N′-(3,4-Dihydroxy­benzyl­idene)acetohydrazide monohydrate

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

doi:10.1107/S1600536809027299

organic compounds

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Volume 65| Part 8| August 2009| Page o1897

doi:10.1107/S1600536809027299

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N′-(3,4-Dihydroxybenzylidene)acetohydrazide monohydrate

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 for Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 10 July 2009; accepted 11 July 2009; online 18 July 2009)

In the title compound, C₉H₁₀N₂O₃·H₂O, the Schiff base molecule is approximately planar, the dihedral angle between the benzene and acetohydrazide planes being 5.40 (7)°. An intramolecular O—H⋯O hydrogen bond is observed. In the crystal, molecules are linked into a two-dimensional network parallel to (100) by O—H⋯O, N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds, and by π–π interactions between symmetry-related benzene rings [centroid–centroid distance = 3.543 (2) Å].

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

C₉H₁₀N₂O₃·H₂O
M_r = 212.21
Monoclinic, P 2₁ /c
a = 9.325 (4) Å
b = 13.877 (7) Å
c = 8.210 (4) Å
β = 106.435 (5)°
V = 1019.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.25 × 0.22 × 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
5060 measured reflections
1765 independent reflections
1640 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.102
S = 1.03
1765 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	2.22	2.6694 (18)	115
O1—H1⋯O1Wⁱ	0.82	2.11	2.8529 (18)	151
O1W—H1F⋯O3ⁱⁱ	0.80 (3)	2.31 (3)	3.031 (2)	152 (3)
O1W—H1F⋯N1ⁱⁱ	0.80 (3)	2.48 (3)	3.101 (2)	135 (2)
O2—H2⋯O1W	0.82	1.96	2.7736 (18)	171
N2—H2A⋯O3ⁱⁱⁱ	0.86	2.09	2.9110 (19)	160
C7—H7⋯O3ⁱⁱⁱ	0.93	2.53	3.311 (2)	142
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536809027299/ci2851sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027299/ci2851Isup2.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 is planar and it forms a dihedral angle of 5.40 (7)° with the benzene 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 O1—H1···O2 hydrogen bond is observed.

In the crystal, the Schiff base and water molecules are linked into a two-dimensional network by O—H···O, N—H···O, O—H···N and C—H···O hydrogen bonds (Table 1). In the network, an intermolecular π-π interaction is also observed between the benzene rings of the molecules at (x, y, z) and (1-x, 1-y, -z), with a centroid-to-centroid distance of 3.543 (2) Å.

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 & Jian (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 (15 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 95% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 460–462 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 asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 40% probability level. Dashed lines indicate hydrogen bonds.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₉H₁₀N₂O₃·H₂O	F(000) = 448
M_r = 212.21	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1765 reflections
a = 9.325 (4) Å	θ = 2.3–25.0°
b = 13.877 (7) Å	µ = 0.11 mm⁻¹
c = 8.210 (4) Å	T = 223 K
β = 106.435 (5)°	Block, colourless
V = 1019.0 (8) Å³	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1765 independent reflections
Radiation source: fine-focus sealed tube	1640 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→11
T_min = 0.977, T_max = 0.979	k = −16→15
5060 measured reflections	l = −9→9

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.061P)² + 0.2305P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1765 reflections	Δρ_max = 0.17 e Å⁻³
148 parameters	Δρ_min = −0.18 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: 0.048 (5)

