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

Abstract

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,

• a = 9.325 (4) Å

• b = 13.877 (7) Å

• c = 8.210 (4) Å

• β = 106.435 (5)°

• V = 1019.0 (8) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

H atoms of the water molecule were located in a difference map and were refined freely. All other H atoms were positioned geometrically (N-H = 0.86 Å, O-H = 0.82Å and C-H = 0.93 or 0.96Å) and refined using a riding model, with U_iso(H) =1.2U_eq(C,N) and 1.5U_eq(C_methyl).

Figures

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.

Crystal data

C9H10N2O3·H2O	F(000) = 448
Mr = 212.21	Dx = 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

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

Refinement

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(Fo2) + (0.061P)2 + 0.2305P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
1765 reflections	Δρmax = 0.17 e Å−3
148 parameters	Δρmin = −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: 0.048 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.