N′-(3,4-Dihydroxy­benzyl­idene)acetohydrazide

Li, W.-W.; Lv, L.-P.; Yu, W.-B.; Zhang, Y.-Z.; Hu, X.-C.

doi:10.1107/S1600536809030712

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2097

doi:10.1107/S1600536809030712

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N′-(3,4-Dihydroxybenzylidene)acetohydrazide

Wei-Wei Li,^a Lu-Ping Lv,^a Wen-Bo Yu,^a Yong-Zhao Zhang ^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 2 August 2009; accepted 2 August 2009; online 8 August 2009)

In the title compound, C₉H₁₀N₂O₃, the Schiff base molecule is approximately planar, the dihedral angle between the benzene ring and the acetohydrazide group (r.m.s. deviation = 0.034 Å) being 8.81 (7)°. An intramolecular O—H⋯O hydrogen bond is observed. In the crystal, molecules are linked into a three-dimensional network by O—H⋯O, N—H⋯O and 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 et al. (2008 ); Tamboura et al. (2009 ).

Experimental

Crystal data

C₉H₁₀N₂O₃
M_r = 194.19
Monoclinic, P 2₁ /c
a = 10.598 (2) Å
b = 8.5017 (16) Å
c = 10.621 (2) Å
β = 107.232 (7)°
V = 913.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.25 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.972, T_max = 0.980
5752 measured reflections
2066 independent reflections
1665 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.111
S = 0.94
2066 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.17	2.9692 (15)	154
O2—H2A⋯O1ⁱⁱ	0.82	1.96	2.7206 (13)	154
O3—H3⋯O2	0.82	2.26	2.7109 (14)	115
O3—H3⋯O2ⁱⁱⁱ	0.82	2.14	2.7784 (14)	134
C9—H9C⋯O3^iv	0.96	2.51	3.445 (2)	166
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z; (iv) x+1, y, z+1.

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/S1600536809030712/ci2878sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030712/ci2878Isup2.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 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).

In the Schiff base molecule, the acetohydrazide group (O1/N1/N2/C8/C9) is planar (r.m.s. deviation 0.034 Å) and it forms a dihedral angle of 8.81 (7)° with the benzene (C1-C6) ring. 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). An intramolecular O3—H3···O2 hydrogen bond is observed.

In the crystal, molecules are linked into a three-dimensional network (Fig.2) by O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1).

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-Dihydroxybenzaldehyde (1.38 g, 0.01 mol) and acetohydrazide (0.74 g, 0.01 mol) were dissolved in stirred methanol (20 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 85% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 475–477 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. The dashed line indicates a hydrogen bond.
	Fig. 2. Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₉H₁₀N₂O₃	F(000) = 408
M_r = 194.19	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2066 reflections
a = 10.598 (2) Å	θ = 2.0–27.4°
b = 8.5017 (16) Å	µ = 0.11 mm⁻¹
c = 10.621 (2) Å	T = 223 K
β = 107.232 (7)°	Block, colourless
V = 913.9 (3) Å³	0.25 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2066 independent reflections
Radiation source: fine-focus sealed tube	1665 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 27.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→13
T_min = 0.972, T_max = 0.980	k = −10→10
5752 measured reflections	l = −13→12

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0674P)² + 0.2108P] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.009
2066 reflections	Δρ_max = 0.21 e Å⁻³
129 parameters	Δρ_min = −0.17 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: 0.019 (4)