Crystal data top

C₉H₁₀N₂O₃·H₂O	V = 1019.0 (8) Å³
M_r = 212.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.325 (4) Å	µ = 0.11 mm⁻¹
b = 13.877 (7) Å	T = 223 K
c = 8.210 (4) Å	0.25 × 0.22 × 0.20 mm
β = 106.435 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1765 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1640 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.979	R_int = 0.020
5060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.17 e Å⁻³
1765 reflections	Δρ_min = −0.18 e Å⁻³
148 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
H1E	0.587 (2)	0.2853 (17)	0.445 (3)	0.074 (7)*
H1F	0.708 (3)	0.3160 (19)	0.554 (4)	0.098 (9)*
O1	0.52471 (13)	0.68267 (7)	0.22048 (14)	0.0454 (3)
H1	0.4899	0.6582	0.2919	0.068*
O2	0.56486 (12)	0.50802 (7)	0.36246 (13)	0.0457 (3)
H2	0.5820	0.4528	0.3981	0.068*
O3	0.95803 (14)	0.14282 (8)	0.12355 (14)	0.0552 (4)
C1	0.70188 (15)	0.45382 (10)	0.16721 (16)	0.0341 (3)
H1A	0.7158	0.3923	0.2140	0.041*
C6	0.75933 (14)	0.47698 (10)	0.03162 (16)	0.0338 (3)
C2	0.62483 (15)	0.52199 (9)	0.23148 (16)	0.0328 (3)
C3	0.60346 (15)	0.61461 (10)	0.16033 (17)	0.0345 (3)
C7	0.84173 (15)	0.40745 (10)	−0.04047 (17)	0.0366 (3)
H7	0.8769	0.4262	−0.1309	0.044*
C8	0.99310 (16)	0.17592 (10)	0.00126 (17)	0.0375 (3)
C4	0.66068 (17)	0.63811 (11)	0.02822 (19)	0.0418 (4)
H4	0.6473	0.6998	−0.0179	0.050*
C5	0.73807 (16)	0.56971 (11)	−0.03575 (18)	0.0412 (4)
H5	0.7765	0.5859	−0.1251	0.049*
N1	0.86712 (13)	0.32131 (8)	0.01702 (14)	0.0364 (3)
N2	0.94966 (13)	0.26400 (9)	−0.06162 (14)	0.0380 (3)
H2A	0.9728	0.2846	−0.1497	0.046*
C9	1.08651 (18)	0.12110 (13)	−0.08811 (19)	0.0483 (4)
H9A	1.1843	0.1107	−0.0117	0.072*
H9B	1.0949	0.1573	−0.1846	0.072*
H9C	1.0403	0.0601	−0.1254	0.072*
O1W	0.62190 (16)	0.32929 (8)	0.51868 (17)	0.0472 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0601 (7)	0.0354 (6)	0.0490 (6)	0.0077 (5)	0.0288 (5)	0.0011 (4)
O2	0.0665 (7)	0.0386 (6)	0.0438 (6)	0.0082 (5)	0.0350 (5)	0.0048 (4)
O3	0.0887 (9)	0.0445 (6)	0.0447 (6)	0.0080 (6)	0.0390 (6)	0.0052 (5)
C1	0.0409 (7)	0.0310 (7)	0.0331 (7)	0.0005 (5)	0.0148 (6)	0.0008 (5)
C6	0.0349 (7)	0.0369 (7)	0.0319 (7)	−0.0028 (5)	0.0133 (5)	−0.0022 (5)
C2	0.0366 (7)	0.0349 (7)	0.0295 (6)	−0.0026 (5)	0.0138 (5)	−0.0019 (5)
C3	0.0365 (7)	0.0322 (7)	0.0362 (7)	−0.0008 (5)	0.0127 (5)	−0.0031 (5)
C7	0.0399 (7)	0.0420 (8)	0.0324 (7)	−0.0034 (6)	0.0175 (6)	−0.0014 (6)
C8	0.0438 (8)	0.0430 (8)	0.0273 (6)	0.0011 (6)	0.0126 (6)	−0.0035 (5)
C4	0.0499 (8)	0.0342 (8)	0.0461 (8)	0.0014 (6)	0.0213 (7)	0.0073 (6)
C5	0.0457 (8)	0.0443 (8)	0.0401 (8)	−0.0023 (6)	0.0229 (6)	0.0055 (6)
N1	0.0408 (6)	0.0401 (7)	0.0336 (6)	0.0012 (5)	0.0191 (5)	−0.0028 (5)
N2	0.0478 (7)	0.0425 (7)	0.0317 (6)	0.0049 (5)	0.0242 (5)	0.0012 (5)
C9	0.0533 (9)	0.0556 (10)	0.0388 (8)	0.0155 (7)	0.0177 (7)	0.0000 (7)
O1W	0.0532 (7)	0.0412 (6)	0.0542 (7)	0.0047 (5)	0.0265 (6)	−0.0013 (5)

Geometric parameters (Å, º) top

O1—C3	1.3713 (17)	C7—H7	0.93
O1—H1	0.82	C8—N2	1.3439 (19)
O2—C2	1.3591 (17)	C8—C9	1.496 (2)
O2—H2	0.82	C4—C5	1.383 (2)
O3—C8	1.2296 (18)	C4—H4	0.93
C1—C2	1.3799 (19)	C5—H5	0.93
C1—C6	1.4025 (19)	N1—N2	1.3868 (16)
C1—H1A	0.93	N2—H2A	0.86
C6—C5	1.392 (2)	C9—H9A	0.96
C6—C7	1.4592 (19)	C9—H9B	0.96
C2—C3	1.4025 (19)	C9—H9C	0.96
C3—C4	1.377 (2)	O1W—H1E	0.85 (3)
C7—N1	1.2823 (19)	O1W—H1F	0.80 (3)

