N′-(3,4-Dimethoxy­benzyl­idene)acetohydrazide

Lv, L.-P.; Yu, T.-M.; Yu, W.-B.; Li, W.-W.; Hu, X.-C.

doi:10.1107/S1600536809027366

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1989

doi:10.1107/S1600536809027366

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N′-(3,4-Dimethoxybenzylidene)acetohydrazide

Lu-Ping Lv,^a Tie-Ming Yu,^a Wen-Bo Yu,^a Wei-Wei Li ^a and Xian-Chao Hu ^b ^*

^aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, and ^bResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 11 July 2009; accepted 12 July 2009; online 25 July 2009)

In the title molecule, C₁₁H₁₄N₂O₃, the acetohydrazide group is planar 0.084 (1) Å and forms a dihedral angle of 19.7 (1)° with the benzene ring. One of the methoxy groups is coplanar with the attached benzene ring within 0.052 (3) Å, whereas the other is slightly twisted [C—O—C—C = 6.3 (3)°]. The molecule adopts a trans configuration with respect to the C=N bond. In the crystal, the molecules are linked into chains along the a axis by N—H⋯O hydrogen bonds and the chains are cross-linked into a three-dimensional network by C—H⋯O hydrogen bonds.

Related literature

For general background to Schiff bases, see: Cimerman et al. (1997 ); Offe et al. (1952 ); Richardson et al. (1988 ). For related structures, see: Li & Jian (2008 ); Tamboura et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₃
M_r = 222.24
Orthorhombic, P b c a
a = 8.794 (3) Å
b = 10.920 (3) Å
c = 24.418 (7) Å
V = 2345.0 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 223 K
0.24 × 0.21 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.977, T_max = 0.979
11332 measured reflections
2070 independent reflections
1819 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.133
S = 1.10
2070 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.86	1.97	2.803 (2)	164
C1—H1C⋯O2ⁱⁱ	0.96	2.55	3.435 (3)	153
C11—H11C⋯O3ⁱⁱⁱ	0.96	2.47	3.425 (3)	174
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+3, -z.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 I, global. DOI: 10.1107/S1600536809027366/ci2855sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027366/ci2855Isup2.hkl

checkCIF report

Comment top

Schiff bases have attracted much attention due to the possibility of their analytical applications (Cimerman et al., 1997). They are also important ligands, which have been reported to have mild bacteriostatic activity and are used as potential oral iron-chelating drugs for genetic disorders such as thalassemia (Offe et al., 1952; Richardson et al., 1988). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various complexes (Tamboura et al., 2009). We report here the crystal structure of the title compound (Fig. 1).

The acetohydrazide group is planar and it forms a dihedral angle of 19.7 (1)° with the benzene ring. One of the methoxy groups is coplanar with the attached benzene ring [C1—O1—C4—C5 = -1.7 (3)°] whereas the other is slightly twisted [C2—O2—C3—C8 = 6.3 (3)°]. The molecule adopts a trans configuration with respect to the C═N bond. Bond lengths and angles are comparable to those observed for N'-[1-(4-methoxyphenyl)ethylidene]acetohydrazide (Li et al., 2008).

The molecules are linked into a chain along the a axis by N—H···O hydrogen bonds (Table 1). The chains are cross-linked into a three-dimensional network by C—H···O hydrogen bonds (Fig.2).

Related literature top

For general background to Schiff bases, see: Cimerman et al. (1997); Offe et al. (1952); Richardson et al. (1988). For related structures, see: Li et al. (2008); Tamboura et al. (2009).

Experimental top

3,4-Dimethoxybenzaldehyde (1.66 g, 0.01 mol) and acetohydrazide (0.74 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 2.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 470–472 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

N'-(3,4-Dimethoxybenzylidene)acetohydrazide top

Crystal data top

C₁₁H₁₄N₂O₃	F(000) = 944
M_r = 222.24	D_x = 1.259 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2070 reflections
a = 8.794 (3) Å	θ = 1.7–25.0°
b = 10.920 (3) Å	µ = 0.09 mm⁻¹
c = 24.418 (7) Å	T = 223 K
V = 2345.0 (12) Å³	Block, colourless
Z = 8	0.24 × 0.21 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2070 independent reflections
Radiation source: fine-focus sealed tube	1819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→10
T_min = 0.977, T_max = 0.979	k = −12→12
11332 measured reflections	l = −27→28

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)] = 0.050	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0593P)² + 0.6946P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2070 reflections	Δρ_max = 0.15 e Å⁻³
149 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0113 (16)

Crystal data top

C₁₁H₁₄N₂O₃	V = 2345.0 (12) Å³
M_r = 222.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.794 (3) Å	µ = 0.09 mm⁻¹
b = 10.920 (3) Å	T = 223 K
c = 24.418 (7) Å	0.24 × 0.21 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2070 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1819 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.979	R_int = 0.034
11332 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.10	Δρ_max = 0.15 e Å⁻³
2070 reflections	Δρ_min = −0.12 e Å⁻³
149 parameters