Crystal data top

C₉H₁₀N₂O₃	V = 913.9 (3) Å³
M_r = 194.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.598 (2) Å	µ = 0.11 mm⁻¹
b = 8.5017 (16) Å	T = 223 K
c = 10.621 (2) Å	0.25 × 0.24 × 0.20 mm
β = 107.232 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2066 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1665 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.980	R_int = 0.023
5752 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 0.94	Δρ_max = 0.21 e Å⁻³
2066 reflections	Δρ_min = −0.17 e Å⁻³
129 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
N2	1.00361 (10)	0.13127 (13)	0.68707 (10)	0.0357 (3)
H2	0.9880	0.0352	0.7029	0.043*
O3	0.47733 (10)	0.25734 (12)	0.01091 (10)	0.0522 (3)
H3	0.4848	0.3492	−0.0093	0.078*
O2	0.64301 (9)	0.48688 (11)	0.14025 (10)	0.0424 (3)
H2A	0.6973	0.5473	0.1870	0.064*
O1	1.13124 (9)	0.34588 (11)	0.75557 (10)	0.0445 (3)
N1	0.93041 (10)	0.20010 (13)	0.56882 (11)	0.0362 (3)
C6	0.75370 (12)	0.15246 (15)	0.36828 (13)	0.0345 (3)
C3	0.56800 (13)	0.22557 (16)	0.12889 (13)	0.0374 (3)
C1	0.74814 (12)	0.30536 (15)	0.31694 (13)	0.0338 (3)
H1	0.8063	0.3821	0.3628	0.041*
C2	0.65615 (12)	0.34155 (15)	0.19818 (12)	0.0333 (3)
C5	0.66449 (13)	0.03947 (16)	0.29930 (14)	0.0397 (3)
H5	0.6673	−0.0617	0.3334	0.048*
C8	1.09751 (12)	0.21065 (15)	0.77666 (13)	0.0336 (3)
C9	1.15560 (15)	0.12587 (18)	0.90450 (13)	0.0440 (3)
H9A	1.1378	0.0153	0.8919	0.066*
H9B	1.1169	0.1653	0.9693	0.066*
H9C	1.2494	0.1427	0.9342	0.066*
C7	0.84748 (13)	0.10590 (15)	0.49377 (13)	0.0359 (3)
H7	0.8468	0.0018	0.5205	0.043*
C4	0.57178 (14)	0.07602 (16)	0.18054 (14)	0.0412 (3)
H4	0.5122	0.0000	0.1357	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0383 (6)	0.0271 (6)	0.0362 (6)	−0.0028 (4)	0.0024 (5)	0.0041 (4)
O3	0.0513 (6)	0.0409 (6)	0.0465 (6)	−0.0082 (4)	−0.0132 (5)	0.0037 (4)
O2	0.0409 (5)	0.0333 (5)	0.0426 (6)	−0.0053 (4)	−0.0036 (4)	0.0054 (4)
O1	0.0454 (5)	0.0301 (5)	0.0501 (6)	−0.0069 (4)	0.0019 (4)	0.0001 (4)
N1	0.0360 (6)	0.0332 (6)	0.0354 (6)	0.0007 (4)	0.0045 (5)	0.0048 (4)
C6	0.0347 (6)	0.0349 (7)	0.0326 (7)	−0.0013 (5)	0.0081 (5)	0.0000 (5)
C3	0.0341 (7)	0.0385 (7)	0.0347 (7)	−0.0021 (5)	0.0024 (5)	−0.0019 (5)
C1	0.0322 (6)	0.0320 (7)	0.0345 (7)	−0.0046 (5)	0.0060 (5)	−0.0027 (5)
C2	0.0326 (6)	0.0304 (6)	0.0350 (7)	−0.0018 (5)	0.0070 (5)	−0.0001 (5)
C5	0.0436 (7)	0.0323 (7)	0.0402 (7)	−0.0048 (5)	0.0079 (6)	0.0020 (5)
C8	0.0332 (6)	0.0288 (6)	0.0376 (7)	0.0014 (5)	0.0086 (5)	−0.0027 (5)
C9	0.0470 (8)	0.0416 (8)	0.0376 (8)	0.0004 (6)	0.0038 (6)	0.0022 (6)
C7	0.0384 (7)	0.0315 (7)	0.0363 (7)	−0.0022 (5)	0.0087 (5)	0.0024 (5)
C4	0.0406 (7)	0.0355 (7)	0.0416 (8)	−0.0097 (5)	0.0031 (6)	−0.0047 (6)