C3—O1—H1	109.5	N2—C8—C9	115.35 (12)
C2—O2—H2	109.5	C3—C4—C5	119.80 (13)
C2—C1—C6	120.24 (12)	C3—C4—H4	120.1
C2—C1—H1A	119.9	C5—C4—H4	120.1
C6—C1—H1A	119.9	C4—C5—C6	120.95 (13)
C5—C6—C1	118.93 (13)	C4—C5—H5	119.5
C5—C6—C7	118.82 (12)	C6—C5—H5	119.5
C1—C6—C7	122.25 (12)	C7—N1—N2	115.60 (11)
O2—C2—C1	125.46 (12)	C8—N2—N1	119.30 (11)
O2—C2—C3	114.74 (12)	C8—N2—H2A	120.3
C1—C2—C3	119.80 (12)	N1—N2—H2A	120.3
O1—C3—C4	119.15 (12)	C8—C9—H9A	109.5
O1—C3—C2	120.57 (12)	C8—C9—H9B	109.5
C4—C3—C2	120.28 (13)	H9A—C9—H9B	109.5
N1—C7—C6	122.05 (12)	C8—C9—H9C	109.5
N1—C7—H7	119.0	H9A—C9—H9C	109.5
C6—C7—H7	119.0	H9B—C9—H9C	109.5
O3—C8—N2	122.18 (13)	H1E—O1W—H1F	103 (2)
O3—C8—C9	122.47 (14)

C2—C1—C6—C5	0.4 (2)	O1—C3—C4—C5	−178.86 (13)
C2—C1—C6—C7	179.90 (12)	C2—C3—C4—C5	0.7 (2)
C6—C1—C2—O2	−179.73 (12)	C3—C4—C5—C6	0.0 (2)
C6—C1—C2—C3	0.3 (2)	C1—C6—C5—C4	−0.5 (2)
O2—C2—C3—O1	−1.26 (18)	C7—C6—C5—C4	179.97 (13)
C1—C2—C3—O1	178.75 (12)	C6—C7—N1—N2	−178.62 (11)
O2—C2—C3—C4	179.15 (12)	O3—C8—N2—N1	2.4 (2)
C1—C2—C3—C4	−0.8 (2)	C9—C8—N2—N1	−177.75 (12)
C5—C6—C7—N1	179.01 (13)	C7—N1—N2—C8	173.80 (12)
C1—C6—C7—N1	−0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.22	2.6694 (18)	115
O1—H1···O1Wⁱ	0.82	2.11	2.8529 (18)	151
O1W—H1F···O3ⁱⁱ	0.80 (3)	2.31 (3)	3.031 (2)	152 (3)
O1W—H1F···N1ⁱⁱ	0.80 (3)	2.48 (3)	3.101 (2)	135 (2)
O2—H2···O1W	0.82	1.96	2.7736 (18)	171
N2—H2A···O3ⁱⁱⁱ	0.86	2.09	2.9110 (19)	160
C7—H7···O3ⁱⁱⁱ	0.93	2.53	3.311 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃·H₂O
M_r	212.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	9.325 (4), 13.877 (7), 8.210 (4)
β (°)	106.435 (5)
V (Å³)	1019.0 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.22 × 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	5060, 1765, 1640
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.102, 1.03
No. of reflections	1765
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18

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
O1—H1···O2	0.82	2.22	2.6694 (18)	115
O1—H1···O1Wⁱ	0.82	2.11	2.8529 (18)	151
O1W—H1F···O3ⁱⁱ	0.80 (3)	2.31 (3)	3.031 (2)	152 (3)
O1W—H1F···N1ⁱⁱ	0.80 (3)	2.48 (3)	3.101 (2)	135 (2)
O2—H2···O1W	0.82	1.96	2.7736 (18)	171
N2—H2A···O3ⁱⁱⁱ	0.86	2.09	2.9110 (19)	160
C7—H7···O3ⁱⁱⁱ	0.93	2.53	3.311 (2)	142

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

Acknowledgements

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

References

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