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
O1	−0.00337 (17)	0.67057 (13)	0.22113 (6)	0.0725 (5)
O2	−0.21387 (16)	0.81158 (15)	0.18477 (6)	0.0738 (5)
O3	−0.07522 (17)	1.32783 (14)	0.01901 (7)	0.0735 (5)
C3	−0.0722 (2)	0.83356 (17)	0.16379 (7)	0.0516 (5)
C7	0.1114 (2)	0.93669 (17)	0.10716 (7)	0.0519 (5)
C4	0.0432 (2)	0.75598 (17)	0.18390 (8)	0.0537 (5)
C6	0.2227 (2)	0.8587 (2)	0.12649 (8)	0.0621 (5)
H6	0.3216	0.8663	0.1135	0.074*
C8	−0.0381 (2)	0.92289 (17)	0.12603 (7)	0.0507 (5)
H8	−0.1143	0.9742	0.1130	0.061*
C10	0.0460 (2)	1.29542 (18)	−0.00180 (8)	0.0556 (5)
C5	0.1896 (2)	0.76932 (19)	0.16500 (9)	0.0625 (6)
H5	0.2663	0.7184	0.1780	0.075*
C9	0.1527 (2)	1.03131 (19)	0.06757 (8)	0.0564 (5)
H9	0.2501	1.0303	0.0528	0.068*
C11	0.1217 (3)	1.3670 (2)	−0.04662 (9)	0.0702 (6)
H11A	0.0706	1.3517	−0.0807	0.105*
H11B	0.2261	1.3423	−0.0496	0.105*
H11C	0.1169	1.4528	−0.0382	0.105*
C2	−0.3390 (2)	0.8771 (3)	0.16274 (10)	0.0825 (7)
H2A	−0.3234	0.9633	0.1680	0.124*
H2B	−0.4307	0.8524	0.1810	0.124*
H2C	−0.3476	0.8600	0.1243	0.124*
C1	0.1076 (3)	0.5863 (2)	0.24102 (11)	0.0827 (8)
H1A	0.1518	0.5429	0.2108	0.124*
H1B	0.0601	0.5291	0.2655	0.124*
H1C	0.1857	0.6303	0.2602	0.124*
N2	0.12042 (19)	1.19408 (15)	0.01359 (6)	0.0569 (4)
H2	0.2071	1.1778	−0.0010	0.068*
N1	0.06138 (18)	1.11504 (14)	0.05240 (6)	0.0544 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0779 (10)	0.0661 (9)	0.0736 (10)	−0.0030 (7)	−0.0097 (8)	0.0243 (8)
O2	0.0572 (9)	0.0863 (11)	0.0779 (10)	0.0039 (8)	0.0052 (7)	0.0262 (8)
O3	0.0634 (9)	0.0642 (10)	0.0929 (11)	0.0057 (7)	−0.0005 (8)	0.0069 (8)
C3	0.0533 (11)	0.0536 (11)	0.0479 (10)	−0.0003 (9)	−0.0020 (8)	−0.0001 (8)
C7	0.0581 (11)	0.0515 (11)	0.0462 (10)	0.0034 (9)	−0.0006 (8)	−0.0017 (8)
C4	0.0650 (12)	0.0477 (10)	0.0486 (10)	−0.0021 (9)	−0.0085 (9)	0.0030 (8)
C6	0.0545 (11)	0.0661 (13)	0.0656 (12)	0.0041 (10)	0.0016 (10)	0.0063 (10)
C8	0.0560 (11)	0.0488 (10)	0.0473 (10)	0.0068 (8)	−0.0032 (8)	0.0010 (8)
C10	0.0587 (12)	0.0505 (11)	0.0576 (11)	−0.0049 (9)	−0.0092 (9)	−0.0037 (9)
C5	0.0624 (12)	0.0574 (12)	0.0679 (13)	0.0097 (10)	−0.0096 (10)	0.0071 (10)
C9	0.0559 (11)	0.0605 (12)	0.0529 (10)	0.0042 (10)	0.0022 (9)	0.0027 (9)
C11	0.0918 (16)	0.0530 (12)	0.0659 (13)	−0.0018 (11)	−0.0030 (12)	0.0071 (10)
C2	0.0548 (12)	0.1042 (19)	0.0886 (17)	0.0095 (13)	0.0055 (12)	0.0167 (15)
C1	0.0994 (18)	0.0651 (14)	0.0836 (16)	0.0000 (13)	−0.0244 (14)	0.0224 (13)
N2	0.0577 (9)	0.0551 (10)	0.0578 (9)	0.0008 (8)	0.0040 (8)	0.0078 (8)
N1	0.0572 (9)	0.0525 (9)	0.0536 (9)	−0.0042 (8)	0.0005 (7)	0.0052 (7)