Geometric parameters (Å, º) top

N2—C8	1.3380 (16)	C3—C4	1.381 (2)
N2—N1	1.3944 (14)	C3—C2	1.4069 (18)
N2—H2	0.86	C1—C2	1.3811 (18)
O3—C3	1.3612 (16)	C1—H1	0.93
O3—H3	0.82	C5—C4	1.3851 (19)
O2—C2	1.3689 (16)	C5—H5	0.93
O2—H2A	0.82	C8—C9	1.4989 (19)
O1—C8	1.2438 (16)	C9—H9A	0.96
N1—C7	1.2783 (17)	C9—H9B	0.96
C6—C5	1.3939 (18)	C9—H9C	0.96
C6—C1	1.4041 (18)	C7—H7	0.93
C6—C7	1.4615 (18)	C4—H4	0.93

C8—N2—N1	121.80 (11)	C4—C5—C6	120.78 (13)
C8—N2—H2	119.1	C4—C5—H5	119.6
N1—N2—H2	119.1	C6—C5—H5	119.6
C3—O3—H3	109.5	O1—C8—N2	122.07 (12)
C2—O2—H2A	109.5	O1—C8—C9	123.01 (12)
C7—N1—N2	113.26 (11)	N2—C8—C9	114.90 (12)
C5—C6—C1	119.34 (12)	C8—C9—H9A	109.5
C5—C6—C7	117.70 (12)	C8—C9—H9B	109.5
C1—C6—C7	122.94 (12)	H9A—C9—H9B	109.5
O3—C3—C4	118.55 (12)	C8—C9—H9C	109.5
O3—C3—C2	121.38 (12)	H9A—C9—H9C	109.5
C4—C3—C2	120.06 (12)	H9B—C9—H9C	109.5
C2—C1—C6	119.86 (12)	N1—C7—C6	123.72 (12)
C2—C1—H1	120.1	N1—C7—H7	118.1
C6—C1—H1	120.1	C6—C7—H7	118.1
O2—C2—C1	124.19 (11)	C3—C4—C5	119.85 (12)
O2—C2—C3	115.73 (11)	C3—C4—H4	120.1
C1—C2—C3	120.09 (12)	C5—C4—H4	120.1

C8—N2—N1—C7	178.32 (12)	C7—C6—C5—C4	179.18 (13)
C5—C6—C1—C2	−0.99 (19)	N1—N2—C8—O1	−5.29 (19)
C7—C6—C1—C2	−179.44 (12)	N1—N2—C8—C9	173.18 (11)
C6—C1—C2—O2	179.96 (12)	N2—N1—C7—C6	176.10 (11)
C6—C1—C2—C3	0.13 (19)	C5—C6—C7—N1	−176.99 (13)
O3—C3—C2—O2	0.93 (19)	C1—C6—C7—N1	1.5 (2)
C4—C3—C2—O2	−178.75 (12)	O3—C3—C4—C5	178.87 (13)
O3—C3—C2—C1	−179.22 (12)	C2—C3—C4—C5	−1.4 (2)
C4—C3—C2—C1	1.1 (2)	C6—C5—C4—C3	0.6 (2)
C1—C6—C5—C4	0.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.17	2.9692 (15)	154
O2—H2A···O1ⁱⁱ	0.82	1.96	2.7206 (13)	154
O3—H3···O2	0.82	2.26	2.7109 (14)	115
O3—H3···O2ⁱⁱⁱ	0.82	2.14	2.7784 (14)	134
C9—H9C···O3^iv	0.96	2.51	3.445 (2)	166

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃
M_r	194.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	10.598 (2), 8.5017 (16), 10.621 (2)
β (°)	107.232 (7)
V (Å³)	913.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.972, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	5752, 2066, 1665
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.111, 0.94
No. of reflections	2066
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

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···O1ⁱ	0.86	2.17	2.9692 (15)	154
O2—H2A···O1ⁱⁱ	0.82	1.96	2.7206 (13)	154
O3—H3···O2	0.82	2.26	2.7109 (14)	115
O3—H3···O2ⁱⁱⁱ	0.82	2.14	2.7784 (14)	134
C9—H9C···O3^iv	0.96	2.51	3.445 (2)	166

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

Acknowledgements

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

References

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