (11)	−0.0016 (10)	−0.0151 (12)
C11	0.0531 (15)	0.0764 (19)	0.0391 (13)	−0.0106 (13)	0.0034 (11)	−0.0216 (13)
C12	0.0527 (15)	0.0576 (15)	0.0411 (13)	−0.0039 (12)	−0.0089 (11)	−0.0198 (11)
C13	0.0486 (15)	0.0778 (19)	0.0495 (14)	−0.0240 (13)	−0.0027 (11)	−0.0251 (13)
C14	0.0519 (15)	0.0768 (18)	0.0394 (13)	−0.0224 (13)	0.0029 (11)	−0.0215 (12)
C15	0.071 (2)	0.102 (2)	0.0701 (19)	−0.0163 (17)	−0.0211 (16)	−0.0415 (18)
C16	0.0693 (19)	0.0626 (19)	0.084 (2)	−0.0067 (15)	−0.0218 (16)	−0.0125 (16)

Geometric parameters (Å, º) top

Cl1—C2	1.745 (2)	C6—H6	0.93
Cl2—C4	1.743 (2)	C7—H7	0.93
N1—C7	1.268 (3)	C8—C9	1.487 (3)
N1—N2	1.378 (2)	C9—C14	1.380 (3)
N2—C8	1.356 (3)	C9—C10	1.389 (3)
N2—H2	0.893 (10)	C10—C11	1.369 (3)
O1—C8	1.226 (3)	C10—H10	0.93
O2—C12	1.360 (3)	C11—C12	1.385 (3)
O2—C15	1.417 (3)	C11—H11	0.93
O3—C16	1.401 (3)	C12—C13	1.374 (3)
O3—H3	0.82	C13—C14	1.387 (3)
C1—C6	1.392 (3)	C13—H13	0.93
C1—C2	1.397 (3)	C14—H14	0.93
C1—C7	1.468 (3)	C15—H15A	0.96
C2—C3	1.378 (3)	C15—H15B	0.96
C3—C4	1.377 (4)	C15—H15C	0.96
C3—H3A	0.93	C16—H16A	0.96
C4—C5	1.380 (3)	C16—H16B	0.96
C5—C6	1.373 (3)	C16—H16C	0.96
C5—H5	0.93

C7—N1—N2	116.93 (19)	C14—C9—C10	117.8 (2)
C8—N2—N1	117.23 (18)	C14—C9—C8	124.5 (2)
C8—N2—H2	123.2 (19)	C10—C9—C8	117.7 (2)
N1—N2—H2	119.4 (19)	C11—C10—C9	121.2 (2)
C12—O2—C15	118.8 (2)	C11—C10—H10	119.4
C16—O3—H3	109.5	C9—C10—H10	119.4
C6—C1—C2	116.9 (2)	C10—C11—C12	120.4 (2)
C6—C1—C7	120.4 (2)	C10—C11—H11	119.8
C2—C1—C7	122.7 (2)	C12—C11—H11	119.8
C3—C2—C1	122.3 (2)	O2—C12—C13	124.8 (2)
C3—C2—Cl1	117.74 (19)	O2—C12—C11	115.8 (2)
C1—C2—Cl1	119.93 (17)	C13—C12—C11	119.4 (2)
C4—C3—C2	118.2 (2)	C12—C13—C14	119.7 (2)
C4—C3—H3A	120.9	C12—C13—H13	120.2
C2—C3—H3A	120.9	C14—C13—H13	120.2
C3—C4—C5	121.8 (2)	C9—C14—C13	121.5 (2)
C3—C4—Cl2	119.34 (19)	C9—C14—H14	119.2
C5—C4—Cl2	118.9 (2)	C13—C14—H14	119.2
C6—C5—C4	118.7 (2)	O2—C15—H15A	109.5
C6—C5—H5	120.6	O2—C15—H15B	109.5
C4—C5—H5	120.6	H15A—C15—H15B	109.5
C5—C6—C1	122.1 (2)	O2—C15—H15C	109.5
C5—C6—H6	119.0	H15A—C15—H15C	109.5
C1—C6—H6	119.0	H15B—C15—H15C	109.5
N1—C7—C1	118.6 (2)	O3—C16—H16A	109.5
N1—C7—H7	120.7	O3—C16—H16B	109.5
C1—C7—H7	120.7	H16A—C16—H16B	109.5
O1—C8—N2	121.9 (2)	O3—C16—H16C	109.5
O1—C8—C9	120.9 (2)	H16A—C16—H16C	109.5
N2—C8—C9	117.20 (19)	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.89 (1)	2.01 (1)	2.889 (3)	167 (3)
O3—H3···O1ⁱⁱ	0.82	1.99	2.780 (2)	163

Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂Cl₂N₂O₂·CH₄O
M_r	355.21
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.7401 (11), 8.9583 (14), 14.567 (2)
α, β, γ (°)	75.085 (2), 81.570 (2), 83.445 (2)
V (Å³)	838.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.924, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	4896, 3557, 2461
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.03
No. of reflections	3557
No. of parameters	214
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)	0.20, −0.31

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···O3ⁱ	0.893 (10)	2.013 (12)	2.889 (3)	167 (3)
O3—H3···O1ⁱⁱ	0.82	1.99	2.780 (2)	163

Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z−1.

Acknowledgements

The authors acknowledge Qiqihar University for funding this study.

References

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