Geometric parameters (Å, º) top

O1—C4	1.365 (2)	C10—C11	1.501 (3)
O1—C1	1.427 (3)	C5—H5	0.93
O2—C3	1.368 (2)	C9—N1	1.272 (2)
O2—C2	1.419 (3)	C9—H9	0.93
O3—C10	1.233 (2)	C11—H11A	0.96
C3—C8	1.375 (3)	C11—H11B	0.96
C3—C4	1.410 (3)	C11—H11C	0.96
C7—C6	1.381 (3)	C2—H2A	0.96
C7—C8	1.401 (3)	C2—H2B	0.96
C7—C9	1.461 (3)	C2—H2C	0.96
C4—C5	1.375 (3)	C1—H1A	0.96
C6—C5	1.386 (3)	C1—H1B	0.96
C6—H6	0.93	C1—H1C	0.96
C8—H8	0.93	N2—N1	1.383 (2)
C10—N2	1.340 (2)	N2—H2	0.86

C4—O1—C1	117.52 (18)	N1—C9—H9	118.5
C3—O2—C2	118.41 (16)	C7—C9—H9	118.5
O2—C3—C8	125.05 (17)	C10—C11—H11A	109.5
O2—C3—C4	114.81 (17)	C10—C11—H11B	109.5
C8—C3—C4	120.14 (18)	H11A—C11—H11B	109.5
C6—C7—C8	119.11 (18)	C10—C11—H11C	109.5
C6—C7—C9	119.09 (18)	H11A—C11—H11C	109.5
C8—C7—C9	121.80 (17)	H11B—C11—H11C	109.5
O1—C4—C5	125.20 (18)	O2—C2—H2A	109.5
O1—C4—C3	115.24 (18)	O2—C2—H2B	109.5
C5—C4—C3	119.55 (18)	H2A—C2—H2B	109.5
C7—C6—C5	121.14 (19)	O2—C2—H2C	109.5
C7—C6—H6	119.4	H2A—C2—H2C	109.5
C5—C6—H6	119.4	H2B—C2—H2C	109.5
C3—C8—C7	120.12 (17)	O1—C1—H1A	109.5
C3—C8—H8	119.9	O1—C1—H1B	109.5
C7—C8—H8	119.9	H1A—C1—H1B	109.5
O3—C10—N2	122.96 (19)	O1—C1—H1C	109.5
O3—C10—C11	122.33 (19)	H1A—C1—H1C	109.5
N2—C10—C11	114.71 (19)	H1B—C1—H1C	109.5
C4—C5—C6	119.93 (19)	C10—N2—N1	121.62 (17)
C4—C5—H5	120.0	C10—N2—H2	119.2
C6—C5—H5	120.0	N1—N2—H2	119.2
N1—C9—C7	122.97 (18)	C9—N1—N2	114.28 (17)

C2—O2—C3—C8	6.3 (3)	C6—C7—C8—C3	0.7 (3)
C2—O2—C3—C4	−173.8 (2)	C9—C7—C8—C3	−179.28 (17)
C1—O1—C4—C5	−1.7 (3)	O1—C4—C5—C6	179.13 (18)
C1—O1—C4—C3	177.38 (18)	C3—C4—C5—C6	0.1 (3)
O2—C3—C4—O1	0.1 (2)	C7—C6—C5—C4	1.1 (3)
C8—C3—C4—O1	−179.94 (16)	C6—C7—C9—N1	−171.95 (19)
O2—C3—C4—C5	179.25 (18)	C8—C7—C9—N1	8.1 (3)
C8—C3—C4—C5	−0.8 (3)	O3—C10—N2—N1	3.4 (3)
C8—C7—C6—C5	−1.5 (3)	C11—C10—N2—N1	−176.62 (17)
C9—C7—C6—C5	178.54 (18)	C7—C9—N1—N2	−178.40 (17)
O2—C3—C8—C7	−179.67 (18)	C10—N2—N1—C9	−171.88 (17)
C4—C3—C8—C7	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.86	1.97	2.803 (2)	164
C1—H1C···O2ⁱⁱ	0.96	2.55	3.435 (3)	153
C11—H11C···O3ⁱⁱⁱ	0.96	2.47	3.425 (3)	174

Symmetry codes: (i) x+1/2, −y+5/2, −z; (ii) x+1/2, y, −z+1/2; (iii) −x, −y+3, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₃
M_r	222.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	223
a, b, c (Å)	8.794 (3), 10.920 (3), 24.418 (7)
V (Å³)	2345.0 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.24 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.977, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	11332, 2070, 1819
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.133, 1.10
No. of reflections	2070
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.12

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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	0.86	1.97	2.803 (2)	164
C1—H1C···O2ⁱⁱ	0.96	2.55	3.435 (3)	153
C11—H11C···O3ⁱⁱⁱ	0.96	2.47	3.425 (3)	174

Symmetry codes: (i) x+1/2, −y+5/2, −z; (ii) x+1/2, y, −z+1/2; (iii) −x, −y+3, −z.

Acknowledgements

The authors thank the Science and Technology Project of Zhejiang Province (grant No. 2007 F70077) and Hangzhou Vocational and Technical College for financial support.

References

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